Layer-Structured Anisotropic Metal Chalcogenides

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org/CR Review
Layer-Structured Anisotropic Metal Chalcogenides: Recent

Advances in Synthesis, Modulation, and Applications
Anupam Giri,∥ Gyeongbae Park,∥ and Unyong Jeong*
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ABSTRACT: The unique electronic and catalytic properties emerging from low symmetry
anisotropic (1D and 2D) metal chalcogenides (MCs) have generated tremendous interest
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for use in next generation electronics, optoelectronics, electrochemical energy storage

devices, and chemical sensing devices. Despite many proof-of-concept demonstrations so far,
the full potential of anisotropic chalcogenides has yet to be investigated. This article provides
a comprehensive overview of the recent progress made in the synthesis, mechanistic
understanding, property modulation strategies, and applications of the anisotropic
chalcogenides. It begins with an introduction to the basic crystal structures, and then the
unique physical and chemical properties of 1D and 2D MCs. Controlled synthetic routes for
anisotropic MC crystals are summarized with example advances in the solution-phase
synthesis, vapor-phase synthesis, and exfoliation. Several important approaches to modulate
dimensions, phases, compositions, defects, and heterostructures of anisotropic MCs are
discussed. Recent significant advances in applications are highlighted for electronics,
optoelectronic devices, catalysts, batteries, supercapacitors, sensing platforms, and
thermoelectric devices. The article ends with prospects for future opportunities and challenges to be addressed in the academic
research and practical engineering of anisotropic MCs.
CONTENTS 3.3. Wet-Chemical Synthesis 3353

3.3.1. Hot Injection Synthesis 3353
1. Introduction 3330 3.3.2. One-Pot Heat-up Process 3353
2. Structures and Properties 3332 3.3.3. Hydrothermal/Solvothermal Synthesis 3353
2.1. Crystal Structures 3332 3.3.4. Microwave-Assisted Synthesis 3353
2.1.1. One-Dimensional (1D) Chalcogenides 3333 4. Vapor-Phase Synthesis 3354
2.1.2. Two-Dimensional (2D) Chalcogenides 3334 4.1. Nucleation 3355
2.2. Properties 3336 4.2. Growth Control Parameters 3356
2.2.1. Semiconducting and Optical Properties 3336 4.2.1. Precursors 3356
2.2.2. Metallic Properties 3338 4.2.2. Temperature 3356
2.2.3. Magnetic Properties 3340 4.2.3. Pressure 3357
2.3. Property Modulation 3341 4.2.4. Substrates 3357
2.3.1. Properties Depending on Diameter and 4.3. Growth Mechanisms 3358
Length 3341 4.3.1. Chalcogenation of Predeposited Metals
2.3.2. Layer-Dependent Properties 3342 or Metal Oxide Thin Films 3358
2.3.3. Defect-Induced Property Tuning 3344 4.3.2. Preferential Surface Diffusion 3359
2.3.4. Doping and Chemical Functionalization 3344 4.3.3. Epitaxial Growth 3359
3. Solution-Phase Synthesis 3348 4.3.4. Step-Edge Epitaxy 3362
3.1. Nonstoichiometric Nucleation and Growth 3348 4.3.5. Vapor−Liquid−Solid Growth 3362
3.2. Growth Mechanisms 3349
3.2.1. Intrinsically Anisotropic Growth 3349
3.2.2. Surfactant-Assisted Anisotropic Growth 3349
Special Issue: Anisotropic Nanomaterials
3.2.3. Anisotropic Growth Driven by Oriented
Attachment 3349 Received: June 30, 2022
3.2.4. Chemical Transformation 3351 Published: January 31, 2023
3.2.5. Template-Assisted Growth 3351
3.2.6. Quantized Growth 3352
© 2023 The Authors. Published by

American Chemical Society https://doi.org/10.1021/acs.chemrev.2c00455
3329 Chem. Rev. 2023, 123, 3329−3442
Chemical Reviews pubs.acs.org/CR Review
4.4. Deposition Methods 3363 7.6.4. Heterostructure Control 3404

4.4.1. Chemical Vapor Deposition (CVD) 3363 7.7. Thermoelectric Devices 3404
4.4.2. Metal−Organic CVD (MOCVD) 3364 7.7.1. Dimension Control 3405
4.4.3. Molecular Beam Epitaxy (MBE) 3365 7.7.2. Phase Control 3405
5. Exfoliation Synthesis 3366 7.7.3. Doping Control 3406
5.1. Mechanical Exfoliation 3366 7.7.4. Heterostructure Control 3406
5.1.1. Direct Peel-off 3366 8. Outlook 3406
5.1.2. Adhesion-Controlled Exfoliation 3367 Author Information 3408
5.1.3. Metal-Assisted Exfoliation 3367 Corresponding Author 3408
5.2. Liquid-Phase Exfoliation 3368 Authors 3408
5.2.1. Solvent-Assisted Exfoliation 3368 Author Contributions 3408
5.2.2. Surfactant-Assisted Exfoliation 3370 Notes 3408
5.2.3. Chemical Intercalation-Induced Exfolia- Biographies 3408
tion 3370 Acknowledgments 3408
5.2.4. Electrochemical Intercalation-Induced References 3408
Exfoliation 3371
6. Modulation of Anisotropic MC Crystals 3371
6.1. Dimension Control 3372 1. INTRODUCTION
6.1.1. Size Sorting 3372 Anisotropic nanomaterials possessing chemical and physical
6.1.2. Surface Energy Adjustment 3373 properties depending on their shape and growth direction are
6.1.3. Salt-Assisted CVD 3375 attractive subjects for both fundamental research and a wide
6.1.4. Growth-Etch Interplay 3376 range of applications. Anisotropic metal chalcogenides (MCs)
6.1.5. Thickness Control 3376 in the forms of nanorods (NRs), nanobelts (NBs), nanowires
6.2. Crystallographic Phase Control 3377 (NWs), nanotubes (NTs), nanoribbons (NRBs), nanosheets
6.2.1. Thermodynamic Lattice Mixing 3377 (NSs), nanoplates (NPs), and thin films have been emerging
6.2.2. Intercalation 3377 rapidly during the past decade. Their exceptional chemical,
6.2.3. Ligand Coordination 3378 physical, optical, and mechanical properties have great
6.2.4. Vapor-Phase Transition 3379 potential applications in diverse fields ranging from elec-
6.3. Chemical Composition Control 3379 tronics,1−14 optoelectronics,1,15−20 battery,21−26 electrocataly-
6.3.1. Thermodynamic Solid Solutions 3379 sis,27−30 sensors,31−34 supercapacitors,35−37 to thermoelectric
6.3.2. Surface Doping 3380 devices.38,39 Novel physical phenomena have been discovered
6.3.3. Lattice Doping 3381 from the anisotropic layered structures, including quantum
6.4. Formation of Heterostructures 3382 spin hall effect,40 valley polarization,41 ferromagnetism,42,43
6.4.1. Sequential Reaction 3383 and superconductivity.44 Those novel properties suggest future
6.4.2. Intercalated Patterning 3384 applications in advanced high performance nanoelectronics
6.4.3. Vertical Heterostructure in CVD 3384 and spintronic devices. The MC NSs have exhibited different
6.5. Defect Engineering 3386 properties from their bulk counterparts, and presented
6.5.1. Growth-Induced Intrinsic Defects 3386 intriguing opportunity for further structural, morphological
6.5.2. Point Defects 3386 engineering to impart or modulate novel functionalities. So far,
6.5.3. Grain Boundary 3388 a variety of 1D and 2D MCs have been explored, including
6.6. Moiré Superlattice Formation 3389 semiconducting transition metal dichalcogenides (TMDCs)
7. Applications 3391 (MoS2, WS2, etc.), V−VI topological insulators (Bi2Se3,
7.1. Electronic Devices 3391 Bi2Te3, Sb2Te3, etc.), and III−VI and IV−VI semiconductors
7.1.1. Transistors 3391 in the chemical compositions of MX, MX2, and M2X3 (M = Ga,
7.1.2. Memtransistors 3392 In, Si, Ge, Sn; X = S, Se, Te).45,46
7.2. Optoelectronic Devices 3392 Among the 1D NRs, NBs, and NWs, II−VI chalcogenides
7.2.1. Photodetectors 3393 such as CdX,47−51 ZnX (X= S, Se, Te),52−54 and their
7.2.2. Light Emitting and Light Harvesting heterostructures55,56 have been widely investigated due to their
Devices 3394 large absorption cross section, linearly polarized emission,57
7.3. Catalysts 3396 and superior charge separation and carrier transport.47,57−59
7.3.1. Heterostructure Control 3396 1D Cu2S60,61 and PbS62,63 NR/NWs have also been studied
7.3.2. Heteroatom Doping 3398 extensively. Very recently, 1D NWs and NRBs of TMDCs,
7.4. Batteries 3398 such as MoS2 and WS2, have also drawn research attention
7.4.1. Heterostructure Control 3399 because of their remarkable electrical and optical proper-
7.4.2. Interlayer Spacing Control 3400 ties.64−68 Particularly for optoelectronics and photonics
7.5. Supercapacitors 3401 applications, NBs and NRBs of 2D layered III−VI semi-
7.5.1. Doping Control 3402 conductor MCs including GaS and GaSe have emerged as a
7.5.2. Interlayer Spacing Control 3402 promising material class.69−71 GaS1−xSex alloy NBs also
7.5.3. Heterostructure Control 3402 showed tunable light emission across the visible spectrum.72
7.6. Sensing Platforms 3403 NBs and NWs of 2D layered GeX (X = S, Se, Te) are also
7.6.1. Flexible Gas Sensors 3403 direct bandgap semiconductors with tunable electronic
7.6.2. Thickness Control 3404 structures, which have been studied widely in recent
7.6.3. Effective Surface Area Increase 3404 experiments.73−79
3330 https://doi.org/10.1021/acs.chemrev.2c00455
Chem. Rev. 2023, 123, 3329−3442
Figure 1. Diverse applications of anisotropic MCs in the forms of NWs, NRs, NSs, NPs, and thin films depending on their intrinsic bonding
characteristics. The important parameters determining the structure−function−morphology−composition are listed. Potential applications that are
actively investigated are shown. Reprinted with permission from ref 10. Copyright 2022 American Chemical Society. Reprinted with permission
from ref 20. Copyright 2013 Publishers, Rights Managed by Nature Publishing Group. Reprinted with permission from ref 26. Copyright 2018,
Rights Managed by Nature Publishing Group. Adopted from ref 11. Copyright 2016 American Institute of Physics. Reprinted with permission from
ref 38. Copyright 2016 American Institute of Physics. Reprinted with permission from ref 35. Copyright 2019 Royal Society Chemistry.
Transition metal trichalcogenides (TMTCs) also exhibit a focused low-energy electron.103 Initial transport measure-
chain-like structures with strong in-plane anisotropy and quasi- ments indicate that such 1D MCs show metallic behavior
one-dimensional physical and electronic structure. The 1D consistent with the Tomonaga−Luttinger liquid, therefore
structure generally consists of an elongated chalcogen shell holding great potential as electronic interconnection in
with a metal core.80 The well-known NWs, NRBs, and NBs of downscaled electronics.8,96
TMTC compounds are TiS3,81−83 NbSe3,84−86 TaSe3,8 The strong covalent bonding between the metal and
TaTe3,87 HfTe3,88,89 ZrTe3,90,91 and others.92 Apart from the chalcogen atoms within the individual 2D crystal lattice
TMTCs, many M−X combinations have also been achieved in preserves the structure of the NSs and NPs, whereas the weak
the NW form, including MX (e.g., MoTe, WTe)80 and M6X6 van der Waals (vdW) bonds between the individual 2D crystal
(e.g., Mo6S6,93−95 Mo6Se6,96 Mo6Te6,97 W6Te698), mono and lattice allows them to be mechanically separated from the bulk
multi MC alloys (e.g., MoSxSe1−x, MoxW1−xS,99 AgSeTe, and crystals, down to single layer 2D NSs.45,104 The properties and
CoSeTe 56 ), chalcogenide-cluster-based semiconducting functions of 2D MCs depend not only on its composition but
NTs,100 and hybrid metal organic chalcogenides.92 Diverse also on its structure, crystal phase, number of layers, doping,
approaches have been implemented so far to produce such 1D defects, grain boundaries, exposed facet, and spatial organ-
MCs, on the basis of template-assisted growth using carbon ization.105−107 Therefore, the rational design and controlled
nanotubes (CNTs)87 and anode aluminum oxide (AAO),92 synthesis are significant in understanding the material growth
chemical vapor deposition (CVD),80 exfoliation,101 post mechanism and exploring the fundamental aspects of the
growth in situ annealing of epitaxial 2D TMDCs,96 mechanical structure−property−function relationships. Mechanical exfoli-
exfoliation,102 and ionization etching of MC monolayers under ation is still an important approach to produce MCs in its
Chem. Rev. 2023, 123, 3329−3442
pristine form, and thus it is a good way for investigating effort and progress made in physical properties, synthesis,
physical properties; however, acquiring scalability is a difficult and applications, many challenges remain to be overcome in
task.108,109 Liquid exfoliation is suitable for large-scale realizing target-oriented practical uses.
production at a low cost, but precise control of size and There have been a few review articles covering the specific
layer number with preservation of the pristine quality is still topics of anisotropic chalcogenides including 1D MCs2,146−148
highly challenging.110,111 Bottom-up synthesis has emerged as and 2D MCs.113,149 Some reviews have focused exclusively on
a versatile scalable approach enabling precise control over the synthetic methodologies,114,150 specific properties,151,152 or
structure, morphology, and composition through the selective particular structures and applications of the chalcoge-
growth process.18,112,113 Vapor phase growth has been the nides.27,30,146,153,154 This review article is an attempt to
major bottom-up approach for the scalable production of provide a comprehensive overview of the recent progress
anisotropic MC thin films with less structural defects and made in the synthesis, mechanistic understanding, properties,
desirable controllability over the thickness, domain size, and and applications of the anisotropic chalcogenides (Figure 1).
shape.114,115 However, there are still some disadvantages for The focus of this article is the layer-structured anisotropic (1D
the bottom-up growth process. In the vapor phase growth, and 2D) binary and ternary MCs. Few selected nonlayered 1D
single crystallinity of thin films is not readily achieved due to MCs are included in the discussion because they can be
the simultaneous growth of the multiple nuclei and the strict transformed to the layered structures. In chapter 2, the
epitaxial condition with the crystal facet of the substrate. The classification of anisotropic chalcogenides is overviewed in
complex vapor transport mechanism, high temperature and terms of their composition, crystal phases, and structures. The
high vacuum synthetic conditions, and the slow synthesis unique properties and the strategies to property modulation
process limit the scale up production of target thin films. In the are discussed. Chapters 3−5 introduce the synthetic
wet chemical approach, further advances are necessary in fine approaches: solution-phase synthesis (chapter 3), vapor-
control of chemical composition, size, and morphology.116,117 phase synthesis (chapter 4), and exfoliation synthesis (chapter
Degradation of the electrical/optical properties once the 5). Overviews and recent successful representative achieve-
ligands/surfactants of the nanocrystals are removed in the ments are introduced in detail. Chapter 6 focuses on
thin film is another technological issue to be solved. modulation of crystal dimension, phase, composition, defects,
Diverse functionalities are found in the 1D MCs, including and heterostructures. The mechanistic details, key experimen-
semiconducting,118 metallic,8 superconducting,119 and ferro- tal parameters, and the control variables for shape-controlled
magnetic with a high Young’s modulus and large fracture growth are described with some comments on their advantages
strain.2,101 For instance, the exfoliated Ta2Pd3Se8 NWs are n- and limitations. In chapter 7, potential applications of the
type semiconductors, whereas isostructural Ta2Pt3Se8 NWs are anisotropic chalcogenides are reviewed in terms of electronic
p-type semiconductors. Both types of NWs show excellent devices, optoelectronic devices, catalysis, batteries, super-
electrical switching performance as the channel material for a capacitors, sensing platforms, and thermoelectric devices. In
field-effect transistor.102 The metallic NWs with robust chapter 8, perspectives to the future research directions and
junctions at designated locations have been used to connect existing challenges are proposed.
atomically thin nanoelectronic components for the fabrication
of fully integrated 2D flexible nanocircuits.103,120 They have 2. STRUCTURES AND PROPERTIES
also been demonstrated to have great potential for practical The family of anisotropic chalcogenides exhibits unique crystal
applications, such as in Na-ion and Li-ion batteries16,121 and structures, a variety of structural polymorphs, a wide range of
phototransistors.122,123 In the case of 2D MCs, while chemical compositions, and diverse material properties. Here, a
significant exploratory research has been achieved, under- brief introduction of the various types of anisotropic
standing 2D electronic transport and carrier dynamics still chalcogenides is provided along with their structure, chemical
remains in a nascent stage.106,124−126 2D MCs are expected to composition, and structural hybrids. Then, their electronic,
be a candidate to replace Si as the channel material in future optical, magnetic properties, and physicochemical modulation
transistors, as they can maintain excellent device electrostatics techniques are summarized.
even at short channel lengths.3,127 To enable the dimension
scaling law to continue without the electric power penalty, a 2.1. Crystal Structures
different transistor mechanism has been achieved to obtain a Contrary to the isotropic nanocrystals, where the electronic
subthermionic subthreshold swing, such as band-to-band motions or interactions are equal in all the three directions,
tunnel field-effect transistors, using an atomically thin MoS2 anisotropic nanocrystals can be categorized into one-dimen-
thin film as the channel material.5 Ultrasmall scale transistors sional (1D), two-dimensional (2D), and three-dimensional
with the atomically thin MoS2 side wall channel have also been (3D) nanostructures based on the direction of the allowed
demonstrated where a physical gate length of sub-1 nm was electronic motions and interactions.155 The anisotropic
achieved using the edge of a graphene layer as the gate physicochemical properties of low symmetry materials are
electrode.3 In addition, electronic interactions between 2D strongly related to their crystal structure and compositions.
MCs in the form of vdW heterojunctions and composite films Reducing the symmetry of materials is generally associated
have been used to realize heterostructures with interesting with exceptional anisotropy in electronic energy band structure
physical properties that have been previously inaccessi- and the low dimensionality in the carrier transport.156
ble.128−130 Apart from the exciting electronic applications, Therefore, the electrical, optical, thermal, and phonon
2D MCs and their heterostructures have also been properties of these anisotropic materials can be largely varied
demonstrated to hold great promise for a variety of according to the in-plane crystal directions.157 In this section,
applications in the field of future optoelectronic devices,131−134 the crystal structures of anisotropic MCs are discussed by
optics,135−138 energy harvesting,139−141 energy storage,142,143 dividing them into two categories, namely, 1D MCs and 2D
catalysis,144 and bioelectronics/sensors.145 Despite all the MCs.
Chem. Rev. 2023, 123, 3329−3442
Figure 2. Crystal structures of 1D MCs. (a) Crystal structural model of ZnS NB. (b) Crystal structural model of ZnS NR. (c) Crystal structural
model of armchair MoS2 NRBs, where the rectangle indicates the unit cell. (d) Crystal structure of a 1D chain of M−X NWs with a 1:1 atomic ratio
of Mo (W) and S (Se). (e) Comparative scanning tunneling electron microscopy (STEM) images of MoSe (orange), MoS (yellow), and WSe
(blue) NWs, with simulated atomic models. (f) Lattice structures of Mo6Te6 NWs by the ball-and-stick model. Green balls represent Mo atoms,
and orange balls represent Te atoms. (g) Crystal structure of ZrTe3 plotted from different angles. (h,i) Crystal structure of CrSbSe3. The unit cell is
marked in black (h). The double-rutile chains extend along the b-axis (i). Green, gray, and yellow spheres represent Cr, Sb, and Se, respectively.
(j,k) Crystal structure of metal organic hybrid NWs. (j) The yellow and red triangles represent the three-atom S and Cu rings, respectively. (k) Unit
cell of the core−shell NW structure. Red and yellow spheres represent the Cu and S atoms, respectively, and the organic moieties (adamantyl
groups) are represented by the gray capped-stick model. (a,b) Reprinted with permission from ref 162. Copyright 2013 Wiley-VCH Verlag GmbH
& Co. KGaA, Weinheim. (c) Reprinted with permission from ref 164. Copyright 2014 American Institute of Physics. (d,e) Reprinted with
permission from ref 103. Copyright 2014, Rights Managed by Nature Publishing Group. (f) Reprinted with permission from ref 167. Copyright
2018 American Chemical Society. (g) Reprinted with permission from ref 91. Copyright 2021 American Chemical Society. (h,i) Reprinted with
permission from ref 101. Copyright 2021 American Chemical Society. (j,k) Reprinted with permission from ref 92. Copyright 2017, Rights
Managed by Nature Publishing Group.
2.1.1. One-Dimensional (1D) Chalcogenides. In recent ZnS with hexagonal symmetry has six equal planes of ±
decades, 1D MC nanostructures, such as NRs, NBs, NRBs, (112̅0), ± (2̅110), and ± (12̅10) of the lowest surface energy,
NWs, and NTs, are considered as useful building blocks for favoring the formation of this type of low-energy NB growing
high performance electronic devices.158−160 For instance, being along the [011̅0] direction with the lowest energy.163Figure 2b
one of the first semiconductors discovered, zinc sulfide (ZnS) shows the atomic structure of the wurtzite-2H ZnS NRs, in
NBs and NRs have been widely used in electronic devices.53 which the growth direction along the polarized [0001] plane is
Wurtzite ZnS has several facets that terminate with either a illustrated. The MoS2 NRB structure is a monolayer MoS2
positively charged Zn cation or a negatively charged S anion. formed along the armchair or zigzag direction.164 The armchair
This characteristic of the crystal structure creates polarized or zigzag structure can be identified by the number of dimer
surfaces, resulting in a dipole moment and spontaneous lines or zigzag chains across the ribbon width. Figure 2c shows
polarization along the axis perpendicular to the plane.161 The the atomic structure of the 1D armchair MoS2 NRB. Figure 2d
surface atomic structure of the wurtzite-2H ZnS NB is shows the atomic structure of a 1D chain of M−X NWs with a
schematically shown in Figure 2a, where the growth direction 1:1 atomic ratio of Mo (W) and S (Se). The consecutive stacks
(011̅0) is indicated by an arrow. The side planes of the NB of the triangular Mo (W) and S (Se) atomic layers are rotated
have polar surfaces, terminated with either Zn or S atoms.162 by 180° along the NW axial direction (marked by the red
Chem. Rev. 2023, 123, 3329−3442
Figure 3. Layered structures of binary MCs. (a) Single nanocrystal consisting of multiple layers stacked along the c-axis by weak vdW force. (b−f)
Side view crystal structure of binary transition and post transition MCs. Different polymorphic structures with different symmetries, such as
tetragonal (g), trigonal prismatic (h), rhombohedral (i), and hexagonal (j) structures.
triangles), with three capping S (Se) atoms located at the atoms in the trigonal pyramidal geometry (Figure 2h). The
vertices of the triangles and three Mo (W) atoms located double-rutile chains of covalently bonded atoms extended
between the S (Se) atoms.103 Adjacent chain-like structures along the b-axis (Figure 2i). The hybrid metal−organic
interact via van der Waals (vdW) forces to form a crystalline chalcogenide NWs with solid inorganic cores have been
NW. Figure 2e shows the comparative scanning tunneling obtained by using metal−organic frameworks and coordination
electron microscopy (STEM) images of MoSe (orange), MoS polymers (Figures 2j,k),92 where the molecular-scale core−
(yellow), and WSe (blue) NWs with simulated atomic models. shell NWs were packed in a 3D supramolecular lattice. The
The atomic positions showed an excellent match with the shell is composed of closely packed adamantane-1-thiol. The
simulated atomic models in Figure 2a. It is worth noting that three-atom wide cross section of the inorganic core consists of
the MX NW structure was theoretically predicted to be alternating three-atom Cu and S trigonal rings, as indicated by
energetically more stable than other alternative structures,165 the yellow and red planes in Figure 2j. Each Cu atom binds to
including Mo5S4.166 Like M−X (1:1) NWs, the unit cell of three S atoms in a twisted trigonal planar geometry, while the S
Mo6Te6 NWs also consists of two staggered stacks. However, atoms are attached to three Cu atoms in a distorted tetrahedral
each stack in Mo6Te6 is composed of an equilateral Mo3Te3 configuration. The core−shell structures pack into a distorted
triangle, with three Te/Mo atoms at its three vertexes/sides hexagonal lattice (Figure 2k) with the inorganic cores
(Figure 2f).97,167 As the representative of TMTCs (M = Ti, Zr, elongating along the b-axis via strong vdW attraction between
and Hf),87,168 the crystallographic structure of monoclinic diamondoids moieties.
ZrTe3 is presented from different angles in Figure 2g. Two of 2.1.2. Two-Dimensional (2D) Chalcogenides. 2D MCs
the ZrTe3 formula units comprise a unit cell of the crystal. The have a variety of crystal structures and compositions. They can
vertical rods shown in the middle figure indicate the direction be structurally categorized into two types: layered and
of high conductivity; these colored rods extend along the b-axis nonlayered MCs. For layered structured materials, the in-
and create the quasi-1D wires. They assemble in sheets, which plane atoms are connected to each other by strong covalent
in turn stack to make up the bulk.91 The ternary chalcogenides bonding with some electrostatic contribution depending on the
such as MAX3 (e.g., CrSbSe3),101 M2AX5 (e.g., Nb2PdS5),119 ionicity of the M−C bonds, while the individual layers are
and M2A3X8 (M = Ta, Nb, A = Ni, Pd, Pt, X = S, Se)169 also stacked together through the vdW interaction (Figure 3a).
have a linear crystal structure.101,170 For instance, CrSbSe3 Figure 3b−e exhibit the side view crystal structures of the
crystallizes in the orthorhombic phase, where the Sb atoms binary layered MCs with formal stoichiometry of MX2 (Figures
occupying the edge of the double-rutile chains bind to three Se 3b,c), M2X2 (Figure 3d), and M2X3 (Figure 3e).171 They have
Chem. Rev. 2023, 123, 3329−3442
Figure 4. Layered crystal structures of ternary (and their extended quaternary) MCs plotted from different angles. Chalcogen atoms in all cases are
marked by orange spheres, and the metal atoms are marked by the spheres with color of the respective elemental symbols used in the name of the
respective MCs.
covalently bonded 2D stacking units of X−M−X, X−M−M− (e.g., Mn3Si2Te6) 2D ternary MC crystals have also been
X, and X−M−X−M−X atomic layers, respectively. Figure 3f reported recently.177
shows the crystal structure of the MX-type group, typically To explore the full potential of these atomically thin 2D
IV−VI MCs, where the structure can be derived from a three- MCs, diverse lateral and vertical heterostructures, and
dimensional distortion of the NaCl structure.172 Depending on superlattices have been fabricated. Those structures have led
the metal-chalcogen coordination environment and stacking to numerous exciting physical phenomena and offered a
sequences within the individual layers, 2D MCs have different plethora of opportunities for materials science, condensed-
polymorphic structures with different symmetries, such as matter physics, and device engineering.183−185 For lateral
tetragonal (1T) (Figure 3g), trigonal prismatic (Figure 3h), heterostructure formation, a strict lattice matching between 2D
rhombohedral (3R) (Figure 3i), and hexagonal (2H) (Figure MC components is highly necessary to achieve the “edge
3j) structures.173 For further discussion on the crystal epitaxy” and a 2D heterointerface. The edge epitaxy can also be
structures and polymorphism of various binary MCs, please performed in a sequential mode to produce multiple
see the review articles by Bergeron et al.174 and Tan et al.113 heterojunctions or arrays of heterojunctions between two
2D ternary MCs are the emerging class of materials with MCs (Figure 5a,b).185,186 Vertical heterostructures are formed
exotic physical properties, having a common chemical formula by stacking different 2D MC layers by weak vdW forces, so a
of MxCyXz (MCX3, M3CX2, M3C2X6, etc.), where M is the fairly large number of combinations and complexity of the
inner transition metal, C is the group III−V metal, and X is the heterostructures can be created with atomic precision (Figure
chalcogen.42,175−177Figure 4 shows both side-view and top- 5c).187,188 For instance, vertical heterostructures of semi-
view crystal structures of some of the representative vdW type conductor-semiconductor MCs (e.g., MoS2/WSe2, WS2/MoS2,
ternary and their extended quaternary 2D MCs, such as WS2/WSe2),187 metal−semiconductor MCs (e.g., VSe2/WSe2,
Cr 2 Ge(Si) 2 Te 6 , 42 Cu 2 WS 4 , 178 Ta 2 NiS 5 , 179 CuSbS 2 , 180 VSe2/MoS2, CoTe2/WSe2),130 and four-layer MoS2/WS2/
ZnIn2S2,181 and MnBi(Sb)2Te4.182 Several non-vdW type MoS2/WS2 superlattice of semiconductors189 have been
Chem. Rev. 2023, 123, 3329−3442
Figure 5. Example layered heterostructures of binary MCs. (a) Scheme of monolayer seed A, A−B heterostructure, A−B−C multiheterostructure,
and A−B−A−B superlattice. (b) Scheme of the lateral heterojunction array of MoS2 and MoSe2. (c) Scheme of the vertical heterostructures of WS2
and MoS2. (d) Scheme of the vertical superlattice formation. (a) Reprinted with permission from ref 183. Copyright 2017 American Association for
the Advancement of Science. (b) Reprinted with permission from ref 186. Copyright 2015, Rights Managed by Nature Publishing Group. (c)
Reprinted with permission from ref 187. Copyright 2014, Rights Managed by Nature Publishing Group. (d) Reprinted with permission from ref
188. Copyright 2015 The Royal Society of Chemistry.
achieved. The weak vdW force between the individual layers gap of a monolayer TiS3 does not change when the number of
also enables the formation of low-strain and rotationally layers increases up to 5 (Figure 6a,b),198 which is very different
commensurate epitaxy of the layers even when they have large from the case of 2D MCs such as MoS2.199 Structural
lattice mismatches causing the moiré superlattices (Figure anisotropy led to highly anisotropic photoluminescence as
5d).190 observed in 1D ZrS3 (Figure 6c), where the exciting light is
2.2. Properties efficiently absorbed when the E-field is polarized along the 1D
1D MCs show strong anisotropy in their electrical and optical chain (b-axis).192 Moreover, anisotropic optical transmission
properties due to their reduced in-plane structural symmetry, measurements in 1D TiS3 showed strong linear dichroism. The
where different material properties can be attained from ratio in the transmission between the b-axis and a-axis reached
different crystal directions.191,192 This anisotropy also contrib- a value as high as 30, which is much greater than that observed
utes to interesting properties, such as strong dichroic in other anisotropic materials such as 2D MCs.82,200,201 M6X6
emission,192 magnetocrystalline anisotropy,101 anisotropic type 1D MCs (such as Cr6Te6, Mo6Te6, and W6Te6) have also
carrier mobility,82 topological insulator,193 charge density been found to be semiconducting.2 Cr6Te6 and Mo6Te6 are
waves,194 and superconductor−insulator transitions.119 Ultra- indirect semiconductors with a band gap of 0.70 and 0.50 eV,2
thin 2D MCs also play an increasingly crucial role in advanced respectively, while W6Te6 has a narrow indirect band gap of
technological applications and next-generation electronics. The 0.24 eV.2 NRs/NWs of direct bandg gap ZnS (Eg = 3.6 eV)
electronic, optical, and magnetic properties of these anisotropic and CdS (Eg = 2.4 eV) are promising materials for
materials are primarily determined by the number of electrons optoelectronic applications in the near-ultraviolet and visible
and their arrangements in the outermost shell. Thus, spectral regions, respectively.202 They also show an adjustable
understanding the electronic structures and its modulation band gap (1.7−3.68 eV) by alloying with other II−VI
by means of atomic and defect structural variations are of compounds (e.g., CdSxSe1−x, ZnxCd1−xS, ZnxCd1−xSe).203,204
immense importance for the design of functional materials with As a layered III−VI semiconductor, GaSe NRBs show intense,
controllable electronic, optical, and magnetic properties.
narrow luminescence across an ∼2.0 eV band gap, so the
2.2.1. Semiconducting and Optical Properties. The
key parameter that determines the electrical and optical absorption of monochromatic laser light creates electron−hole
properties of semiconductors is the band gap. With the pairs which rapidly thermalize to the band-edges and
exception of semimetallic ZrTe3 , HfTe3, and metallic recombine across the direct band gap.69 Interestingly, the
NbSe3,195,196 most 1D MX3 type compounds are semi- properties of 1D Mo/WS2 NRBs are greatly affected by the
conducting with a band gap of 1−2 eV. For instance, TiS3 type of the edges. The armchair NRBs are semiconducting as
NWs had a direct optical band gap of ∼1 eV and showed that of bulk, whereas zigzag NRBs exhibit a metallic
ultrahigh optical responsivities (∼3000 AW−1).197 With both property;68 thus, by controlling the edge structures saturated
conduction band minimum (CBM) and valence band with H atoms, their conductivity can be tuned to either
maximum (VBM) located at the Γ point, the direct band semiconducting (n- or p-type) or half metallic.205 Similar
Chem. Rev. 2023, 123, 3329−3442
Figure 6. Semiconducting and optical properties of anisotropic MCs. (a,b) Calculated band structure of monolayer (a) and five-layer (b) 1D TiS3.
(c) Comparative polar plot of integrated photoluminescence (PL) peak area of a 50 nm-thick 1D ZrS3 and a monolayer MoS2 with azimuthal flake
angle (φ) in orthogonal arrangement. (d,e) Calculated band structures of bulk MoS2 (d) and a monolayer MoS2 (e). (f) Absorbance spectra of
MoS2 flakes according to the number of layers. (g) Room temperature PL spectra of MoS2 flakes of different number of layers. (a,b) Reprinted with
permission from ref 197. Copyright 2016 The Royal Society of Chemistry. (c) Reprinted with permission from ref 192. Copyright 2016 The Royal
Society of Chemistry. (d,e) Reprinted with permission from ref 201. Copyright 2016, Multidisciplinary Digital Publishing Institute. (f) Reprinted
with permission from ref 212. Copyright 2021, Rights Managed by Springer Nature Publishing Group. (g) Reprinted with permission from ref 196.
Copyright 2010 American Chemical Society.
observations regarding the edge-dependent property have also 2H-MoS2, the calculated band gap for bulk (indirect) and
been reported for PdS2 NRBs.206 monolayer (direct) are 0.88 and 1.71 eV, respectively.209
For 2D TMDCs, the ligand field splitting of the nonbonding The layered structure of MCs restricts the electronic
metal d-orbitals under the chalcogen coordination environ- movement in the thickness direction; hence the dielectric
ment (e.g., trigonal prismatic) leads to the formation of the screening for the electric field outside the material becomes
band gap.207 As a semiconductor, the thermodynamically weak, giving rise to strong Coulomb interaction. Therefore,
stable 2H phase of the 2D TMDCs exhibits an intrinsic band upon optical illumination, tightly bound electron−hole pairs
gap ranging from visible to near-IR frequencies, and shows (excitons) having strong binding energies on the order of
distinct excitonic absorption and emission features. With few several hundreds of meV are formed.210 In the case of
exceptions,208 generally the bulk crystals of TMDCs are a rigid monolayer MCs, the strong in-plane quantum confinement of
and indirect band gap semiconductor. Whereas, upon reducing the excitons enhances the exciton binding energy and hence
the thickness from bulk to monolayer, the indirect band gap alters the wavelength of light they absorbs and emits.211Figure
turns into a direct band gap due to the change in the position 6f shows the absorbance spectrum for MoS2 flakes ranging
of the valence and conduction band edges (Figure 6d,e). For from single to 4-layers, showing pronounced peaks (labeled as
Chem. Rev. 2023, 123, 3329−3442
Figure 7. Metallic property of anisotropic MCs. (a−c) Scanning transmission electron microscope (STEM) images showing the initial formation of
1D MoSe thick wire (a), formation of 1D MoSe thin NW (b), and breaking of the NW (c). The corresponding current (I)−voltage (V)
measurements are shown below the SETM images. (d) Three crystalline phases of 2D MCs. (e) Strain-induced tuning of lattice parameters to
produce a particular phase. (f) Energy diagram of 2H- and 1T-MoS2, and the corresponding crystal fields of Mo 4d orbitals. (g) 2H-to-1T′ phase
transition as observed by the change in the I−V curves. (a−c) Reprinted with permission from ref 103. Copyright 2014, Rights Managed by Nature
Publishing Group. (d,e) Reprinted with permission from ref 218. Copyright 2014, Rights Managed by Nature Publishing Group. (f) Reprinted with
permission from 221 Copyright 2019 Frontiers Media SA. (g) Reprinted with permission from ref 220. Copyright 2016 American Chemical
Society.
A, B, and C) corresponding to the generation of intraband relaxation rate of the excitonic state in monolayer
excitons.199,212 For monolayer MoS2, the generation of A MoS2 contributed to their enhanced PL, compared to indirect
exciton near the absorption band edge of ∼670 nm (∼1.85 eV) band gap bulk MoS2 flakes.199 Several recent reviews cover the
corresponds to the direct band gap. Meanwhile, the origin of B optical properties of semiconducting MCs as well as their use
exciton at ∼627 nm (∼1.98 eV) is due to the splitting of the in various photonic and optoelectronic applica-
valence band through the spin−orbit interactions. For a tions.46,117,213−217
multilayer system, a combination of spin−orbit coupling and 2.2.2. Metallic Properties. As mentioned in the previous
interlayer interaction contributes to the splitting of the valence section, among the MX3 type 1D MCs, ZrTe3 and HfTe3
band.199,209Figure 6g demonstrates the room temperature exhibit the semimetallic property, whereas NbSe3 shows
photoluminescence (PL) spectra of MoS2 flakes of different metallic behavior.195,196 NWs with the stoichiometry of MX
layer thicknesses. The PL spectrum of direct band gap (M = Mo or W, X = S or Se) have also been found to be
monolayer MoS2 shows two broad bands associated with metallic (Figure 7a−c).103,165Figure 7a−c display STEM
direct electronic transitions of A and B excitons. The decreased images of a thick, thin, and disconnected MoSe NW fabricated
Chem. Rev. 2023, 123, 3329−3442
Figure 8. Magnetism in anisotropic MCs. (a) Comparison of the magnetic moment (M)−applied magnetic field (H) data for bulk and exfoliated
NWs of CrSbSe3 at 2 K. (b) Temperature-dependent field-cooled (FC) and zero-field-cooled (ZFC) molar magnetic susceptibility curves of the
bulk and exfoliated CrSbSe3 NWs under an applied field of 1 kOe. (c) For 3D collinear magnets, Coulombic exchange interaction is the main
driving force. (d) For 2D systems, long-range ferromagnetic ordering is originating due to the presence of spin-wave excitation gap, resulting from
strong uniaxial magnetic anisotropy. (e) Temperature-dependent reflective magnetic circular dichroism (RMCD) signal of a 3.2 nm thick exfoliated
Fe3GeTe2 (FGT) 2D flake. (f) Thickness−temperature phase diagram of Fe3GeTe2 for different magnetic states, paramagnetic (PM), single-
domain ferromagnetic (FM1), and ferromagnetic with labyrinthine domains (FM2). (a, b) Reprinted with permission from ref 101. Copyright
2021 American Chemical Society. (c, d) Reprinted with permission from ref 175. Copyright 2019 American Association for the Advancement of
Science. (e, f) Reprinted with permission from ref 227. Copyright 2018, Rights Managed by Nature Publishing Group.
from the MoSe2 monolayer, respectively. The corresponding chalcogens around M atoms leads to the formation of metallic
electrical data taken during in situ fabrication exhibit a 1T and 1T′ phase, respectively (Figure 7d).218 Selective
substantial increase in electrical conductance as the NW was formation of any particular phase can be achieved by
formed from the MoS2 monolayer. The result proves the controlling the lattice parameters (a and b) of the monolayer
conversion of the semiconducting MoSe2 monolayer to a MCs during the growth process. The application of strain or
metallic MoSe NW. Semiconductor-to-metal transitions have growth of the MCs over a strained substrate can affect the
been reported. A single WTe NW is a narrow-band gap lattice constants of the thermodynamically stable phase and
semiconductor, while bundles of a few NWs are metallic.80 A hence can induce the formation of a particular phase (Figure
superconductor-to-insulator transition has also been observed 7e).218 Alkali metal intercalation into 2H MCs can also induce
in Nb2PdS5 single crystal NWs. The transition was driven by phase transition into 1T phase through charge transfer from
both the cross-sectional area of the NW and external magnetic the alkali metal, which induces the formation of density of
field.119 The hexagonal coordination of chalcogens (X) around states at the Fermi level and renders metallicity.219Figure 7f
the metal atoms (M) leads to a semiconducting 2H phase in shows the crystal field splitting of Mo 4d orbitals and
NSs. However, when one of the X layers in the 2H structure is corresponding energy diagram of 2H- and 1T-MoS2. The
shifted, the octahedral and distorted octahedral coordination of completely occupied valence band (4dz2) by two electrons of
Chem. Rev. 2023, 123, 3329−3442
Figure 9. (a) Diameter-dependent linear absorption and photoluminescence spectra of CdSe NWs. (b) Photoluminescence spectra of CdSe NRs
with increasing length. (c) Band gap variation of CdSe NRs with length and width of the NWs. (a) Reprinted with permission from ref 47.
Copyright 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. (b,c) Reprinted with permission from ref 232. Copyright 2001 American
Chemical Society.
Mo4+ in the 2H phase renders semiconducting behavior, curve for these NWs clearly suggest persistent long-range
whereas the incomplete occupation of 1T t2g valence band ferromagnetic ordering in the NWs even after exfoliation from
orbitals makes the 1T phase metallic in nature and displays bulk CrSbSe3 (Figure 8a). The temperature dependent field-
increased low-bias conductivity (Figure 7g).219−221 Although cooled (FC) and zero-field-cooled (ZFC) molar magnetic
the majority of the thermodynamically stable 2H phase of MCs susceptibility curves of bulk and exfoliated CrSbSe3 NWs
is semiconducting, very few 2H phases such as 2H-TaS2, 2H- under an applied field are also consistent with the expected
TaSe 2 , 2H-NbS 2 , and 2H-NbSe 2 exhibit the metallic behavior of hard magnets (Figure 8b). 1D armchair NRBs of
property.222−224 Mo/WS2 are nonmagnetic in nature, while the zigzag NRBs
2.2.3. Magnetic Properties. 1D atomic wires of Co6S6, exhibit ferromagnetic behavior. The ferromagnetic states are
Co6Se6, Co6Te6, Fe6S6, Fe6Se6, and Re6S6 are predicted to be enhanced by H-saturation of their edge states.68,205 Recently,
magnetic with preferential ferromagnetic order as the ground strongly ferromagnetic Cr2Te3 NRs were reported, where the
state. Ferromagnetism is originated due to the presence of the observed ultrahigh coercivity was attributed to the large
unpaired d electrons in the transition metal atoms. The magnetocrystalline anisotropy of ordered Cr2Te3 NRs.226
calculated magnetic moment per transition metal atom is The recent discovery of ferromagnetic 2D vdW MCs has
around 1.71−2.02 μB for Fe6X6 (X = S, Se), 0.97−1.18 μB for provided an ideal platform for exploring and understanding the
Co6X6 (X = S, Se, Te), and 0.62 μB for Re6S6, respectively.2 In fundamental physics of magnetism in low-dimensional systems
the case of N-a-TiS3 NRBs (here, a indicates the viewing axis and opened opportunities for developing innovative 2D
of the NRBs, and N indicates the number of Ti atoms in the spintronic heterostructures and devices.42,176,227,228 Moreover,
monoclinic cell of the ribbons), theoretical works found that for atomically thin vdW MC crystals, the long-range magnetic
the magnetic ground state is a ferromagnetic metal when N is ordering stabilized by magnetic anisotropy can be combined
equal to an odd number, whereas it behaves like an with their rich electronic and optical properties to achieve
antiferromagnetic metal when N is equal to an even multifunctional magnetoelectric and magneto-optic devices
number.225 Recently, strong magneto-crystalline anisotropy that have a faster operating speed and lower power
has been observed in the exfoliated NWs of CrSbSe3, where consumption.229,230 In the case of a 3D (anti)ferromagnet,
the NWs showed a reduced Curie−Weiss temperature, but the driving force underlying the ordering of electrons’ spin
higher coercivity and remanence than the bulk phase (Figures magnetic moments is the Coulombic exchange interaction,
8a,b).101 The hysteresis loop observed in the magnetization relating to the antisymmetric wave function of the electron’s
Chem. Rev. 2023, 123, 3329−3442
Figure 10. Layer-dependent optical properties of 2D MCs. (a) Optical microscope (OM) images of MoS2 flakes with different thickness. Scale bar:
5 μm. (b,c) Thickness-dependent Raman spectra, peak frequency variation, and peak position difference of the MoS2 flakes. (d) Thickness-
dependent PL peak position and intensities of the MoS2 flakes. (g) Optical second-harmonic generation (SHG) intensities of the MoS2 flakes. (f)
Variation of the surface potential of the MoS2 flakes with different number of layers. (g) Band gaps and conduction band onsets for monolayer
(ML), bilayer (BL), trilayer (TL), and multilayer (nL, ∼8 layer) MoS2 films. (a−e) Reprinted with permission from ref 234. Copyright 2017 Wiley-
VCH Verlag GmbH & Co. KGaA, Weinheim. (f) Reprinted with permission from ref 236. Copyright 2015 American Chemical Society. (g)
Reprinted with permission from ref 237. Copyright 2021, Rights Managed by Nature Publishing Group.
(Figure 8c). This concept does not work in the low- electronic states by thickness control, controlling charge
dimensional length scale of 2D systems because of the reduced transfer or dipole interactions, adjusting carrier concentration
magnon (quanta of spin wave) dispersion and an abrupt onset by means of p-(n-)type doping processes, and functionalization
of magnon density of states (DOS). For 2D systems, to by molecular adsorption.
harness a long-range ferromagnetic ordering at a nonzero 2.3.1. Properties Depending on Diameter and
temperature, the presence of a spin-wave excitation gap Length. The 1D quantum-confined structures of MC NRs
resulting from strong uniaxial magnetic anisotropy is essential and NWs exhibit electronic and optical properties different
(Figure 8d). As the system progresses from 2D to 3D, the from isotropic quantum dots. The band gap or optical
spectrum of magnon DOS per spin changes from a step absorption/emission properties can be tailored by adjusting
function to a progressive increasing function.42 So, for a 3D the width and length that confine the electrons and holes. For
system, a spin-wave excitation gap is not necessary to achieve instance, if the width of the NRs or diameter of the NWs is
long-range magnetic ordering at a finite temperature.175Figure much smaller than the exciton Bohr radius of the material (e.g.,
8e presents the temperature dependent reflective magnetic 5.6 nm in bulk CdSe), carrier confinement in the radial
circular dichroism (RMCD) signal of a 3.2 nm thick exfoliated direction falls in the “strong confinement regime”. Therefore,
Fe3GeTe2 (FGT) 2D flake, showing persistent ferromagnetic the band gap varies significantly with the length of the NRs or
ordering evidenced by prominent hysteresis.227Figure 8f shows NWs due to the substantial band mixing. However, when the
a thickness-temperature phase diagram of FGT for different width of CdSe NRs or NWs is greater than 5.6 nm, increasing
magnetic states such as paramagnetic (PM, TC), single-domain
the length slightly lowers the band gap due to the minimal
ferromagnetic (FM1, TC1), and ferromagnetic with labyrin-
band mixing.232Figure 9a shows the linear absorption spectra
thine domains (FM2, TC2).227 With increasing temperature, a
obtained from a series of CdSe NWs with a variable diameter
decreasing ratio of the strength of magnetic anisotropy to that
of exchange interaction determines the magnetic domain of 5.2 to 10.6 nm. An apparent blue-shift of the band edge can
formation.231 be seen with decreasing NW diameter because the band gap
and the excited state level spacings increase due to the carrier
2.3. Property Modulation confinement.47 Similar property control by dimension variation
To get the best output of the anisotropic MCs for various has also been achieved with CdTe NWs.48 To understand the
applications, it is important to adjust their intrinsic chemical relationship of the band gap with width and length, Li et al. has
and electrical properties. Frequently used property modu- measured photoluminescence (PL) spectra of CdSe NRs with
lations of the anisotropic MCs include tuning the surface different widths and lengths.232Figure 9b shows the PL spectra
Chem. Rev. 2023, 123, 3329−3442
Figure 11. Layer-dependent electronic and magnetic properties of 2D MCs. (a) Linear mobility curves of bottom gate-controlled FETs with 1-, 2-,
and 3-layered MoS2. (b) Field-effect mobilities of the MoS2 FETs fabricated on different substrates as a function of the layer number of MoS2. MS,
MB, and MBG stand for MoS2 FETs on SiO2, SiO2-supported hBN, and MoS2 FETs with hBN dielectric and few-layer graphene as gate,
respectively. (c) Transition temperatures (T*C) of a Cr2Ge2Te6 thin film as a function of layer numbers, as obtained from Kerr measurements (blue
squares) and theoretical calculations (red circles). (d) Remanence and coercive force at zero field for 1T-CrTe2 thin films with various thicknesses.
(a) Reprinted with permission from ref 238. Copyright 2013 The Royal Society of Chemistry. (b) Reprinted with permission from ref 240.
Copyright 2013 American Chemical Society. (c) Reprinted with permission from ref 42. Copyright 2017, Rights Managed by Nature Publishing
Group. (d) Reprinted with permission from ref 245. Copyright 2021, Rights Managed by Nature Publishing Group.
of 3.7-nm-wide CdSe NRs with different lengths of 9.2, 11.5, layer), respectively.234 The apparent color of the flakes
28.0, and 37.2 nm. The PL peak shifted to a lower energy by depends both on the number of layers and on the SiO2
increasing the length of the NRs. Figure 9c represents the band thickness of the Si substrate. From the optical contrast of
gap variation of CdSe NRs depending on the aspect ratio 1L, 2L, and 3L MoS2 on different SiO2/Si substrates, Hsu et al.
ranging from 1 to 12, which shows the general tendency of has recently determined the corresponding complex refractive
decreasing band gap with an increase in either width or length index.235 It is demonstrated that the refractive index is greatly
of the NRs. influenced by the band gap. The refractive index of thin MCs
2.3.2. Layer-Dependent Properties. For 1D NRBs of converges to the bulk value with increasing thickness due to
the layered Mo/WS2, zigzag NRBs showed ferromagnetic and reduction of quantum confinement in bulk. Figure 10b exhibits
metallic behavior, which were independent of the width and the Raman spectroscopic features of the as-grown MoS2 flakes
thickness variation. On the other hand, the armchair NRBs with a thickness of 1−10L. The A1g Raman peak blue-shifted
were nonmagnetic and semiconducting, in which the band and E2g1 red-shifted up to 4−6L and remained the same,
gaps converged to a constant value of ∼0.56 eV as the ribbon elucidating that the MoS2 appears to have the bulk electronic
width increased.233 The physical property and electronic property when the thickness is over 6L (Figure 10c).234Figure
structures of 2D MCs can be tuned by reducing the thickness 10d displays the layer-dependent PL intensities. The layer-
due to the strong excitonic effect resulting from the 2D dependent symmetry and stacking configuration of MoS2 were
quantum confinement. Figure 10a shows the optical micro- investigated by optical second-harmonic generation (SHG)
scopic image of MoS2 flakes of 1, 2, 3, 4, 6, 9, and 10L (L = spectroscopy, which shows a monotonic increase in intensity as
Chem. Rev. 2023, 123, 3329−3442
Figure 12. Defect engineering of 2D MCs. (a) Various types of intrinsic defects of a hexagonal MC lattice. (b−d) STEM-annular dark-field
(STEM-ADF) images of single sulfur vacancy (VS), double sulfur vacancy (VS2), and substitution defect (MoS2) where one Mo atom occupied two
sulfur sites in a MoS2 monolayer. (e) Simulated STEM image of a relaxed grain boundary (GB) representing the 4|8 structure. (f) Comparative
diagram describing the charge carrier trapping and relaxation between pristine and defective MoS2 monolayers. (g) Calculated formation energies
of the various defects in their neutral charge state of MoS2 monolayer, as a function of the S chemical potential. (h) Schematic diagram of the in-
gap defect levels for three different types of defects such as VS, VS2, and S2Mo. (a) Reprinted with permission from ref 246. Copyright 2019, Rights
Managed by Nature Publishing Group. (b−e, h) Reprinted with permission from ref 253. Copyright 2013 American Chemical Society. (f)
Reprinted with permission from ref 258. Copyright 2018 American Chemical Society. (g) Reprinted with permission from ref 259. Copyright 2015
American Physical Society.
the layer number increased (Figure 10e). Kaushik et al. showed device structure and materials (electrode, dielectric, and
that the surface potential, hence the work function of MoS2, is substrate). As shown in the figure, the observed linear mobility
strongly dependent on the number of layers (Figure 10f).236 (μlin) decreased from the single layer (13 cm2 V−1 s−1) to the
For the monolayer and few layer samples, the localization of triple layer (1 cm2 V−1 s−1) FETs.238 This monotonic decrease
the carriers at the crystal/lattice defect sites resulted in a large of current modulation with increasing layer number can be
spread in surface potential compared to the counterpart bulk attributed to the interlayer scattering of electrons during
samples. Figure 10g compares the band gap and conduction source-to-drain transport, which is suppressed completely in
band onset for monolayer (ML), bilayer (BL), trilayer (TL), the single layer channel.239 However, Lee et al. reported a
and multilayer (nL, ∼8 layer) MoS2 films. The band gap reverse trend of increasing electronic mobility with increasing
continued to decrease with increasing number of layers, and thickness of MoS2 of 1−5 layers.240Figure 11b shows the field-
the conduction band approached the Fermi level.237 effect mobilities (μFE) of the MoS2 FETs fabricated on
Since the indirect-to-direct band gap crossover occurs at the different substrates as a function of number of MoS2 layers.
monolayer limit in a majority of MCs, the electrical properties MS, MB, and MBG stands for MoS2 FETs on SiO2, SiO2-
of MCs are strongly correlated with their layer number or supported hBN, and MoS2 FETs with hBN dielectric and few-
thickness. In order to ascertain the electrical properties of layer graphene as the gate, respectively. The mobility increase
MCs, the dependence of their charge carrier mobilities with was more pronounced on the FETs with hBN as the dielectric
layer number or channel thickness is the principle issue. layer compared with the SiO2 dielectric. FETs with the trilayer
However, the dependence of the carrier mobility on the cannel MoS2 on hBN reached a high mobility of ∼45 cm2 V−1 s−1. For
thickness of the MC-based transistors is not yet clearly the monolayer MoS2, the mobility on hBN (∼10 cm2 V−1 s−1)
understood, because it varies widely according to the contact was an order of magnitude higher than that of monolayer
resistance, work function of the contact materials, gate MoS2 on SiO2 (<1 cm2 V−1 s−1). The use of graphene as the
dielectric, passivation with high-k dielectric layer, measuring gate electrode along with the hBN dielectric, however, did not
environment, etc. Figure 11a compares the carrier mobility in affect the mobility significantly. The increasing mobility trend
single, double, and triple layer MoS2 FETs, with the same with increasing layer number can be explained by the reduced
Chem. Rev. 2023, 123, 3329−3442
contact resistance and dielectric screening effect of the vacancy types (i.e., S, Ti, TiS, and double S).247,248 While a
additional MoS2 layer from the gate dielectric interface, single S vacancy results in a nonmagnetic, semiconducting
which enhances screening of long-range disorder.241 Therefore, character with an enhanced band gap, other vacancy types
substantial efforts are now being devoted to identify the induce metallic behavior with spin polarization of 0.3−0.8 μB.
optimal contact materials and thickness to achieve the best Introduction of S vacancy slightly increases the band gap
electronic performance out of 2D MCs.242 because the highest occupied molecular orbital is lowered in
In order to exploit ferromagnetic vdW materials as building energy. This effect partially diminishes the overlapped wave
blocks for spintronic applications, a hard magnetic phase and a functions between electron and hole, which greatly reduces
large magnetic remanence to saturated magnetization (MR/ nonradiative electron−hole recombination in pristine 1D TiS3
MS) ratio is essential. The MR/MS ratio is found to be strongly NRBs.249 The oxidation of 1D TiS3 NRBs and subsequent
reliant on the domain structure of the magnetic material, which desorption of S atoms also play an important role in the high
is thickness dependent.243 Therefore, the layer-number- breakdown current density of up to 1.7 × 106 A cm−2 in 1D
dependent magnetic properties of the vdW MCs crystals TiS3 NRB-based field-effect transistors (FETs).250 The
were of great significance for exploring their topological observed breakdown current density is the highest among
phenomena and magneto-optic applications. When the thick- semiconducting nanomaterials. The defect structure of single-
ness of the 2D materials is reduced, due to the change in the crystal TiS3 whiskers with different resistivity has also been
band structure, indirect magnetic exchange mechanisms are studied.251 It was reported that the density of sulfur vacancies
altered to be sensitive to the energy of the intermediate states was noticeably higher in the TiS3 low-resistivity whiskers.
and the corresponding hopping energy.244 To investigate the Figure 12b−d show the scanning transmission electron
long-range magnetic ordering in the vdW crystals, the microscopic annular dark-field (STEM-ADF) images of single
fundamental quantity to monitor is the ferromagnetic sulfur vacancy (VS), double sulfur vacancy (VS2), and
transition temperature (TC), which is expected to evolve substitution defect where one Mo atom occupies two sulfur
from its bulk value TC3D to its 2D value TC2D as the number of sites (MoS2) in a MoS2 monolayer, respectively.252 Other types
layers is reduced. Figure 11c shows the transition temperatures of point defects such as a vacancy complex of Mo with three
of 2D Cr2Ge2Te6 films of varying thickness, obtained from nearby sulfur atoms (VMoS3), a vacancy complex of Mo with
Kerr measurements (blue squares) and theoretical calculations three nearby disulfur pairs (VMoS6), and antisite defect where a
(red circles), showing a strong dimensionality effect. With pair of S’s column occupies the Mo site (S2Mo) were also
increasing layer number, near the excitation gap, the density of investigated by Zhou et al.253 Since MoS2 crystal structure has
states per spin for the magnon modes was rapidly reduced. To a 3-fold symmetry, coalescence of individual crystals with
destroy the long-range magnetic ordering, a higher TC was misorientation angles from 0° to 60° can lead to the formation
required to ensure sufficient excited state populations, which of dislocation cores with various odd-membered (e.g., 4|4, 4|6,
led to the observed strong dimensionality effect.42 In contrary and 4|8) or even-membered (e.g., 5|7) ring motifs at the grain
to the expected trend, Meng et al. has recently demonstrated boundary.254−256Figure 12e shows the simulated STEM image
that, with reducing the thickness of 2D metallic 1T-CrTe2 from of a grain boundary relaxed structure reproducing the 4|8
tens of nanometers (∼130 nm) to several nanometers (∼7.6 structure.253,257Figure 12f presents the comparative schematic
nm), the transition temperature increased monotonically and diagram of the charge carrier trapping and relaxation dynamics
the magnetic easy axis changed from in-plane to out-of-plane between pristine and defective MoS2 monolayers.258 The
(Figure 11d).245 This anomalous thickness dependence of population of a trap state is determined through competing
magnetism could be due to the electrostatic coupling with the trapping and detrapping processes.258 Due to the defects, trap
substrate or weakening of the Coulomb screening in the 2D states are generated within the band gap, which provides
limit. additional recombination pathways during the photoexcitation
2.3.3. Defect-Induced Property Tuning. As a result of and relaxation process. On the basis of theoretical study on
thermal equilibrium and the processing kinetics, anisotropic monolayer MoS2, Figure 12g shows the formation energies of
MCs contain structural defects that can significantly alter their various defects in their neutral charge state as a function of the
properties. So, engineering the defects in chalcogenides is an S chemical potential.259 S vacancies are the most abundant
effective way to modulate the properties. The optical, electrical, defects under all practical growth conditions, specifically under
and chemical properties can be significantly altered, and novel Mo-rich conditions, due to the lower formation energy.
functionalities and superior performance can be invoked. However, defect-free high-quality crystal growth is expected
However, creation of controllable defects and manipulation of under S-rich conditions because all formation energies are
the nature of defects to induce certain target functionality is relatively high. Figure 12h shows a schematic diagram of the
challenging. Atomic defects are the most common type of in-gap defect levels for three different types of defects such as
defect observed in a wide range of MCs. They can be formed VS, VS2, and S2Mo.253 With a lower formation energy, VS and
during the initial growth stage or created by deliberate VS2 defects have two unoccupied deep levels (∼ 0.6 eV) below
postprocessing. Figure 12a summarizes various types of the conduction bands minimum (CBM), whereas the S2Mo
intrinsic defects for a hexagonal MC lattice, including vacancy, defect has a relatively higher formation energy under the S-rich
antisite, substitution, edges termination, and grain boundary conditions and creates only occupied deep levels. Large defects
(GB).246 These different types of intrinsic defect or disorder are generated in the VMoS6 and VMoS3 defects; hence, their
can modify multiple properties by locally introducing variation formation energies are considerably high over the whole range
in the electrostatic potential, electronic band structure, and of S chemical potential.253,259
scattering of charge carrier. 2.3.4. Doping and Chemical Functionalization. Adapt-
In the case of 1D TiS3 NRBs, the formation energy ing the idea of the specially controlled doping strategy used in
investigation for possible vacancies revealed that the formation Si-based semiconductor technology for fabricating both p-type
of a single S vacancy was the most likely among the considered and n-type semiconductors, doping in MCs has also been
Chem. Rev. 2023, 123, 3329−3442
Figure 13. Doping of anisotropic MCs. (a,b) UV−vis absorption spectra (a) and PL emission spectra (b) of Mn2+-doped ZnSe NWs with various
Mn2+ doping levels. The inset in (b) is the optical photograph of the doped ZnSe NW samples under 365 nm light excitation. (c) Photoresponses
of photochromic cards by printing the ZnSe NW (2.1 nm diameter with 0.28% Mn2+ and 4.5 nm diameter with 0.62% Mn2+) under 365 nm UV
radiation and to 405 nm visible light radiation. (d) High-resolution scanning tunnelling microscopy (STM) image of a O-substituted (bright spots)
basal plane of MoS2 crystal. The inset shows the simulated STM image of the same. (e,f) Enthalpy of formation for S vacancy and calculated kinetic
energy barrier for O-substitution at the MoS2 basal plane. (g, h) Enthalpy of formation for S vacancy and calculated kinetic energy barrier for O-
substitution at the MoSe2 basal plane. (i) Schematic illustration of the spontaneous MoS2/Pd (II) redox reaction. (j) Influence of the Pd doping
concentration on the total phase energy of both the 1T-MoS2 and 2H-MoS2. (a−c) Reprinted with permission from ref 266. Copyright 2017 The
Royal Society of Chemistry. (d−h) Reprinted with permission from ref 274. Copyright 2018, Rights Managed by Nature Publishing Group. (i, j)
Reprinted with permission from ref 283. Copyright 2018, Rights Managed by Nature Publishing Group.
extensively explored. Researchers have doped the 1D MCs to topological states (nontrivial Zak phase).263 Substituting sulfur
increase the electronic, optoelectonic, and catalytic activities or by iodine atoms in Mo6S4I2 not only shifts the Fermi level but
to induce local magnetic moments.147 Recent work has shown also opens a narrow band gap, while introducing a new band
that electron doping with specific metal atoms (e.g., Ti doping above the Fermi energy (EF), suggesting high electron
in 1D ZrS3 NRs) leads to shifting of the Fermi level as well as mobility.264 This nearly free-electron band of the predominant
increased conductivity.260 Similarly, p-type doping was induced Mo 4d character was also observed in the Li-doped Mo6S6
in NbS3 by doping Ti which has one less electron in the system.265 According to density functional theory (DFT)
valence shell compared to Nb.261 Doping with electron- calculations, a higher density of sulfur vacancies in the 1D TiS3
donating halogen atoms such as iodine has also been found to leads to an increase in the n-type doping level.262 With the Ti
increase the effective conductance of NWs. An intrinsic defect doping of 1D ZrS3 NRs, the transport measurements of
such as sulfur deficiency in TiS3 has also been utilized to Zr0.82Ti0.18S2.86 revealed an n-type electron mobility of about 2
induce a heavy n-type doping effect.262 For Mo3nS3n+2 (n, an cm2 V−1 s−1.260 Controllable Mn doping in ultrathin ZnSe
integer) NWs, it was found that iodine doping acts as electron NWs was also used to tune the photoluminescence, and used
donor and can be used to tailor the electronic conductivity. in the application of UV−visible photodetection (Figure 13a−
Therefore, for iodine doped Mo12S8I4 NWs, both electrons and c).266 The UV−vis absorption spectra (Figure 13a) and PL
holes were found to contribute to the overall conduction.165 emission spectra (Figure 13b) of the Mn2+-doped ZnSe NWs
Doping of M6X6 (M = Mo and W; X = S, Se, and Te) NWs are shown for various Mn2+ doping levels. The constant
with halogens (Cl, Br, and I) resulted in the formation of 1D absorption spectra indicate that the absorption edges and ZnSe
Chem. Rev. 2023, 123, 3329−3442
Figure 14. Covalent functionalization of 2D MCs. (a) Scheme of the functionalization strategy of MoS2. The 2H phase is converted to 1T phase
through lithiation by using butyllithium (BuLi). The nucleophilic substitution reaction with 2-iodoacetamide or iodomethane (R-I) produces
functionalized product. (b) XRD spectra of pristine and functionalized MoS2. (c) Distributions of hole and electron mobilities of the pristine WSe2,
and NBD-doped WSe2, and DETA-doped WSe2. (d) Scheme of the “click” reaction between f-MoS2-N3 (2) and terminal acetylenes (3−5) to
produce multifunctional MoS2 derivatives (6−8). (a) Reprinted with permission from ref 285. Copyright 2015, Rights Managed by Nature
Publishing Group. (b) Reprinted with permission from ref 287. Copyright 2019, Rights Managed by Nature Publishing Group. (c) Reprinted with
permission from ref 288. Copyright 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. (d) Reprinted with permission from ref 289.
Copyright 2018 American Chemical Society.
host emission peak (at 438 nm) of the doped NWs do not charge transfer.271−274 Doping with other elements of different
show any shifts even when the dopant concentration changes. valence electrons (e.g., replacing Mo of MoS2 by Re)275,276 has
However, PL emission (at 590 nm) gradually increased with been commonly performed through thermal diffusion of
increasing Mn (Figure 13b). Utilizing this unique PL property, foreign atoms277 or plasma exposure.278 During charge transfer
a film of Mn-doped ZnSe NWs was used as a photochromic doping, Lewis bases such as NH2-containing molecules can
card for visually detecting UVA and near-visible radiation induce the n-type doping effect,279 whereas metal halides,
(Figure 13c). The band gap of CdS NRs was decreased with a acids, or halogens can induce the p-type doping.280 Use of
significant shift in their respective valence and conduction redox active molecules which can undergo electron-transfer
band positions and also with increasing doping content of Ag+ reaction with 2D MCs can also produce a stronger doping
(from 2.56 to 2.29 eV) and Cu2+ (from 2.56 to 2.31 eV) effect.281,282Figure 13d shows the high-resolution scanning
ions.267 Although MoS2 NRBs with armchair-terminated edges tunneling microscopy (STM) image of the O-substituted
are generally semiconducting in nature, DFT calculations (bright spots) basal plane of the MoS2 crystal, with an inset
revealed that they can be converted into half metals upon showing the simulated STM image.274 Theoretical calculations
deposition of transition metal (e.g., Ti) atomic chains, allowing indicated that the enthalpy of reaction for creating S vacancy at
transport of 100% spin-polarized currents.268 The observed the MoS2 basal plane is −0.49 eV (Figure 13e), implying a
magnetism is considered to originate from competition thermodynamically favorable process. The calculated kinetic
between the exchange splitting and crystal-field splitting.269 energy barrier for O-substitution in MoS2 also shows a lower
For the zigzag-terminated MoS2 NRBs, N-doping at the S-edge barrier of ∼1 eV (Figure 13f), which can be overcome even at
or in the center changed the ground state energy level and a room temperature. Meanwhile, a positive (0.75 eV) enthalpy
negative differential resistance effect was observed within a of reaction for Se vacancy formation at the MoSe2 basal plane
certain bias voltage range.270 makes the process thermodynamically unfavorable (Figure
Doping in 2D MCs can be achieved either by atomic 13g).274 The barrier for MoSe2 was calculated to be about 1.5
substitution of elements or by molecular surface doping via eV with a thermodynamically unfavorable final step (Figure
Chem. Rev. 2023, 123, 3329−3442
Figure 15. Nonstoichiometric nucleation and growth. (a) Scheme of nonstoichiometric reaction in nucleation and growth process. (b) Scheme of
chemical transformation from chalcogen and metal into MC, following the surface nucleation−detachment−reorganization process. (c) Time-
dependent TEM and EELS analysis on MoTe2 synthesis. (a) Reprinted from permission from ref 295. Copyright 2014, American Chemical Society.
(b) Reprinted from permission from ref 292. Copyright 2017, American Chemical Society. (c) Reprinted from permission from ref 294. Copyright
2018, American Chemical Society.
13h), making the basal plane of MoSe2 more stable toward Covalent functionalization of 2D MCs by organic molecules
oxidation. These theoretical results agree with the experimental is another approach that can lead to profound changes in the
observations.274Figure 13i shows a scheme of substitutional Pd properties of these materials.284 The formation of chalcoge-
doping in the MoS2 basal plane through a spontaneous nide−carbon covalent bonds is essential for solubilizing them
interfacial MoS2/Pd (II) redox reaction.283 Pd was atomically in common solvents, providing chemical functionality for
further reaction.285 Functionalization of 2D MCs can be used
substituted at the Mo site simultaneously creating S vacancy,
as surface passivation against corrosion or charge carrier
and Pd doping consequently converted the semiconducting
recombination; also, the surface dipoles induced by the
2H-MoS2 phase into the 1T phase. Figure 13j exhibits the functionalization can alter the relative energy of the band-
influence of Pd doping concentration on the total phase energy edges.286 Covalent conjugation of functional groups on 2D
of both the 1T and 2H-MoS2, indicating that the 1T-MoS2 MCs is generally achieved by interaction with unsaturated
phase with a higher Pd doping concentration becomes more metal atoms at the edges or defect sites on the basal plane.
stable than the 2H-MoS2 phase. Such conjugation facilitates electron transfer from the electron-
Chem. Rev. 2023, 123, 3329−3442
Figure 16. Growth mechanisms in solution-phase synthesis. (a) Crystal structures of 1D Bi2S3 (left) and 2D TiS2 (right). (b) Scheme of the
surfactant-assisted anisotropic growth enabled by surface energy decrease through surfactant passivation on the crystal facets. (c−e) Anisotropic
growth by the oriented attachment. (c) HRTEM images of in situ oriented attachment of Bi2Se3 nanoparticles to nanodiscs. (d) Atomic model and
TEM images of ex-situ oriented attachment of presynthesized PbS nanocrystals. (e) Scheme of the oriented attachment of presynthesized CuSe and
In2S3 induced by electrostatic interaction. (a) Reprinted from permission from ref 46. Copyright 2014, The Royal Society of Chemistry. (b)
Reprinted with permission from ref 308. Copyright 2018, Rights Managed by Nature Publishing Group. (c) Reprinted from permission from ref
322. Copyright 2012, American Chemical Society. (d) Reprinted from permission from ref 329. Copyright 2018, American Chemical Society. (e)
Reprinted with permission from ref 330. Copyright 2013, The Royal Society of Chemistry.
rich metallic 1T sites to the electrophilic organohalide reactant, mediated azide−alkyne cycloaddition reactions (Figure
creating covalent bonds between the functional group and 14d).289
chalcogen atoms (Figure 14a).285 Upon covalent functionaliza-
tion of the MoS2 NSs, the interlayer spacing increases due to 3. SOLUTION-PHASE SYNTHESIS
the presence of grafted functional groups at the edges and basal
The bottom-up solution-phase synthesis enables sophisticated
plane. This is evident from displacement of (002) peak from
control over broad chemical composition, morphology,
∼13.9° (interlayer spacing d ∼ 6.3 Å) for pristine MoS2 to the
dimension, aspect ratio, and crystalline phase. Rational
lower angles at ∼8.8°, ∼7.5°, and ∼8.2° (10.6 Å < d < 11.4 Å)
synthesis design can be realized on the basis of understanding
for acetamide-, methyl-, and ethyl-2-ol- functionalized MoS2,
on nucleation, growth, and reaction environment. This chapter
respectively (Figure 14b).287 Depending on the polarity of the
describes nonstoichiometric nucleation, growth mechanisms,
functional group, the surface polarity of the functionalized
and wet-chemical synthesis approaches for the anisotropic
MCs also changes. The contact angle of MoS2 changed from MCs.
∼58° for pristine MoS2 to 90° for methyl (less polar)-
functionalized MoS2. Noncovalent chemical functionalization 3.1. Nonstoichiometric Nucleation and Growth
of the 2D WSe2 thin film by 4-nitrobenzenediazonium The underlying principles of nanocrystal formation follow the
tetrafluoroborate (4-NBD) and diethylenetriamine (DETA) stoichiometric nucleation and growth (N&G) proposed by
molecules was found to allow efficient charge transfer to WSe2 LaMer and co-workers in the early 1950s.290 When it comes to
and consequent conversion of the ambipolar WSe2 into a p- the MC nanocrystal synthesis, the concentration of MC
type and n-type semiconductor, respectively. The doping clusters increases with time as the metal and chalcogen
enhanced carrier mobilities considerably for both holes and precursors react. Once the concentration of MC clusters
electrons (Figure 14c).288 To produce multifunctional MC reaches a supersaturation, the MC clusters starts to gather into
platforms, “click” chemistry based multistep covalent function- small nuclei via homogeneous nucleation. The nuclei grow into
alization has recently been employed. The phenyl-azido nanocrystals of larger size until an equilibrium state is reached
functionalized MoS2 was used to produce homo- and between clusters on the surface of the nanocrystal and that in
heterodecorated MoS2 through “click” chemistry of copper- the solution.291 In typical synthesis of MC nanoparticles, metal
Chem. Rev. 2023, 123, 3329−3442
and chalcogen precursors are separately added to the reaction hydrate under hydrothermal conditions.303 Strong growth
medium, which leads to the time difference in the preferences in the c-axis resulted in their length bieng hundreds
decomposition of the precursors and supply of elements. of micrometers with an average diameter of 90 nm. For 2D
Even when the precursors are mixed homogeneously by the ZrS2 nanodiscs, surface energies are 0.194 J m−2 for the (001)
stoichiometric ratio, the decomposition rates of the precursors surface and 0.928 J m−2 for the (100) or (010) surface;304
are not same in most reaction conditions; thus, the elements hence, ZrS2 grows in the (100) or (010) direction, and the
are not supplied by the stoichiometric ratio.292−294 This (001) basal plane with low surface energy is exposed.
process results in the nonstoichiometric reaction, which is 3.2.2. Surfactant-Assisted Anisotropic Growth. MCs
followed by a continuous chemical transformation toward the without preferential surface energy and anisotropic binding
stoichiometry during the reaction process (Figure 15a).295 energy grow in an isotropic shape. Surfactants binding to
Systematic investigation revealed that the transformation specific facets can tailor the surface energy and induce
process from chalcogen to MC or from metal to MC follows anisotropic growth. For example, Cu2‑xSe (cubic), Bi2S3
the surface nucleation−detachment−reorganization process.292 (orthorhombic), and FeSe2 (orthorhombic) tend to grow in
Initial nucleation of MC happens at the surfaces of the pure 0D nanoparticles or in 1D NWs.305−307 McCarthy et al.
chalcogens, then the nuclei are detached from the surface, and succeeded in synthesizing 2D Cu2‑xSe, Bi2S3, and FeSe2 NPs by
the detached nuclei are reorganized to form 2D MC using oleylamine as a surfactant (Figure 16b).308 They
nanocrystals, as shown in the M2X3 composition (Figure reported that the amine groups in oleylamine form a secondary
15b). Regardless of starting from chalcogen NWs or metal complex after being mixed with the metal or chalcogen
microparticles, addition of a metal source or chalcogen source precursors at an intermediate temperature. At an elevated
converted the initial material into NSs. Giri et al. revealed that temperature, the complexes are decomposed and oleylamine
formation of MX2 NS follows the same reaction pathway binds to a specific facet to modify the surface energy.309−311
(Figure 15c).294 Time-dependent TEM analysis showed that Surfactants can serve as soft templates for 2D MCs crystals.
Te-rich NWs and irregular amorphous Mo-rich aggregates are Zhang et al. synthesized 3D radially oriented MoS2 by using
formed as intermediate products, and they are transformed poly(vinylpyrrolidone) (PVP).312 Due to tight binding of PVP
into MoTe2 NSs. to the (002) surface of MoS2, the lattice distance of (002)
3.2. Growth Mechanisms
increased to 0.707 nm compared to that (0.63 nm) of bulk
MoS2. The MoS2 NSs were radially oriented, providing
Various growth mechanisms of anisotropic MC crystals have catalytically active edge sites. When the synthesis was
been proposed to control the shape, thickness, dimension, and conducted without PVP, pure hexagonal MoS2 NSs were
composition. Anisotropic growth mechanisms can be divided obtained.
into (1) intrinsically anisotropic growth, (2) surfactant-assisted 3.2.3. Anisotropic Growth Driven by Oriented Attach-
anisotropic growth, (3) oriented-attachment anisotropic ment. The classical growth mechanism and the Ostwald
growth, (4) chemical transformation, and (5) template-assisted ripening assume the sequential atom-by-atom growth of
growth. This section explains the principles of the growth nanocrystals.313 Penn et al. proposed an oriented attachment
mechanisms and introduces successful advances in each growth mechanism for MC anisotropic nanocrystals in
mechanism. 1998.314 In the proposed growth mechanism, primary
3.2.1. Intrinsically Anisotropic Growth. During thermo- nanocrystals collide and form loosely bound aggregates with
dynamic growth of nuclei, the shape of nanocrystals is random orientation. These primary nanocrystals rearrange
dominated by the surface energy of crystallographic facets. themselves to form irreversible attachments along thermody-
The Wulff theorem states that the crystal grows at a faster rate namically preferential orientations. The oriented attachment
in a high-energy facet direction and the facet eventually has been observed in time-dependent investigations on the
disappears to minimize the total surface energy. Most of MCs crystal growth in several anisostropic MCs nanocrystals.315−321
with chemical compositions of MX, MX2, and M2X3 are grown Single-crystalline Bi2Se3 nanodiscs with a thickness of ∼4 nm
in 2D shapes (NPs, NSs, nanodiscs, and nanoflakes) due to the and a lateral dimension of ∼150 nm were synthesized by hot
vdW-bonded layered structures.296−298 While Bi2S3, Sb2S3, and injection (180 °C) of reducing agent (hydroxylamine,
Sb2Se3 prefer to grow in the 1D shape (NRs and NWs) due to NH2OH) into Bi(NO3)3·5H2O and Na2SeO3 solution mixed
the chain-like molecular conformation, the vdW interaction in ethylene glycol.322 The TEM analysis captured the growth
still exists between the chains.299−301 Using first-principle DFT process which followed the formation of Bi2Se3 seed
calculations, it was shown that the surface free energy of the nanocrystrals and their continuous attachment to form larger
(001) surface of Bi2S3 (0.423 J m−2) was higher than those of seed crystals. The attached nanocrystals were in situ self-
other low-index surfaces (0.359 J m−2 and 0.350 J m−2 for organized and produced a single crystal nanodisc within 30 s
(100) and (010) surfaces, respectively) (Figure 16a).302 Single (Figure 16c). It is because the oriented attachment is
precursors containing both metal and chalcogen sources ensure thermodynamically favorable and the nanocrystals are strongly
stochiometric elemental supply to the solution phase so that stabilized. Ultrathin PbS NSs were formed within reaction
undesired initial growth of chalcogen or metal nanocrystals can times of 1−3 min,323 and various shapes of PbSe NWs
be minimized. With the advantage of a single precursor, Wang (including undulated, zigzag, straight, star-shape branches,
et al. prepared Bi2S3 NRs with lengths of 30−100 nm and tapered branches) have been obtained within 5 min.324 Once
diameters of 7−18 nm by using decomposition of the single the oriented-attachment takes place, the growth process could
precursor (Bi(S2CNR2)3 where R = alkyl) in solvothermal be shifted to Ostwald ripening when the surfaces of
conditions and also synthesized long Bi2S3 NWs with nanocrystals are sparsely capped with ligands/surfactants.325
diameters of 59−84 nm and lengths of 2−3 μm.302 As well Ex situ oriented attachment can be achieved by separating
as Bi2S3 NWs (NRs), Luo et al. synthesized ultralong Sb2Se3 the formation of nanocrystals and the oriented attachment
NWs by reducing Sb(CH3COO)3 and Na2SeO3 by hydrazine process. The ex situ oriented attachment enables detailed
Chem. Rev. 2023, 123, 3329−3442
Figure 17. Chemical transformation, template-assisted growth, and quantized growth as the growth mechanisms in solution-phase synthesis. (a)
Scheme showing the concepts and principles of the chemical transformation reactions including compound formation, cation exchange, and anion
exchange. (b) Scheme of the template-assisted growth to create a hierarchical MoS2 microboxes and corresponding SEM images. (c) TEM images
of CdSe quantum NWs with different diameters. (d) Scheme of structure evolution of 2D, 1D, and 0D quantum crystals with varying reaction
temperature. (e) Potential energy landscape for the structural formation of different dimensionality from molecular precursors to 1D, 2D, and 3D
crystals. (a) Reprinted from permission from ref 117. Copyright 2018, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. (b) Reprinted with
permission from ref 358. Copyright 2014, The Royal Society of Chemistry. (c) Reprinted from permission from ref 377. Copyright 2006, American
Chemical Society. (d) Reprinted from permission from ref 379 Copyright 2017, American Chemical Society (e) Reprinted from permission from
ref 380. Copyright 2020, American Chemical Society.
mechanistic study and controllability over attachment attachments were observed after the solvent was completely
geometry.326−328 Overbeek et al. demonstrated square-, line-, evaporated. The square- and linear-type oriented attachments
honeycomb-, and zigzag-type ex situ oriented attachments by were attributed to the bonds through the ⟨100⟩ direction, and
controlling the surface area per nanocrystals at the liquid the honeycomb- and zigzag-type oriented attachments were
interfaces.329 They first synthesized PbS, PbSe, and PbTe achieved by the bonds through the ⟨111⟩ direction (Figure
nanoparticles with sizes of 5.1, 5.5, and 4.8 nm, respectively. 16d). The authors addressed that the optimal temperature for
Those nanoparticles were dispersed in an apolar solvent, and controlled oriented attachment decreased in the order of PbS >
the solution was carefully drop-casted onto ethylene glycol PbSe > PbTe due to the increased surface reactivity (PbTe >
which acted as a liquid substrate. Various types of oriented PbSe > PbS).
Chem. Rev. 2023, 123, 3329−3442
Not only oriented attachment between identical nanocryst- As well as binary MCs, anisotropic 1D ternary and
als but also oriented attachment between different nanocrystals quaternary MCs can be formed via chemical transformation.
can be achieved. Lim et al. demonstrated oriented attachment Typically Te, or the solid solution of TexSey, has been widely
between In2S3 and CuS(Se) nanocrystals.330,331 After the applied as an chemical transformation template.348−350 Zhou et
oriented attachment, compounds of CuIn5S8 and CuInSxSe1−x al. developed a general method of ultrathin (<20 nm) ternary
were created. Due to the adsorption of sulfide ions, zeta- MC NWs including Bi 2 (Te x Se 1 − x ) 3 , Ag 2 Te x Se 1 − x ,
potentials of individual In2S3 (−33 mV) and CuS (−20 mV) Cu1.75TexSe1−x, CdTexSe1−x, and PbTexSe1−x.351 Their syn-
nanocrystals were negatively charged, inhibiting the oriented thetic method was composed of three steps: (1) synthesis of
attachment by electrostatic repulsion. The authors modified Te NWs as a template, (2) incorporation of Se atoms into Te
the surface charge by anchoring polyelectrolytes such as NWs to form TexSe1−x NWs with tunable compositions, and
poly(acrylic acid) (PAA) and polydiallyldimethylammonium (3) chemical transformation of the TexSe1−x into ternary
chloride (PDAC). Zeta-potentials of PDAC-In2S3, PDAC-CuS, alloyed metal TexSe1−x by adding metal precursors. As the
and PAA-CuSe were +38.0 mV, +36.7 mV, and −43.0 mV, transformation proceeds, the diameter of NWs increased from
respectively. Due to the strong electrostatic attraction by 6 nm (Te NWs), 11 nm (Te0.5Se0.5 NWs), to 20 nm
polyelectrolytes, the oriented attachment between CuS(Se) (Bi2Te1.5Se1.5 NWs). Not only single metal/multi chalcogenide
and In2S3 took place to form the alloys (Figure 16e). A control alloys but also multi metal/single chalcogenide alloy NWs
experiment conducted without surface modification produced could be produced such as BiSbTe-PbTe,352 PdAgTe,353 and
a simple mixture of separate In2S3 and CuSe, indicating PtPdTe.354 Ma et al. synthesized quaternary chalcogenide NTs
electrostatic attraction played a critical role. with the composition of PtPdRuTe.355 They first synthesized
3.2.4. Chemical Transformation. Chemical transforma- Te NWs with a diameter of 7−9 nm and transformed the Te
tion is a powerful strategy to obtain nanocrystals with diverse NWs to RuTe2 NTs by adding an aqueous solution of RuCl3.
morphologies and chemical compositions that is difficult to Due to the Kirkendall effect where the net outward flow of a
synthesize directly from the conventional synthetic methods. faster-diffusing species is balanced by the opposite flow of
In the typical chemical transformation process, premade vacancies, Te NWs turned into RuTe NTs rather than NWs.
nanocrystals serve as an inorganic template and their After transformation to RuTe2, a mixed solution of K2PtCl6
morphologies are maintained while their compositions vary and K2PdCl4 with varying molar ratio was dropwise added and
(Figure 17a). The transformation can be accomplished by further transformed to quaternary MC NTs by galvanic
eliminating homogeneous nucleation and controlling the replacement. The authors demonstrated that a wide range of
composition could be tuned including Pt7Pd35Ru21Te37,
reaction kinetics with experimental variables. Among three
Pt 1 0 Pd 2 7 Ru 2 3 Te 4 0 , Pt 2 6 Pd 1 2 Ru 2 3 Te 3 9 , Pt 3 4 Ru 2 5 Te 4 1 ,
categories of chemical transformation (galvanic replacement,
Pt27Pd22Te51, Pd51Te49, and Pt52Te48 NTs.
alloy formation, ion exchange reaction), ion exchange reaction
Recently, Ramasmy et al. demonstrated sophisticated
has been widely applied in the synthesis of anisotropic MCs,
chemical transformation from Cu2‑xSe NSs to quinary
including NTs (Ag2Se, Bi2Te3, CoTe, CoTe2, PtTe2),332−335
Cu2ZnGeSxSe4‑x involving both cation and anion exchange
NWs (Ag2Se, Ag2Te, Bi2Te3, CdSe, CdTe, PbTe, ZnTe,
reactions.356 Also atomic composition of incorporated S was
La2Te3),336−340 and NRs (PbS and ZnSe).62,341 The driving controlled by reaction temperature since initial Cu2‑xSe NSs
force for the ion exchange reaction is solubility difference.342 were capped with 1-dodecanethiol. To induce cation exchange,
Moon et al. demonstrated that adding the appropriate ligand GeI4 was added at room temperature and a ZnCl2 solution was
that reverses the solubility of MCs can induce chemical added at a high temperature (>210 °C) to produce
transformation which is thermodynamically unfavorable with- Cu2ZnGeSe4 NSs. When the reaction proceeded at a higher
out the ligand.343 Te NWs could be transformed into Ag2Te temperature (250 °C), 1-dodecanethiol was decomposed and
NWs via the topotactic alloying process, and then further participated in the anion exchange reaction to create
converted to CdTe, ZnTe, PbTe NWs and PtTe2 NTs. Cu2ZnGeSxSe4‑x. EDS analysis revealed that the chemical
Because the solubility parameter of CdTe, ZnTe, PbTe is composition was homogeneous in a single NS, and S
larger than that of Ag2Te in polar solvents, cation exchange concentration (x) varied from 0.35 at 210 °C to 1.67 at 250
reactions converting Ag2Te to CdTe, ZnTe, and PbTe are °C in Cu2GeSxSe3‑x. In and Ga could be also inserted to form
thermodynamically prohibited. Introducing a complex agent CuIn1−xGaxSe2 NSs through the same procedure by using
(tributylphosphine) which selectively forms a complex with Ag InCl3 and GaCl3 instead of GeI4 and ZnCl2.
made the cation exchange reaction possible. 3.2.5. Template-Assisted Growth. MCs can grow from a
In most MC crystals, chalcogen anions act as a network pre-existing organic or inorganic template through weak local
holding the relatively mobile metal cations. Exchanging the interactions (e.g., vdW forces, hydrogen bonds, π−π
anions is accompanied with an overall structural change of the interactions). Removing the template produces MCs with
network and typically leads to a large volume change; hence, controlled pores. Recently, Deng et al. prepared a foam
anion exchange of MC crystals has been relatively less consisting of uniform mesoporous MoS 2 NSs. 3 5 7
investigated. Some studies demonstrated anion exchange; (NH4)6Mo7O24 was homogeneously coated on the surfaces
from Cd(OH)2 NWs to Cd(S, Se, Te) NTs,344 from SnSe of the SiO2 colloids by wet impregnation. Chemical reaction
NSs to porous SnTe NSs,345 and from Mo(W)O3 NWs to between (NH4)6Mo7O24 and CS2 on the SiO2 surface created
Mo(W)S2 NSs.346,347 The large volume change makes it small MoS2 domains which further self-assembled into
difficult to preserve the morphology of the starting nanocryst- vertically aligned MoS2 layers around the SiO2 particles.
als. For example, dense Mo(W)O3 NWs were transformed into Finally, mesoporous MoS2 foam was obtained after etching the
Mo(W)S2 hierarchical nanostructures. Although the length of SiO2 template with HF. Zhang et al. synthesized hierarchical
the NW was preserved, the resulting Mo(W)S2 consisted of microboxes composed of ultrathin MoS2 NSs.358 Highly
small NSs.346,347 uniform MnCO3 microcubes with an average size of 2.5 μm
Chem. Rev. 2023, 123, 3329−3442
Figure 18. Wet-chemical synthesis of anisotropic MCs. (a) TEM image of TiS2 2D nanocrystals synthesized by the hot-injection method. (b)
HRTEM image of PbS nanocrystals showing atomically intimate interfaces obtained by the one-pot heat-up process. The inset shows a low
magnification TEM image of the PbS nanocrystals. (c) TEM image of the edge of 1T-WS2 NRBs with an expanded interlayer distance. (d) Scheme
of the localized microwave heating of a conducting substrate, which allowed the growth of 2D thin films without any crystal formation in the bulk
solution. (e) Cross-sectional HRTEM image of the monolayer WSe2 thin film produced by the microwave heating. (a) Reprinted from permission
from ref 390. Copyright 2012, American Chemical Society. (b) Reprinted with permission from ref 401. Copyright 2015, American Chemical
Society. (c) Reprinted from permission from ref 421. Copyright 2015, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. (d,e) Reprinted with
permission from ref 15. Copyright 2017, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
was employed as a template. In hydrothermal conditions, the highly uniform ZnSe NB.375 Zhang et al. produced ZnTe
reaction between Na2MoO4 or MnCO3 and L-cysteine formed MSCs with triangle NPs, square plates, and NWs with a small
MnS@MoS2 core−shell microcubes. Then, MnS was etched FWHM (<6 nm) in the absorption spectra. It was found that
by HCl solution to form the microboxes (Figure 15b). the MSCs consisted of (ZnTe)13 and (ZnTe)19 clusters.376
The templates may be transformed to other materials during Pradhan et al. synthesized CdSe quantized wires with a
the reaction process, which creates heterostructures on the diameter range of 1.5−6 nm.377 The CdSe quantized NWs
resulting MCs. Carbon-based templates have been investigated were produced by reacting cadmium acetate and selenourea in
for in situ creation of the MC heterostructures with graphene, amines. The diameter of the NWs increased with the alkyl
reduced graphene oxide (GO), and CNTs.359−365 Choi et al. chain length of amines (Figure 17c). The thinnest NW (2.1
prepared 3D MoS2-graphene microspheres by ultrasonic spray nm) corresponded to the magic size.
pyrolysis from a colloidal solution of polystyrene (PS), GO, While the origin of anisotropic MSCs has been thought to
and (NH4)2MoS4.366 During pyrolysis at 800 °C under be lamellar mesophases resulting from the primary alkylamine
nitrogen, GO and (NH4)2MoS4 were converted into reduced (e.g., oleylamine, octylamine) soft template, the literature has
GO and MoS2, respectively. After thermal decomposition of reported that the lamellar structures are absent at the
the PS particles, porous 3D MoS2-graphene microspheres were temperature where the anisotropic MSCs are formed.
obtained. The large surface area (33 m2 g−1) was beneficial for Riedinger et al. synthesized CdSe NPs in Cd(carboxyalte)2
electrochemical reactions. and elemental Se at 200 °C without any solvent.378 The
3.2.6. Quantized Growth. In recent decades, 1D and 2D precursors and synthesis conditions applied for 2D, 1D, and
anisotropic magic-size clusters (MSCs) have been intensively 0D MSCs were similar, except the reaction temperature. The
studied.367−373 The term “magic-size cluster” is used to denote 1D MSCs were obtained at higher reaction temperature than
atomically precise clusters of semiconductors with a well- the 2D MSCs (e.g., 100−180 and 25−100 °C, respectively).
defined number of atoms.374 MSCs tend to grow in a Berends et al. proposed that the dimensionality of the resulting
discontinuous and quantized manner, where MSCs with one MSCs is determined by the thermal stability of the soft
magic size grow to the next without intermediate sizes. This templates formed by the ligands.379 Because of the short-range
quantized growth is different from continuous growth which is and weak vdW interaction between alkyl chains, it is preferred
typically encountered for colloidal MC nanocrystals. The to align in 2D structures at low temperature. As temperature
formation of MSCs has been understood on the basis of the increased, thermal fluctuations disrupted the long-range in-
nonclassical nucleation model, where each magic size locates at plane ordering of the 2D templates and the 1D structures were
a local free energy minimum during reaction from precursors stabilized. Further annealing at higher temperature resulted in
to nanocrystals. Park et al. synthesized a 1.4-nm-thick ZnSe NB 0D MSCs as in the typical hot injection method (Figure 17d).
with narrow absorption peak width (<10 nm), indicating a However, this explanation cannot describe recent experimental
Chem. Rev. 2023, 123, 3329−3442
results reported by Cunningham et al., in which ZnSe 0D, 1D, ∼100 nm to 2 μm, and the thickness increased from 0.4 to 2.6
and 2D MSCs were produced at 120, 130, and 150 °C, nm. In metal sulfides, a metal oleate complex and
respectively.380 The authors excluded the templating effect dodecanethiol have been often used as the metal and S
through the study with small-angle X-ray scattering analysis sources.393 Vaughn et al. synthesized 5-nm-thick 2D GeS by
and found that Zn-amine precursor lamellar structure at room reacting GeI4 and dodecanethiol in the presence of oleylamine,
temperature disappeared at lower temperature (60 °C). To oleic acid, and hexamethyldisilazane (HMDS).394 GeSe NSs
rationalize their observations, the authors suggested a unified with a thickness of 5−100 nm were obtained using the same
reaction pathway. In this model, a sufficiently high temperature synthetic procedure except using a trioctylphosphine-selenium
is required to overcome an isotropic homogeneous nucleation (TOP:Se) complex instead of dodecanethiol.
barrier. Since the isotropic homogeneous nucleation barrier is Thermal decomposition of a single precursor containing
high at low temperature, the reaction products are trapped in both metal and chalcogen elements has been investigated to
local free energy minimum regime so that they can be secure simultaneous supply of the elemental sources.395−408
stabilized (Figure 17e). Among the various single precursors, metal xanthates have
3.3. Wet-Chemical Synthesis been often used due to its high solubility in nonpolar organic
solvents and a relatively low decomposition temperature (<200
Wet chemical synthesis of MCs has been widely studied due to °C).395,401,403,404,407 It is notable that side products caused by
the tunability over broad range chemical compositions,
decomposition of metal xanthates are volatile; hence, nano-
morphology, lateral dimension, thickness, and crystal phases.
crystals without organic capping agents at the surfaces can be
The synthesis can be categorized in (1) hot injection synthesis,
obtained. Lewis et al. synthesized PbS nanocubes and NWs by
(2) one-pot heat-up synthesis, (3) hydro/solvothermal
using Pb n-alkylxanthate, and they successfully achieved
reduction, and (4) microwave-assisted reduction. There have
atomically intimate contact between nanocrystals due to the
been several review articles on the wet-chemical synthesis of
capping agent-free surfaces of the nanocrystals.401 For Mo-
MCs;150,342,381 this section briefly introduces recent advances
based single precursors, Savjani et al. synthesized ligand-free
in the solution-based synthesis.
3.3.1. Hot Injection Synthesis. The hot injection has 1H-MoS2 NSs with various precursors of xanthate or
been widely applied for preparation of single-crystalline, size- dithiocarbamate (Mo2O4(S2CNEt2)2, Mo2O2S2(S2CNEt2)2,
and shape-controlled nanocrystals. An anionic precursor Mo2S4(S2CNEt2)2, Mo2O2S2(S2COEt)2, and
solution containing a chalcogen precursor is injected into a Mo2S4(S2COEt)2).408 It was reported that
hot mixture solution of metal precursors and capping agents. Mo2O2S2(S2COEt)2 was ideal for the production of single-
Elemental chalcogen, organic-chalcogen, and CS2 have been layer MoS2 because of the fast thermolysis kinetics in
often used as the chalcogen source. Metal chlorides, metal homogeneous intermediate species.
carbonyl, metal acetylacetonate, and metal carboxylate 3.3.3. Hydrothermal/Solvothermal Synthesis. Hydro/
precursors have been used for the metal source.382−389 Jeong solvothermal synthesis is typically conducted in a sealed
et al. developed generalized synthetic protocols for colloidal autoclave at an elevated temperature and pressure in order to
2D MCs including metal sulfides (TiS2, VS2, NbS2, TaS2, ZrS2, promote the formation of crystals in water (hydrothermal) or
and HfS2) (Figure 18a).390 2D metal sulfide nanocrystals were in nonaqueous solution (solvothermal).409−412 For the syn-
synthesized through the reaction between the metal chloride in thesis of MX2 stoichiometry, ammonium (sodium) molybdate
oleylamine and the injected CS2 at 300 °C. The obtained TiS2 or tungstate has commonly been used as the metal precursor,
nanocrystals were in a disc shape with the lateral size of 100 and thiourea, elemental S, SeO2, and elemental Se have been
nm and the thickness of 10 nm. The reaction occurred used as the chalcogen source.413−421 In hydrothermal syn-
between TiCl4 and the in situ generated H2S as an thesis, since counter cations in metal precursors (i.e., Na+ or
intermediate reactant. It was found that an appropriate NH4+) can be intercalated in the resultant MCs during the
chalcogen source with less reactive radical species led to the synthesis, the cations can stabilize the metastable 1T
formation of well-defined colloidal 2D MCs. The elemental S phase.419−423 Liu et al. obtained stable WS2 NRBs with widths
that was converted into highly reactive radical species in of 50−200 nm and a thickness of 3.9 nm (Figure 18c).421 The
oleylamine at a high temperature (300 °C) made poorly interlayer distance of the (002) plane of the NH4+-intercalated
defined 2D MCs particles. When elemental S was reacted with WS2 NRBs was 9.58 Å which was 3.42 Å larger than the bulk
well-defined TiS2 nanocrystals, the S radicals promoted 2H-WS 2 . DSC measurement revealed an endothermic
structural degradation of TiS2 nanocrystals. Owing to the deintercalation of the NH4+ ion at 270 °C.424 By adjusting
soft nature of Se radical species, this synthetic protocol was the concentrations of the precursors, ultrathin defect-free and
generally applicable to various transition metal selenide defect-rich MoS2 NSs could be selectively obtained.416 During
nanocrystals such as TiSe2, VSe2, NbSe2, TaSe2, ZrSe3, and chemical reaction between hexaammonium heptamolybdtate
HfSe3. tetrahydrate and thiourea, the excess thiourea (Mo:S = 1:4.3)
3.3.2. One-Pot Heat-up Process. In the one-pot heat-up adsorbed on the surface of the primary nanocrystals and
process, the reaction components (metal precursor, chalcogen partially hindered oriented crystal growth, leading to the
precursor, capping agent) are mixed at low temperature, and formation of defect-rich structure with quasi-periodicity. When
then the mixed solution is heated to a high temperature to a stoichiometric amount (Mo:S = 1:2) of thiourea was used in
trigger the chemical reaction.391 Single-layer VSe2 NSs were the synthesis, defect-free MoS2 NSs were obtained.
produced by reacting vanadyl acetylacetonate (VO(acac)2) 3.3.4. Microwave-Assisted Synthesis. Microwave-assis-
and elemental Se in oleylamine at 330 °C (Figure 18b).392 ted synthesis uses microwave heating, in which microwave
Time-dependent study revealed that increasing the reaction energy is absorbed by the reactants and leads to decom-
time produced larger and thicker VSe2 hexagonal NSs by the position. The microwave energy loss at unit volume can be
oriented attachment. The lateral dimension increased from expressed in the following equation:
Chem. Rev. 2023, 123, 3329−3442
Figure 19. (a) Scheme of the possible nucleation and growth route to multilayer MoS2, in which Mo-oxysulfide (MoOxS2−y, y ≥ x) seeds are
involved. (b) Possible nucleation and growth route to a monolayer MoS2, in which atomic scale MoS2 monolayer clusters are generated as seeds.
(c) The effect of salt in the vapor−solid (VS) and vapor−liquid−solid (VLS) phase transition, and a scheme describing the VS transition without
assisted by salt and the VLS transition involving the salt-assisted growth. (a, b) Reprinted with permission from ref 440. Copyright 2017, Rights
Managed by Nature Publishing Group. (c) Reprinted with permission from ref 444. Copyright 2021, Rights Managed by Nature Publishing Group.
1 localized at Au NW electrodes, uniform coating of 8-nm-

P= |E|2 + pf 0 r |E|2 + p f 0 r |H|2
2 thick MoS2 was achieved in a short time (10 min). Giri et al.
have fabricated a variety of 2D MC thin films (MX2, M = Mo,
where P, E, H, σ, f, ε0, εr″, μ0, μr″, p, and p′ represent energy W, V, Nb, and X = S, Se, Te) directly on the conducting
loss at unit volume, electric field intensity, magnetic field substrates.15,294,431 They dissolved metal and chalcogen
intensity, electric conductivity, frequency, permittivity of free
precursors in an electrolyte and placed the solution on a
space, dielectric loss, permeability of free space, magnetic loss,
and coefficients, respectively. The microwave heating efficiency conductive Si wafer. Since microwave heating was localized on
is determined by conductivity, dielectric loss, and magnetic loss the surface of the conductive substrate, crystal formation and
of the absorbing materials as well as frequency, electric field growth took place only at the surface of the substrate (Figure
intensity, and magnetic field intensity of microwave appara- 18d). With varying concentration of metal and chalcogen
tus.425,426 precursors in the liquid electrolyte, precise thickness control of
Compared to the conventional thermal heating, microwave the MC films was readily achieved (Figure 18e).
heating is instantaneous, direct, and volumetric. The micro-
wave heating facilitates homogeneous rapid temperature rise in 4. VAPOR-PHASE SYNTHESIS
the entire solution. Another important feature of the
microwave heating is selectivity to precursors.427−429 If one Vapor phase deposition is a powerful route to synthesis of
reactant interacts strongly with microwaves, microwave heating high-quality anisotropic MCs with controllable layer number,
can be localized in the vicinity of the reactant while grain size, orientation, and morphology. This section reviews
maintaining a lower temperature in others. Lee et al. various vapor-phase strategies to grow anisotropic MCs. The
synthesized MoS2 grown on 3D-structured Au NW electrodes key parameters for structural and morphological engineering
by microwave heating.430 Because microwave heating is and modulation of their intrinsic properties are also discussed.
Chem. Rev. 2023, 123, 3329−3442
Figure 20. (a) SEM (on top) and optical microscope (OM) images (at bottom) of MoS2 on a c-sapphire obtained from NaCl-free growth and
NaCl-assisted growth, respectively. (b) The role of nucleation density on the evolution of lateral dimension of NiTe2 single crystals grown at
different temperature. Scale bars: 5 μm. (c) Epitaxy-guided seed formation and alignment of 2D crystals dependent on sulfur flux. (d) Different
growth behaviors of MoS2 during deposition on stationary substrate and moving substrate. (a) Reprinted with permission from ref 456. Copyright
2017 American Chemical Society. (b) Reprinted with permission from ref 436. Copyright 2018 American Chemical Society. (c) Reprinted with
permission from ref 463. Copyright 2020 Elsevier Ltd. (d) Reprinted with permission from ref 492. Copyright 2019 IOP Publishing.
4.1. Nucleation the reaction temperature, which is explained by the increase of

Vapor-phase deposition of anisotropic MCs generally involves the adatom mobility and desorption rate at higher temper-
three steps: thermal decomposition and evaporation of the atures. Elevation of the substrate temperature can be used to
precursors, transport and migration of reactants, and reduce or regulate the nucleation rate and nucleation density
nucleation and growth of MCs crystals on a target substrate. for better controllability over crystal growth. Zhao et al. has
demonstrated that low substrate temperature accelerates the
As a model example of 2D MCs, various nucleation pathways
nucleation rate of NiTe2, producing a thin film, whereas high
to MoS2 and the controlling factors are discussed in this
substrate temperature leads to a low nucleation rate and
section. Due to the low melting temperature (795 °C) of
produces thick NiTe2 single crystals.436 Distribution of the
MoO3, sulfurization of MoO3 has been the primary approach
carrier gas speed at the substrate surface can also be used to
to MoS2 growth.432−434 Upon partial reduction with sulfur
modulate nuclei formation. Once initial nuclei are formed,
vapor at a high temperature zone, MoO3 forms a volatile crystal growth is initiated by diffusion of the reactants and
MoO3‑xSy, which is then conveyed downstream by the carrier subsequent attachment to the edge of the lattice of the nuclei.
gas. MoS2 is deposited on a growth substrate through Since the metal atoms are passivated by chalcogens at the
subsequent adsorption and surface-bound reaction with sulfur. edges of MCs, their edge formation energies are usually smaller
When the concentration of the segregated adatoms reaches a than that of graphene and hBN so that the energy barrier for
critical supersaturation level, nucleation takes place.435 The stable nuclei formation is smaller. Controlling the nucleation
saturation density (Ns) for nuclei formation is expressed by the density of MCs is a challenging task which has a major effect
following relationship which assumes atomic size critical nuclei on the resultant film formation.437−439 The adatoms on the in-
at the precursor partial pressure (P) and nucleation activation plane surface readily migrate to the edges due to the chalcogen
energy of G*,435NS3 PeG * /kT . Ns is inversely proportional to passivation; hence, lateral growth is usually preferred. Zhu et al.
Chem. Rev. 2023, 123, 3329−3442
has directly probed the nucleation seeds and tracked the edge position, and compound formation. Solid chalcogen powders
structures and shape evolution of MoS2 2D crystals.440 Two are often used as chalcogen sources. For the metal sources,
types of nucleation seeds were observed: (i) Mo-oxysulfide metal oxides (e.g., Mo/WOx, In2O3), metal ammonium salts
(MoOxS2−y, y ≥ x) nanocrystals that will be ultimately (e.g., (NH4)6Mo7O24·4H2O and (NH4)10W12O41·xH2O),
transformed into multilayer MoS2 (Figure 19a), and (ii) metal oxychlorides ((e.g., Mo/W)OxCly), metal chlorides
atomic scale MoS2 monolayer clusters that will produce large- (e.g., MoCl5, WCl6, SnI2), or sometimes metal foils are
area monolayer MoS2 films (Figure 19b). When the metal used.432,434,448,452−455 A difference in the partial pressure of the
precursor concentration was too high, the MoOxS2‑y nano- precursors created by sublimation results in the spatially
crystals were formed on the substrate and served as the nonuniform growth dynamics, which produces uncontrollable
heterogeneous nucleation sites for the growth of MoS2 few- growth. Generally, uniform vapor pressure of the metal
layers structures (nucleation route 1).440,441 The formation of precursors through slow sublimation is essential for layer-
nanoparticles or multilayer domains could be reduced by controlled growth of uniform MCs. Fast sublimation leads to
introducing H2 gas due to the etching effect.442,443 When the excessive nucleation sites and forms thick domains. Kim et al.
metal precursor concentration was moderately high, molecular has demonstrated that exposing c-sapphire substrates to alkali
clusters ((MoO2)n or (MoO3)n) were sulfurized completely metal halide salts such as KI or NaCl together with the Mo
through homogeneous gas phase reaction before they were precursor prior to the start of the growth process enables large
deposited on the substrate as monolayer MoS2 (nucleation area growth of MoS2 single crystalline domains by more than 2
route 2).440 orders of magnitude (Figure 20a).456 Instead of traditional
Apart from this conventional conversion through the vapor− powder-type metal sources, gas phase metal−organic com-
solid transition (VS transition), a vapor−liquid−solid (VLS) pounds (e.g., Mo(CO)6, W(CO)6 and (t-BuN�)2W(NMe2)2)
growth can be triggered by the reaction between MoO3 and provide better feeding rate control so that wafer-scale uniform
NaCl (Figure 19c). Alkali metal salts can act as catalysts to MC thin films can be reproducibly obtained.457−459 Use of
decrease the energy barrier and increase the surface reaction gaseous chalcogen precursors such as (C2H5)2S, (C2H5)2Se2,
rate. NaCl chemically reacts with MoO3 at temperatures much (t-C4H9)2S2, (C4H9)2Te, and H2S has also recently been
below the melting point of the compound, resulting in the utilized for controlled growth of uniform wafer-scale
formation of molten Na−Mo−O droplets through the monolayer to multilayer MC thin films.457,459−461 Kim et al.,
following reaction.6 Chaudhury et al., and Wang et al. have recently summarized
the up-to-date metal and chalcogen precursors reported for the
3MoO3 (s) + 2NaCl (s) growth of 2D MCs.115,462,463
4.2.2. Temperature. Since the concentration ratio of the
Na 2Mo2O7 (l) + MoO2 Cl 2 (g)
precursors is critical for controlling the growth of MCs,
The process goes through a two-step nucleation, in which the effective kinetic control of the precursor mass flux is important.
initial metastable clusters are formed through the aggregation The precursor mass flux determines the amount of metal
of the droplets and the solid MoS2 nuclei are created precursor involved in the nucleation and domain growth.464 At
subsequently inside the metastable clusters.444 Suppressing high metal flux, small-grain polycrystalline thin films are
the nucleation density down to one nucleus (single nucleation formed when the growth rate is low, whereas large-grain
approach) on a substrate and letting it develop into a large-area polycrystalline films are generated at a high growth rate.465 At
single crystal is desired to obtain a large-area single-crystal low mass flux, the low growth rate promotes the formation of
MoS2.445 Reduction of nucleation density has been realized by small flakes,466 whereas the higher growth rate produces
different approaches such as etching of unstable nuclei,446 use millimeter-size large single crystal grains.467 In general, growth
of a catalytically active substrate,447 use of a molten temperature is a fundamental parameter directly affecting the
substrate,448 or introducing growth promoters.445 Multi- rate of chemical reactions of the gaseous precursors, nucleation
nucleation approaches have also been developed to obtain at the vapor−solid interface, deposition rate of the products,
large-area single crystal MoS2 NSs, where seamless stitching of domain size, number of layers, and the quality of crystallization
unidirectional MoS2 islands on an epitaxial substrate can lead of MCs during thermodynamically controlled growth pro-
to a large single crystal.449 cesses.468,469 It also affects the flow rate of carrier gas in the
growth chamber and, thereby, influences the growth rate by
4.2. Growth Control Parameters modulating the nucleation density on the growth substrate.450
The grain size, phase, and morphology of the synthesized MC Temperature of the source zone in the growth chamber
crystals are highly dependent on several growth parameters controls the saturation pressure of the gaseous precursors, and
such as the precursor, substrate, pressure, reaction kinetics, and hence the growth rate is also controlled. Similarly, the
temperature. For rational design and controlled growth, it is temperature of the reaction zone can influence the mass
important to understand the key parameters affecting the heat transport of the gaseous precursors and their reaction at the
and mass transport. This section discusses the key growth vapor−solid interface, which also provides an effective
parameters in the vapor phase deposition processes. approach to modulate the reaction rate. So, the overall growth
4.2.1. Precursors. The vapor phase growth of anisotropic rate of MCs can be either controlled by chemical reaction rate
MC crystals is reliant on the supply of metal and chalcogen at the source zone or by mass transport at the reaction zone.
precursors to the growth front; hence, maintaining a steady For nucleation at the vapor−solid interface in the reaction
vapor flux of the source materials is critical for controllable zone, a high temperature generally leads to a thermodynami-
growth. The growth is also dependent on the type of cally controlled process, while a low temperature results in a
precursors, growth temperature, vapor pressure, and flow rate kinetically controlled process.470,471 To understand the impact
of the carrier gas.450,451 The conversion of precursors into the of growth temperature on domain size and the layer number,
desired products involves chemical transport, thermal decom- there have recently been systematic studies for 2D MoSe2 and
Chem. Rev. 2023, 123, 3329−3442
WSe2 flakes.469,472 The impact of growth temperature on the PMo, nucleation for the second layer is favored only at the grain
growth behavior of NiTe2 NSs, including the layer number, boundaries, thus predominately monolayer products are
lateral dimension, and grain shape, has also been studied for formed. Comparatively, random nucleation of the second
NiTe2 NSs.436 By controlling the growth temperatures, the layer takes place under a high PMo, which thus leads to a
layer number of ultrathin single crystal NiTe2 NSs could be mixture of monolayer and multilayer products.
precisely controlled from multilayer down to monolayer. 4.2.4. Substrates. Crystal symmetry, lattice constant,
While, at a lower growth temperature of ∼530 °C, 1−2 layer miscut angle, microstructure, and surface energy are the
NiTe2 NSs of truncated triangular shapes with an average edge major factors of a substrate which impact the orientation and
size of 4−5 μm were obtained. Meanwhile, 13−17 layer surface coverage of the deposited MC crystals. Amorphous
hexagonal NiTe2 NSs with an average edge size of 17 μm were substrates such as SiO2/Si generally lead to polycrystalline MC
produced as the growth temperature increased to 650 °C films, whereas a single crystal substrate can possibly grow
(Figure 20b). epitaxially a single crystal thin film. For vapor phase growth of
4.2.3. Pressure. Operating pressure has a significant 2D MCs, insulating single crystals such as SrTiO3 (STO),
influence on the gas flow in the vapor phase deposition. (0001) sapphire (α-Al2O3), and mica have been considered as
Depending upon their operating pressure, CVD reactors are suitable epitaxial substrates due to their strong interfacial
classified into atmospheric pressure (AP) (= ∼760 Torr) CVD interactions with MC layers, atomic flatness of the surface, and
and partial vacuum or low pressure (LP) (= ∼0.1−1 Torr) excellent thermal stability.474−478 GaN and GaAs (111) have
CVD. The possibility of gas phase reaction is high in APCVD also been used as the epitaxial substrates for several MCs
due to the high reactant concentration, which makes it difficult including MoS2, WS2, MoSe2, etc.477,479 vdW substrates like
to maintain the atomic smoothness of the synthesized films graphene and hBN have also been explored for the growth of
and often leads to nonuniform coverage of the film on rough or 2D MCs.480,481 Strong interfacial interaction between the
patterned surfaces. However, using the APCVD method, Gong substrate and an MC adlayer is believed to significantly
et al. has recently grown millimeter-scale monolayer MoSe2 influence the adsorption/desorption of precursor species and
single crystals and continuous films consisting of millimeter- their surface diffusion dynamics.482 Lattice-matched single-
size grains on a SiO2/Si wafer.467 They succeeded in crystal sapphire and mica substrates are expected to induce the
suppressing the nucleation density from 105 to 25 nuclei/ multiple MC nucleation sites on the substrates to grow
cm2. Chen et al. have found that the isotropic surface of molten epitaxially with uniform orientation, which then results in the
glass can also suppress the nucleation events under APCVD seamless coalescence of the unidirectionally aligned 2D islands
conditions, and considerably improves the growth of large into a single crystal-like film.13,480 For instance, aligned growth
triangular monolayer MoSe2 crystals with sizes reaching ∼2.5 of MoS2 monolayer grains was achieved with the controlled
mm.448 Moreover, using alkali metal salt as the reaction orientation of seeds on c-plane sapphire.483 A high S/MoO3
promoter, Zhou et al. have recently demonstrated a universal ratio was needed in the early stage of growth in order to
APCVD method to produce a library of 2D MC compounds generate a small number of seeds that are aligned along the
and their heterostructures, where the formation of low melting substrate lattice structures. The ratio was decreased during the
metal oxychlorides promotes the reaction.445 lateral growth stage to suppress the additional nucleation and
Under a low base pressure of the reactor, the concentration enlarge the size of the monolayer (Figure 20c).
of the impurities, residual gases, and H2O can also be The technological challenge of epitaxial degeneracy is mainly
minimized. So, the LPCVD process can produce high purity caused by the noncentrosymmetric C3v lattice (3-fold
films and improve stoichiometric control along with exhibiting symmetry) of the MCs, which causes evolution of antiparallel
excellent uniformity even on rough surfaces. However, it is domains (0° and 60° orientations) and inevitable twin
complex and expensive, and its deposition rates are relatively boundary formation on the high-symmetry (6-fold) surfaces
low and the reaction temperature is high. When the molar flow of sapphire and mica.465 The degeneracy of nucleation energy
of the carrier gas remains constant at low-pressure conditions, for the antiparallel domains can be broken by using a c-plane
the velocity of the gas increases significantly; thereby, the sapphire with step-edges (atomically flat terraces) and miscut
precursor concentration decreases. The low precursor orientation perpendicular to the substrate.484 Without affecting
concentration and the high precursor feed rate in LPCVD the epitaxial relationship, the step-edged sapphire substrates
facilitate the controllable and suitable film growth in wafer lead to unidirectional self-alignment (>99%) of the 2D
scale.114,432,452 Adopting this LPCVD process, Yang et al. have domains. The validity was recently proven with the synthesis
reported the growth of a 6-in. wafer-scale uniform MoS2 of single-crystalline wafer-scale monolayer MoS2 NRBs114 and
monolayer film having an average domain larger than 400 WS2 films.484,485 Similar edge-directed epitaxy on β-Ga2O3
μm.455 Li et al. have recently demonstrated the epitaxial (100) substrate has also been demonstrated to produce
growth of 2-in. monolayer MoS2 and MoSe2 single crystals on a continuous, self-aligned monolayer and single-crystalline MoS2
c-plane sapphire in an LPCVD system under sulfur-rich NRBs.486 The sixfold symmetry of the Au (111) top surface
conditions. Kim et al. has recently reviewed the results and the chemical inertness of Au toward chalcogen atoms
regarding operating pressure and corresponding grain size of make it a suitable substrate for epitaxial growth of large-
the synthesized films in the CVD methods.115 Partial pressure domain monolayer MC films.487−490 On the basis of the facet-
of a specific precursor can also play an important role in dependent binding energy calculations of MoS2 domains on
controlling the layer-by-layer growth of MCs through Au, Shi et al. have shown preferential nucleation and growth of
regulation of the secondary nucleation. For instance, high MoS2 domains on Au (100) and Au (110) rather than on Au
partial pressure of the gaseous MoS2 species (PMo) compared (111).491 Using the atomic sawtooth Au surface with periodic
to the vapor pressure of MoS2 thin films (PoMo) provides the step edges and low Miller index terraces (such as (100), (110)
thermodynamic driving force for precipitation reaction; hence, and (111) facets), Choi et al. have demonstrated the growth of
layer number can be controlled by adjusting PMo.473 At a low monolayer WS2, WSe2, MoS2, MoSe2/WSe2 heterostructure,
Chem. Rev. 2023, 123, 3329−3442
Figure 21. (a) Experimental scheme to prepare patterned WTe2 films on a substrate. (b) Optical image of the as-grown large-scale WTe2 patterns
on a 4-in.-scale SiO2/Si substrate (left) and representative OM images of the thin film taken at the marked points on the left image (right). Scale
bar, 100 μm. (c) Digital image of a Nb film and a selenized NbSe2 film on a sapphire wafer. AFM images of the as-sputtered Nb film and the NbSe2
film are shown. (d) Schematic of the thin film growth of epitaxial 2D Cr2Ge2Te6 starting from an as-deposited Cr film on a Ge (111) substrate. (e)
FESEM images showing the step-by-step growth mechanism of the Cr2Ge2Te6 thin film; starting from Cr dewetting and preferential Te seed
formation on the dewetted Cr. (a−b) Reprinted with permission from ref 493. Copyright 2020, Rights Managed by Nature Publishing Group. (c)
Reprinted with permission from ref 494. Copyright 2019, Rights Managed by Nature Publishing Group. (d, e) Reprinted with permission from ref
176. Copyright 2021 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
and a W1−xMoxS2 film in centimeter scale.491 The periodic step 4.3. Growth Mechanisms
edges act as energetically favorable adsorption sites and This section focuses on introducing the recent advances in the
promote the epitaxial growth of coherent MC grains to yield various CVD growth (metal−organic CVD and salt-assisted
unidirectional single-crystal films. In contrast to the above- CVD) and ultrahigh vacuum (molecular beam epitaxy)
mentioned substrate effect on MC growth, where the growth approaches for binary and ternary anisotropic MCs. Other
methods such as direct chalcogenation of predeposited metals
substrate was kept stationary in all cases, He et al. have recently
or metal oxides and surface diffusion induced MC formation
introduced a moving substrate APCVD method.492 By linearly are also presented.
moving the substrate across the concentration gradient of Mo- 4.3.1. Chalcogenation of Predeposited Metals or
containing species, continuous MoS2 films with controllable Metal Oxide Thin Films. To obtain high-quality MC films
thickness from monolayer to ∼30 layers were obtained. with a desired number of layers and wafer-scale uniformity, a
simple strategy is the two-step vapor deposition which
Moreover, compared with the stationary substrate growth
combines the typical physical vapor deposition (PVD) and
methods, the monolayer film grown on a moving substrate chemical vapor deposition (CVD). By tuning the thickness of
showed preferable 2D epitaxial growth with a much smoother the predeposited (via PVD) metal or metal oxide film on a
surface morphology (Figure 20d). target substrate, the number of atomic layers in the MC film
Chem. Rev. 2023, 123, 3329−3442
can be precisely varied, through controlled chalcogenation microcrystals was comparable to the FETs prepared by
under CVD conditions. For instance, Song et al. recently mechanically exfoliated pristine MoS2 flakes. Industrial
demonstrated the wafer-scale production of patterned 2D 1T′- implementation of 2D MCs as an alternative semiconductor
WTe2 and 1T′-MoTe2 thin films through tellurization of to Si demands low-cost production of wafer-scale single-crystal
magnetron-sputtered W and Mo films (1−20 nm) from a thin films. Giri et al. recently demonstrated a generalized
NixTey eutectic compound as the Te source. The Te source synthetic strategy to produce wafer-scale single-crystal MC thin
was used in a sandwich geometry with the W/Mo source films via surface diffusion and epitaxial self-planarization of
substrate placed directly on top, to avoid any Te deficiency randomly oriented grains.500 The synthesis used single-crystal
during the process (Figure 21a).493 To grow the patterned commercial wafers (Si, Ge, GaAs, etc.) as both a metal source
WTe2 film, the as-deposited W film on the SiO2/Si substrate and an epitaxy collimator. This study showed the growth of
was first micropatterned by photolithography and the metal- Si2Te3, GeTe, GeSe, and GaTe single-crystal thin films (Figure
reactive ion etching process, followed by tellurization from the 21d). Through theoretical calculations and experimental
NixTey eutectic compound (Figure 21b). Large-scale WTe2 analysis, it was proved that chalcogen (Se, Te) diffusion into
patterns on a 4-in. SiO2/Si substrate was successfully the wafer substrates (Si, Ge, GaAs, etc.) is energetically
produced. The synthesized WTe2 and MoTe2 thin films favorable, and the diffused chalcogens tend to migrate
(∼4.26 nm in thickness) exhibited a high stoichiometric nature preferentially along the surface of the single crystal wafer
and electrical performance comparable to that of mechanically substrates and create MxCy crystal domains at the surfaces.
exfoliated single crystals. Lin et al. also recently reported the Multiple crystal domains with variation in thickness were
generalized growth of environmentally stable superconducting formed by continuous supply of chalcogens, and the relatively
NbSe2 and TiSe2 films with superior structural stability and thicker domains flew over the thinner domains to produce an
wafer-scale homogeneity, through the structural transformation atomically smooth film without grain boundaries. This self-
of the sputtered Nb and Ti by controlled selenization in a two- planarization took place for surface energy minimization when
zone CVD tube furnace under H2/Ar (1:10) mixture gas the elemental mobility is sufficient at the thermal annealing
(Figure 21c).494 The as-deposited Nb (∼0.7 nm in thickness) temperature. The epitaxial relationship of the initial MxCy
was transformed into a NbSe2 film (∼1.5 nm in thickness) on a crystal domains with the substrate enabled unidirectional
2-in. sapphire wafer. Similarly, Islam et al. also demonstrated alignment of the synthesized thin film; hence, single-crystal
the formation of vertically stacked few layer 2D MoS2/WS2 thin film formation over the entire substrate was facilitated. In
vdW heterostructures on a Au/SiO2-based substrate, where Au another study, Giri et al. recently demonstrated the epitaxial
was used as both a sacrificial layer and a growth substrate.495 wafer-scale thin film growth of 2D ferromagnetic ternary
The process started with deposition of Mo and W seed layers crystals, such as Cr2Ge2Te6, Cr2Si2Te6, Mn3Si2Te6, etc.176 The
on top of Au/SiO2 substrate, followed by sulfurization in a low- epitaxial growth was achieved by flux-controlled surface
pressure CVD chamber, which led to the chemical conversion diffusion of Te into a Cr or Mn metal film that was
of Mo/W into 2D MoS2/WS2 vdW heterostructures. The predeposited on the conventional wafer substrates (Ge, Si).
synthesized vdW heterostructures was then transferred to a The ternary films experienced epitaxial planarization, which
foreign substrate by exploiting the enhanced debonding of the reduced the surface roughness of the synthesized ternary thin
Au-SiO2 interface within a water bath. Zhou et al. observed films. The wafer substrates acted as both an elemental source
that MoO3 reacted easily with Te and formed 2H-MoTe2 at and an epitaxy provider, thus eliminating the complex vapor
700 °C which is above the Te sublimation temperature (∼600 phase transport of the reacting elements. As a model system,
°C), whereas Mo (sublimation onset >2400 °C) and MoOx (x the Cr2Ge2Te6 thin film formation is shown in Figure 21e for
< 3) precursors formed 1T′-MoTe2 at the same temper- the growth at different growth temperatures. The reaction
ature.496 This difference is attributed to the differences in process started with dewetting of Cr on the Ge (111) substrate
sublimation temperature and atomic migration behavior under at 480 °C, and then preferential Te seed formation on the
the reaction conditions. Similarly, Hussain et al. demonstrated dewetted Cr at 540 °C due to a low formation energy of CrTe
monolayer to few-layer MoS2 films on the SiO2/Si substrate by (−0.36 eV/atom). Ge began to join the reaction to form the
sulfurizing a MoO3 film under an Ar atmosphere.497 Chow et ternary compound at 630 °C simultaneously with the lateral
al. also synthesized a large-area, continuous monolayer of WS2 spreading and merging of the preformed binary crystals.
and MoS2 films by thermal reduction and sulfurization of WO3 Finally, a uniform Cr2Ge2Te6 thin film was formed during the
and MO3 thin films on the SiO2/Si substrates.498 reaction for 3 min. This surface diffusion of chalcogens into
4.3.2. Preferential Surface Diffusion. Although the metallic single crystal substrates (such as Cu, Ni, Pt) and
strategy of controlled chalcogenization of metal or metal subsequent formation of epitaxial monolayer films or multi-
oxide thin films can produce large-area MC films and their layer thin films of CuSe/Cu (111),501,502 NiSe/Ni (111),503
heterostructures, the synthesized thin films are generally NiSe2/Ni (111),504 and PtSe2/Pt (111),502,505 have also been
polycrystalline and their grain size varies from tens of reported recently.
nanometers to submicron. Since the large number of grain 4.3.3. Epitaxial Growth. In epitaxial growth, a crystalline
boundaries restrict the applications in high-performance epilayer (overlayer) is deposited on top of another crystalline
electronic and optoelectronic devices, controlled growth of substrate having the same crystalline orientation with the
giant grains or single-grain thin films remains a challenge for epilayer, so that the epilayer grains can coalesce into a uniform
practical applications. Through a layer-by-layer sulfurization film with a reduced density of grain boundaries, defects, and
approach, Wang et al. demonstrated the layer controlled dislocations.506 Due to the lack of out-of-plane chemical
growth of large grain (∼10 μm) MoS2 atomic layers, by bonding in 2D MCs, a sufficiently strong electrostatic
sulfurization of MoO2 microcrystals.499 Due to the bigger grain interaction between the 2D film and the substrate with a
size of the synthesized atomically thin MoS2, the performance small lattice mismatch minimizes the interfacial energy. The
of field-effect-transistors (FETs) made from these MoS2 crystal symmetry of the substrate has been used to control the
Chem. Rev. 2023, 123, 3329−3442
Figure 22. (a) Scheme of the MoS2 grains grown on c-plane and a-plane sapphire substrate. The structure is dependent on the surface atomic
arrangement of the substrate. (b) Scheme of single-crystal WS2 film growth on an atomic sawtooth Au surface. (c) Cross-sectional annular dark-
field STEM (ADF-STEM) image of the as-grown WS2 on an atomic sawtooth Au (533) surface (top) and the corresponding ball-and-stick model
(bottom). (d) False-color SEM image of a single-crystal WS2 monolayer on vicinal a-plane sapphire after O2 etching. The etched holes have similar
shapes and the same orientation. (a) Reprinted with permission from ref 507. Copyright 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
(b, c) Reprinted with permission from ref 516. Copyright 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. (d) Reprinted with permission
from ref 484. Copyright 2022, Rights Managed by Nature Publishing Group.
in-plane crystallographic alignment, crystal phases, and the rule is not necessary; however, it is difficult to align the lattice
exposed facets of the epilayer. orientation of the epilayer grains for the growth of a
Based on the type of interaction between a substrate and an homogeneous single crystal thin film. The epilayer by the
epilayer 2D film, epitaxy can be categorized as either vdW epitaxy has a sharp interface and is readily peeled off. As a
conventional commensurate epitaxy or vdW (vdW) epitaxy. case study of the conventional epitaxy, Ma et al. demonstrated
Conventional epitaxy is governed by strong bonding between that a threefold symmetry c-plane sapphire favors the growth of
the substrate and the epilayer through electron transfer or triangular MoS2 grains, while a 2-fold symmetry a-plane
sharing. So, a small lattice mismatch (<5%) is a crucial sapphire leads to the epitaxial growth of rectangle MoS2 grains
criterion for successful epitaxial growth. In the case of a (Figure 22a).507 Yu et al. has demonstrated wafer-scale
substrate−epilayer system with a larger mismatch, the epilayer epitaxial growth of a highly oriented and continuous MoS2
is strained up to a certain critical thickness, and the strain is monolayer film enabled by coalescence of adjacent domains
relaxed beyond the critical thickness as a result of misfit with the same orientation on the c-plane sapphire surface.474
dislocations. In the vdW epitaxy, the substrate and the epilayer However, Lin et al. has showed that misoriented and isolated
are bound through vdW forces only. The strict lattice matching WSe2 flakes were predominantly formed on the c-plane (0001)
Chem. Rev. 2023, 123, 3329−3442
Figure 23. (a) Scheme of the growth process of CdSe NWs. (b) Scheme of the continuous vapor−liquid−solid (VLS) growth steps for 1D
nanostructure formation. (c) Low-magnification SEM image of the CdSe NWs. (d) High-magnification SEM image of a single CdSe NW. (e)
Scheme of the VLS growth of MoS2 NRBs on a NaCl crystal surface, indicating the formation of Na−Mo−O droplet formation, dissolution of S
(vapor) in the Na−Mo−O droplet (liquid), and finally horizontal growth of the NRBs. (f) OM image of the MoS2 NRBs grown on a
presynthesized monolayer MoS2 film. (a, c, d) Reprinted with permission from ref 520. Copyright 2011 Elsevier B.V. (b) Reprinted with permission
from ref 519. Copyright 2006 American Chemical Society. (e, f) Reprinted with permission from ref 6. Copyright 2018, Rights Managed by Nature
Publishing Group.
sapphire when using gaseous metal and chalcogen precursors, this study, the formation of 60°-rotated antiparallel domain
whereas a continuous monolayer film was obtained on the formation was largely suppressed by adopting a high growth
annealed sapphire.508 Au (111) has also been extensively used temperature and very low precursor flux. In a defect-controlled
as an epitaxy provider for the growth of oriented monolayer approach, Zhang et al. has demonstrated vdW epitaxial growth
MoS2 and NbSe2 films.465,487,490,509 Through single step direct of WSe2 on an hBN substrate. Rather than the thermodynamic
chalcogenation on single crystal metal substrates, high quality factors, nucleation density and lattice orientation of WSe2 were
epitaxial films were synthesized such as NiSe/Ni (111),503 controlled by the hBN surface defect density. Reduced density
CuSe/Cu (111),501 Si2Te3/Si (111),484 GeTe/Ge (111), of domain boundaries was observed upon coalescence of the
GeSe/Ge (111),500 and PtSe2/Pt (111).505 domains to form a WSe2 monolayer film.480 The vdW epitaxy
Wafer-scale monolayer MoS2 films with perfectly aligned of MoS2 on graphene has also been achieved by involving Mo
grains merged seamlessly into a highly crystalline film by evaporation on graphene and subsequent sulfurization under a
means of the vdW epitaxy on an h-BN/sapphire wafer.510 In H2S atmosphere.511,512
Chem. Rev. 2023, 123, 3329−3442
4.3.4. Step-Edge Epitaxy. Although the epitaxial growth 1D nanostructures are produced by precipitation from
of MCs on a lattice-matched or vdW substrate allows the supersaturated catalytic liquid droplets. During the VLS
evolution of aligned multiple nucleation sites to grow in the process, a seed particle collects atoms and directs the growth
same orientation and then coalesce into a single crystal-like of nuclei. Three well-defined stages can be identified during
film, ensuring the co-orientation of the nuclei still cannot this process: alloying, crystal nucleation, and axial
guarantee the formation of a single crystal large-area film. The growth.517,518 From the viewpoint of growth kinetics, the
high symmetry of such substrates (sixfold) has been found to VLS mechanism emphasizes that surface diffusion of reactant
be incompatible for the low symmetry (threefold) MCs, and species and their preferential incorporation at high-surface-
usually leads to the formation of antiparallel domains (0° and energy sites.519Figure 23a shows a scheme of the on-substrate
60° orientations). Therefore, polycrystalline films with mirror growth of CdSe NWs, using Au nanoparticles as the catalyst.520
twin boundaries (inversion grain boundaries) are inevitably At the initial stage of the reaction, Ar+H2 gas carried the CdSe
obtained.474,513 Theoretical works suggested that the energy vapor into the liquid Au nanoparticles, followed by the
degeneracy of the antiparallel domains can be broken if the dissolution of CdSe in Au particles. Upon supersaturation of
substrate surface has atomically flat vicinal step-edges or CdSe in liquid phase, they precipitate at the liquid−solid
terraces.514 The presence of the step-edges facilitates easier interface to form CdSe NWs. The growth mechanism of CdSe
heterogeneous nucleation to the step-edges than on the and ZnS NWs involving four consecutive steps (1−4) is
pristine terrace plane. The binding preference of the 2D layers schematically depicted in Figure 23b: (1) reactant species
to the step-edge determines the overall orientation. If the steps adsorbing on both the catalyst droplet and side surface of the
on the vicinal plane are all exactly parallel, then all emerging growing NWs, (2) dissolution of reactant species at the droplet
2D domains are also oriented alike, with a prospect of eventual surface, (3) reactant species diffusing inside the droplet, and
merging of the grains into a large single crystal.515 Choi et al. (4) precipitation followed by crystal growth at the liquid−solid
recently demonstrated the single crystal growth of various MC interface.519Figure 23c, d show a low-magnification SEM
monolayers (WS2, WSe2, MoS2, MoSe2/WSe2 heterostruc- image and a magnified SEM image of the CdSe NWs (with
tures) using an atomic sawtooth Au surface with periodic step- length up to several tens of micrometers and a diameter ∼100
edges and low Miller index terraces, including (100), (110), nm). In a similar study, Wang et al. also reported catalytic
and (111) facets, as a universal growth platform (Figure growth of large-scale single-crystal CdS NWs.521 Wang et al.
22b).516 In WS2 growth, density-functional theory (DFT) also reported the synthesis of CdS NBs and CdSe NWs using
calculations presumed that the growth proceeds with the the liquid cluster of the Au catalyst, where CdS NB growth
formation of a W3S6 cluster, sequentially followed by surface proceeds by the VLS mechanism in the axial direction and the
migration, nucleation, and growth. With a relatively larger vapor−solid mechanism in the lateral direction.522 Exploiting
adsorption energy of 1.43 eV at the Au (221) step-edge of the an in situ formation of elemental Pb as catalyst, Bierman et al.
Au (111) terrace facet, S atoms of W3S6 clusters energetically reported the VLS growth of hyperbranched PbS and PbSe
favor a rotational angle of 0° at the step-edge. Figure 22c NWs.523 Morphology control of the layer-structured GaSe
shows the cross-sectional annular dark-field STEM (ADF- NWs (such as straight, zigzag, and sawtooth shapes) was
STEM) image (top) and the corresponding ball-and-stick achieved by controlling the growth temperature and time so
model (bottom) of the as-grown WS2 on an atomic sawtooth that the actual catalysts have a chemical composition of Au,
Au (533) surface. Au−Ga alloy, or Ga.524 Very recently, using a low temperature
Aljarb et al. previously demonstrated the growth of Au- and Ag-catalyzed VLS growth, basal-plane oriented high-
continuous, self-aligned, and single-crystalline MoS2 monolayer quality single crystals of GaSe NRBs with uniform morphology
NRB arrays on a β-gallium(III) oxide (β-Ga2O3) (100) and low edge roughness have been reported by Sutter et al.69
substrate through ledge-directed epitaxy (LDE).486 The The same group has also tailored the orientation and
observation of unidirectional MoS2 seeding flakes on the morphology of 1D GeS vdW nanostructures by adding a
atomically textured β-Ga2O3 (100) substrate, and their small amount of SnS during Au-catalyzed VLS growth.
subsequent coalescence into continuous NRBs with single Modification of the catalyst during VLS growth enables large
crystallinity, clearly indicates the existence of an energetically differences in surface energy between the basal plane and facets
minimized MoS2-β-Ga2O3 ledge configuration. Also, the across layer edges, resulting in preferential wetting of the liquid
growth of individual domains was found to be strongly VLS catalyst drop, hence providing opportunities for tailoring
dependent on the diffusion path so that the domains were the morphology.525 Recently, the alkali metal was also
directed along the ledges of β-Ga2O3 (100). Based on the accountable to play a crucial role for initializing the growth
unidirectional domain alignment, Li et al. has also demon- via the VLS mechanism. For instance, Lim et al. reported
strated wafer-scale MoS2 single crystal growth on a step-edged wafer-scale growth of 1D MoTe and WTe NWs, where Te
2-in. c-plane sapphire.485 In a recent study, Wang et al. also reacted directly with Na2WO4 and created islands of molten
employed the vicinal step-edged a-plane sapphire for epitaxial intermediate droplets. Upon supersaturation of the droplet,
growth of a 2-in. single crystal WS2 monolayer film.484 The WTe NWs began to emerge and grew as the reaction
epitaxial growth is known to be driven by dual coupling of proceeded.80 Li et al. also reported VLS growth of monolayer
sapphire plane-WS2 interaction which leads to two preferred MoS2 NRBs. The growth was triggered by the reaction
antiparallel orientations of the WS2 crystal. The sapphire step between MoO3 and NaCl, resulting in the formation of molten
edge-WS2 interaction broke the energy degeneracy of the two Na−Mo−O droplets, which crawled on the substrate surface in
antiparallel WS2 domains and facilitated unidirectional align- a regular horizontal motion and facilitated the highly
ment. Seamless stitching of nearly all WS2 islands produced a anisotropic growth of the NRBs (Figure 23e, f).6 This VLS
wafer-scale single-crystal WS2 monolayer film (Figure 22d). growth process allowed homoepitaxial growth of 1D NRBs on
4.3.5. Vapor−Liquid−Solid Growth. Vapor−liquid− a presynthesized monolayer MoS2 film, thereby forming
solid (VLS) crystal growth is an attractive approach where unique 1D-on-2D structures (Figure 23f). Kwak et al.
Chem. Rev. 2023, 123, 3329−3442
Figure 24. (a) Scheme of the fundamental steps involved during CVD growth of MCs. (b) OM images of MoS2 monolayer film, GaSe/MoS2
lateral heterostructure, GaSe/MoS2 hybrid structure, and GaSe/MoS2 vertical heterostructure. (c) Scheme of the growth mechanism by pulsed
MOCVD process. (d) Calculated energy diagram of Mo adsorption on the basal plane of MoS2. (e) PL intensity mapping of the MoS2 film grown
by pulsed MOCVD on the wafer scale. Inset shows the PL spectrum of the MoS2 film. (f) Scheme of the epitaxial growth of an atomically thin
Bi2O2Se film on a (001)-oriented SrTiO3 (STO) substrate. Bi and Se precursors were coevaporated in oxygen atmosphere. (g) Cross-sectional
HAADF-STEM image and atomic-resolution HAADF-STEM image of the interface between the Bi2O2Se film and the STO substrate. (a)
Reprinted with permission from ref 552. Copyright 2021 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. (b) Reprinted with permission from
ref 555. Copyright 2021 American Chemical Society. (c-e) Reprinted with permission from ref 560. Copyright 2020 Wiley-VCH Verlag GmbH &
Co. KGaA, Weinheim. (f, g) Reprinted with permission from ref 581. Copyright 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
demonstrated the VLS-mediated formation of single-crystalline provides a brief overview of these vapor phase deposition
MoTe2 and WTe2 1D NBs via the use of Te-rich eutectic metal techniques for 2D MC growth.
alloys. The evaporated Te vapor forms a liquid-like eutectic 4.4.1. Chemical Vapor Deposition (CVD). CVD has
alloy (CuxTey) with predeposited Cu, which acted as a Te been considered as a promising route to producing high-
reservoir, and the thin M (Mo, W)-Cu-Te intermixed layer quality anisotropic MC monolayers and thin films in a scalable
under CuxTey droplets acted as the nucleation seeds for the and controllable way. In the past decade, researchers have
NBs growth.526 Taking advantage of the VLS growth, Li et al. made enormous achievements in the CVD growth of a series of
recently demonstrated that, when liquid Na2MoO4 is saturated 2D MC compounds and their lateral/vertical heterostructures
with S vapor, solid MoS2 can be precipitated in the monolayer with a large domain size and controllable number of layers.
form at the wafer-scale. The grain size of the synthesized Usually, solid chalcogen (S, Se, or Te) powders are used as the
continuous MoS2 film reached as high as 100 μm on the chalcogen source, and powders of metal salts or metal oxides
sapphire substrates.527 (MoCl5, WCl5, MoO3, WO3, etc.) are used as the metal source.
4.4. Deposition Methods MC thin films are grown in a horizontal multitemperature-zone
To date, different strategies have been applied in the synthesis CVD furnace under a constant flow of inert background gas.
technique to obtain high-quality large-scale mono- and few- The upstream heating belt evaporates the chalcogen source,
layer MCs to explore their promising properties in various whereas the downstream temperature gradient acts as a cold
fields of application. The vapor phase deposition methods such trap. The downstream process facilitates solidification of the
as chemical vapor deposition (CVD), metal organic chemical confined reactive species and eventual formation of crystalline
vapor deposition (MOCVD), and molecular beam epitaxy anisotropic MCs on the cooler receiver substrate.451,528 The
(MBE) facilitate strict control over the precursor flux. They gaseous precursors either can adsorb first on the substrate and
have been considered the most promising approach to produce form MCs nuclei through subsequent heterogeneous on/near
ultrathin MCs with high crystal quality, scalable size, tunable substrate or, in another way, can homogeneously react directly
thickness, and excellent electronic properties. This section in the gas phase with the resulting MC clusters adsorbing,
Chem. Rev. 2023, 123, 3329−3442
nucleating, and growing on the substrate (Figure edge length of domain n (Ln, n = 0, 1, 2). It is observed that
24a).115,451,529−532 Various 2D MC monolayers and thin temperature and adatom flux are the main controlling factor
films, such as MoS2,12,115,234,533 WSe2,534 MoTe2,535 V/Nb/ for deciding the mode of self-assembled growth, while the size
TaTe2,536 HfS2,537 VS2,538 VSe2,13 Cr2S3,539 CrSe,540 CuSe,541 of the initial layer dictates the final structure of the multilayer
ReS2,445 GaSe,542,543 InSe,544−546 and SnSe2547 have recently assembly.532 Using temperature as the main controlling factor
been obtained by CVD using the solid phase precursors. in a two-zone CVD furnace operating under atmospheric
Epitaxial growth of vertical, lateral, and multijunction lateral pressure, Cheng et al. has reported controlled growth of
heterostructures of different 2D MCs has been accomplished, ultrathin nonlayered hexagonal and layered tetragonal FeTe
including WSe2/MoSe2,548 WSe2/MoS2,549 MoSe2/WSe2, NSs on mica substrates.554 Zou et al. has demonstrated
MoS2/WS2,185,453,550 and NbS2/MoS2.551 Multiheterostruc- controlled growth of vertical GeSe/MoS2 heterostructures by
tures (such as WS2−WSe2−MoS2 and WS2−MoSe2−WSe2) dynamically tuning the Ge/Se ratio, and modulating the
and superlattices or multiple alternating blocks (such as WS2− nucleation density and growth direction (Figure 24b).555
WSe2−WS2−WSe2−WS2)183 have also been achieved recently Active clusters with different diffusion barriers were created to
using the multistep sequential CVD growth process.552 For induce the lateral growth at a high Ge/Se ratio or the vertical-
sequential growth, the nucleating primary block (e.g., WS2) stacked growth at a low Ge/Se ratio.555
was placed at the downstream end, and the powder source of 4.4.2. Metal−Organic CVD (MOCVD). Despite the
the selected secondary block (WO3 and Se for WSe2) was enormous progress in the metal oxide based CVD process to
heated for evaporation under the carrier gas (e.g., Ar) at the achieve high-quality thin films and large-area single crystal 2D
upstream end. The edges of the primary block acted as a lateral MCs, high-throughput production of uniform continuous MC
epitaxy provider for continued lateral growth, whereas the basal thin films is still difficult due to the limited control over the
plane acted as a vdW epitaxy provider for vertical vapor phase composition, deposition rate, and nucleation
heterostructure formation at the downstream end of the density.115,456,556 Instead of metal oxides, recently several
CVD furnace.183 groups began to use metal organic compounds such as
Modifying the classical nucleation theory, Kim et al. recently W(CO) 6 , Mo(CO) 6 , (t-BuN�) 2 W(NMe 2 ) 2 , and (t-
proposed the thermodynamic and kinetic aspects of the BuN�)2Mo(NMe2)2 as the metal source under MOCVD
reaction pathways and growth mechanisms for lateral and conditions.457,459,557,558 Due to the high vapor pressure of
vertical heterostructure formation of 2D MCs under the vapor metal−organic solid precursors, it is easier to control the
phase deposition condition.115 At the early stage of the precursor concentration within the gaseous mixture simply by
reaction, the meniscus geometry of the initial nuclei on the controlling the evaporation rate and mass flow rate.559 The
substrate was cap-shaped, with radius r and wetting angle θ. easy control of flow rate enables reproducible wafer-scale
The corresponding free energy change (ΔG) of the process growth of MC thin films with excellent spatial homogeneity
was directly correlated with the Gibbs free energy change per and grain size over the entire wafer area.457,560 Kang et al. grew
volume (Δgv) and the surface tension corresponding to the wafer-scale monolayer MoS2 and WS2 films by using gas-phase
film−vapor (γfv), film−substrate (γfs), and substrate−vapor Mo(CO)6 and W(CO)6 as the metal precursors, respec-
(γsv) interfaces. Growth of the 2D film structure was favored tively.457 This process enabled precise control of the metal
only when γfs was sufficiently smaller, γfs ≤ γsv − γfv. The precursor feeding rate during the film growth which suppressed
tendency to maximize the film−substrate interfacial area led to the secondary nucleation on the presynthesized domains.
the lateral growth of 2D MCs along the substrate surface. Kim Wafer-scale production and batch fabrication of atomically thin
et al. has theoretically correlated the ΔG for the formation of integrated circuitry was successfully demonstrated.457,561 By
n-layer vdW MC nucleus with their interlayer binding energy employing a modulated MOCVD process, Park et al. has
(ε11), substrate (0)-first MC layer (1) binding energy (ε01), recently produced WS2−WSe2 superlattices through the
and edge formation energy (λ). ε11 was always positive, and ε01 coherent epitaxy, where the growth process was precisely
and ε11 were similar in magnitude when n > 2; hence, the controlled by accurate modulation of the gaseous metal−
nucleus should be larger than the critical size for spontaneous organic precursors.553 Seol et al. has recently proposed a
growth. Also, since the nucleation barrier is minimum when n pulsed MOCVD, in which periodic interruption of the
= 1, which means that MC nuclei are formed predominantly as precursor supply led to high-throughput, large-scale produc-
a monolayer at the onset of the growth process. If the rate of tion of monolayer MoS2 and WS2 films. Despite the high
the incoming material flux remains constant, additional nuclei precursor concentration, periodic interruption in the precursor
either can form vertically on top of the initial monolayer nuclei supply facilitated vertical Ostwald ripening and prevented
or can form at the lateral position by stitching with the initial secondary nucleation (Figure 24c).560 The adsorption rate
nuclei through the boundary interface. Vertical growth is rapidly decreased when precursor supply was interrupted after
favored when ε12 > ε02, even with maximum interface length optimum injection, hence the unstable MC clusters (MoSx or
(i.e., one side of the primary triangular nucleus, lmax) between WSx) deposited on the presynthesized domains could not grow
the primary and secondary nuclei. However, lateral growth is up to the critical size of stable nucleus. The unstable clusters or
favored when ε12 < ε02, even with an arbitrarily small l.115 adatoms moved to the edges of the presynthesized domains by
Laterally integrated in-plane superlattices can be formed surface diffusion or vertical Ostwald ripening so that the layer-
when the primary and secondary nucleus has isotropic lattice by-layer growth was dominated by suppressing the vertical
structure, so that a fully matched lattice constant across the growth. Figure 24d shows the calculated reaction energy
heterointerfaces is maintained.553 Through multiscale model- diagram of the adsorbed Mo atoms on the basal plane of the
ing and experiments, Ye et al. described a predictive growth presynthesized MoS2 domain during the growth process. The
model for vertically stacked 2D MCs.532 The key parameters of calculation suggests that, in the presence of certain periodic
consideration were temperature, adatom concentration in interruption in precursor supply, Mo adatoms can sponta-
domain n, flux of adatoms to the domain boundary, and the neously diffuse to the edges of presynthesized domains before
Chem. Rev. 2023, 123, 3329−3442
Figure 25. Adhesion-controlled mechanical exfoliation. (a) Scheme of adhesion control by oxygen plasma cleaning, annealing, and cooling process.
(b) Scheme of PVA-assisted exfoliation (left) and selective removal of PVA (right). γ denotes the adhesion energy at the interface between two
respective materials in contact. (a) Reprinted from permission from ref 588. Copyright 2015, American Chemical Society. (b) Reprinted with
permission from ref 599. Copyright 2020, Rights Managed by Nature Publishing Group.
desorption. A 6-in. wafer-scale MoS2 monolayer film with good allows the rotational alignment of the epilayer.568,572 In the
spatial homogeneity was proven by a uniform color-coded non-vdW epitaxy, the strong chemical interaction between the
rendering of the spatially resolved photoluminescence (PL) substrate and epilayer limits the mobility of adatoms and
intensity mapping (Figure 24e). increases the nucleation rates.476,577,578 MBE growth of MCs
4.4.3. Molecular Beam Epitaxy (MBE). MC thin films has been mainly focused on Se and Te compounds due to their
prepared by CVD and MOCVD typically contain a high low vapor pressure, except for a few cases.510,579 Apart from
density of structural defects, impurities, and a large degree of numerous recent reports of 2D MCs, growth of several 1D
spatial and electronic variability across the same sample.562−564 MCs has also been reported recently. Sherman et al. have
Molecular beam epitaxy is a state-of-the-art ultrahigh vacuum grown both 1D and 2D MoSe2 on both vdW and non-vdW
(UHV) technique, which uses a high-purity elemental source substrates.572 Barja et al. also reported the growth of 1D
and ultralow anisotropic growth rate, which enables accurate MoSe2 through vdW epitaxy on bilayer graphene and
thickness control by adjusting the molecular beam flux and measured charge density wave order in the twin boundaries
growth temperature.565−567 By coupling the vapor−solid of single-layer MoSe2.573
growth mechanism and epitaxy, the MBE process can produce Growth of various compounds and intercalated 2D MC
clean-surface thin films that are suitable for investigating films such as VxMo1−xSe2,569 tantalum-intercalated TaSx(Se)y,
fundamental physical properties and electronic struc- self-intercalated V11S16, In11Se16, and FexTey has also been
tures.568−573 MBE-grown MCs on the vdW substrates (e.g., produced recently in a metal-rich MBE growth environ-
graphene, hBN)510 have been of superior quality than those ment.580Figure 24f shows a scheme of the layer-by-layer MBE
grown on the non-vdW substrates (Al2O3, mica, 111-GaAs, Cu, growth process for an atomically thin Bi2O2Se film grown on
Pt, Si, etc.).476,574 For the conventional heteroepitaxial growth the (001) SrTiO3 (STO) substrate.581 Along with the high-
mechanism, the same lattice symmetry and good lattice purity elemental sources, MBE chambers are generally
matching between the substrate and the epilayer are the equipped with a reflective high-energy electron diffraction
prerequisite conditions. In the vdW epitaxy, those require- (RHEED) analyzer and quartz crystal microbalance (QCM)
ments can be greatly relaxed so that heteroepitaxial growth of for in situ monitoring of the growth process. Due to the small
2D MCs is possible even under a different lattice symmetry lattice mismatch (∼0.5%) with the cubic STO substrate, the
and a large lattice mismatch as high as 50% (e.g., NbSe2 on tetragonal Bi2O2Se crystal layer was grown epitaxially without
mica).575,576 It is because the weak vdW interaction between any in-plane misfit strains and dislocations at the Bi2O2Se/
the materials does not induce strain or misfit dislocations and STO interface. Figure 24g demonstrates the high-angle annular
Chem. Rev. 2023, 123, 3329−3442
Figure 26. Metal-assisted exfoliation. (a) Scheme of the Au (111)-assisted exfoliation. (b) Binding energy of a monolayer MoS2 on a pristine Au as
a function of the separation distance between Mo and Au atomic planes. (c) Scheme of the adhesion forces depending on the surface
contamination thickness. The interface of peel-off is determined by the relative adhesion force. (d) WS2/MoS2 heterostructure array obtained by
depositing MoS2 pattern array and then depositing WS2 pattern array on top. From left to right, scale bars are 200 μm, 200 μm, and 100 μm. (a)
Reprinted from permission from ref 108. Copyright 2020, Rights Managed by Nature Publishing Group. (b,c) Reprinted from permission from ref
601. Copyright 2018, American Chemical Society. (d) Reprinted with permission from ref 603. Copyright 2019, The American Society of
Mechanical Engineers.
dark-field (HAADF)-STEM images showing an atomically tional direct peel-off by adhesive layer (e.g., tape, PDMS),
sharp interface with perfect epitaxial matching between adhesion-controlled exfoliation, and metal-assisted exfoliation
Bi2O2Se and STO. It is observed that while the heteroepitaxial for scalable, large-area device fabrication.
growth of the first layer required 2 h for complete reaction, 5.1.1. Direct Peel-off. Since graphene was successfully
homoepitaxial growth of the subsequent Bi2O2Se layers peeled off by using the Scotch tape,582 mechanical exfoliation
required ∼20 min per layer under the same growth conditions. has been widely applied to obtain few layer contamination-free,
pristine MC NSs with high quality.583 The exfoliated NSs
5. EXFOLIATION SYNTHESIS enabled the investigation of the intrinsic properties of 2D
nanocrystals, including superconductivity, magnetism, topo-
Top-down exfoliation has been extensively explored because
logically protected states, and quantum transport.584−593 In the
high-quality natural or synthetic bulk crystals can be used as
the source flakes. The exfoliation method does not undergo typical mechanical exfoliation process, freshly cleaved MC
chemical reactions between metal and chalcogens, allowing crystals on the adhesive layers (3M Scotch white tape, Nitto
collection of highly crystalline MC nanocrystals. This section blue tape, PDMS) are brought into contact with target
discusses various exfoliation techniques including mechanical substrates and mechanically pressed. After adhesive layers are
exfoliation and liquid-phase exfoliation. removed, mono- or few-layer MC NSs and NPs remained on
the target substrates. In this process, γMC‑Substrate should exceed
5.1. Mechanical Exfoliation γMC‑MC, where γ denotes the adhesion energy at the interface.
Because mechanical exfoliation requires only bulk crystals, it This process has suffered from low yield and small lateral
has been a popular method to obtain a clean MC specimen and dimension, which limits scalable production and practical
served as a platform for fundamental physical studies and applications. To overcome the issue, most of the research has
device prototyping. This section briefly reviews the conven- been focused on adjusting γMC‑Substrate. As well as the
Chem. Rev. 2023, 123, 3329−3442
intrinsically layered 2D MCs, quasi 1D vdW NRBs that consist 1−10 s) in acetone delaminated the MoS2 flakes from the Au
of atomic threads weakly bound by vdW interaction can be (111) surface, leaving a monolayer MoS2 on the Au (111)
directly exfoliated by adhesion tape into quasi 1D NBs.594−597 surface. A variety of MC monolayers (MoS2, WSe2, Bi2Te3)
Typically, bulk crystals are first synthesized by the chemical with a lateral dimension of hundreds of microns were obtained
vapor transport method, then exfoliated, and transferred onto by the gold-assisted mechanical exfoliation. The mechanism of
desired substrates. Geremew et al. fabricated ZrTe3 NRBs with the gold-assisted mechanical exfoliation was investigated by
a thickness of ∼50 nm by direct peel-off.595 Kim et al. repeated Velický et al.601 First-principles calculation revealed that the
the mechanical exfoliation process by using the wafer dicing binding energy of a monolayer MoS2 on a pristine Au is −0.41
tape.596 At the first exfoliation, the thickness of NRBs was 31 eV which is higher than that (−0.34 eV) of a monolayer MoS2
nm and it decreased to 2 nm after the second exfoliation. with bulk MoS2 (Figure 26b). The distance between Mo and
Finally, the authors demonstrated atomically thin (0.8 nm) Au planes significantly affects the binding energy. The
V2Se9 NRBs made of bundles of single chains on the SiO2/Si equilibrium distance was calculated to be 4.5 Å, and it
substrate. dramatically decreased with increasing distance. From an
5.1.2. Adhesion-Controlled Exfoliation. Huang et al. HAADF-STEM image, they found the average closest distance
demonstrated that the process involving oxygen plasma between Mo and Au plane was 5.1 Å, which presented a
cleaning and heating−cooling can enhance the adhesion calculated binding energy of −0.34 eV. Exfoliation of the
between the crystals and substrates by removing organic monolayer MoS2 was successful on the freshly deposited Au
contaminants (Figure 25a).588 They suggested that the edges surface with a yield of 70−80% and lateral dimension reaching
of the nanoflakes act as a one-way valve during the heating− 1 cm (limited by the bulk crystal); however, the yield of
cooling process. Gas molecules between 2D crystals and monolayer gradually decreased with increasing exposure time
substrates are released during heating up to 110 °C and of the Au surface to the air. They found that the temporal
increased pressure at the interface (valve-opened). After decrease of the yield was because the thickness of the airborne
cooling down to room temperature, periphery of nanoflakes contaminants adsorbed on the Au surface increased with
tightly contacts with the substrate (valve-closed) and makes exposure time and inhibited the interaction between MoS2 and
uniform contact by the reduced internal pressure. Statistical Au (Figure 26c). By density functional theory calculation,
investigation on the size and yield of the nanoflakes on a SiO2/ Huang et al. investigated the interlayer binding energies
Si substrate with respect to experimental parameters (temper- between the Au(111) surface and 58 layered materials
ature, time, presence of precooling) revealed that the heating− including not only MCs but also graphene, black phosphorus,
cooling process enhanced the size and yield of the exfoliated black arsenic, boron nitride, metal halides, and metal
flakes.598 The maximum surface free energy (53.60 mJ m−2) of nitrides.108 The calculation indicates that the adhesion energies
the substrate, thus highest surface-to-nanocrystal adhesion and between 2D layer and Au (111) are sufficiently strong to
highest yield, was found at 110 °C. Although this technique facilitate exfoliation. They demonstrated a variety of
can produce an improved yield of large flakes, control of the monolayers of those materials that were exfoliated on the Au
number of layers should be further investigated. surface. This method could be applied to various substrates
The adhesion could be controlled by coating a polymer film such as SiO2/Si, sapphire, and plastic film coated with Au film.
on an exfoliating substrate. Huang et al. demonstrated that a 5- Metal-assisted exfoliation was successfully applicable to not
nm-thick poly(vinyl alcohol) (PVA) film coated on a SiO2/Si only layered 2D MCs but also quasi-1D TaSe3‑δ vdW NRBs.
substrate can modulate the adhesion between the MoS2 The electrical properties of TaSe3-related materials have not
crystals and the substrate (Figure 25b).599 MoS2 crystals on been clearly understood due to the low superconducting
the Scotch tape were pressed onto the PVA-coated substrate, transition temperature Tc ∼ 2 K and defects. With the help of
followed by heat treatment at near the glass transition the clean, impurity-free metal-assisted exfoliation method
temperature of PVA (85 °C). Then, the tape was slowly combined with the chemical vapor transport method, a Se
pulled back so that a monolayer MoS2 was left onto the PVA vacancy effect on electrical properties of TaSe3 was recently
layer. To transfer the exfoliated MoS2 to new substrates, a revealed. Kargar et al. prepared TaSe2.75 and TaSe2.85 NRBs,
PDMS stamp coated with polypropylene carbonate (PPC) was and their electrical properties were examined by tip-enhanced
put on the MoS2 flakes on the PVA layer. A water drop was Raman scattering spectroscopy (TERS) and photolumines-
injected to dissolve the PVA layer and free the exfoliated MoS2 cence (PL) analysis.597 It was revealed that TaSe2.75 NRBs
flake from the substrate, and then the monolayer MoS2 flake exhibited a strong broad PL peak centered at 922 nm and
was transferred onto a new substrate. This gel-assisted TERS response under 785 nm laser excitation, indicating the
mechanical exfoliation consistently yielded monolayer MoS2 semiconducting behavior. In contrast, TaSe2.85 NRBs showed
flakes with large areas (<1000 μm2). However, the use of PVA neither a PL nor TERS response, which was consistent with
and water increases the chance to make blisters at the the metallic characteristic.
interfaces. With the advent of metal-assisted mechanical exfoliation,
5.1.3. Metal-Assisted Exfoliation. To improve mono- micropatterning was available by conventional photolithog-
layer selectivity and the dimension of flakes, metal films (Au, raphy (Figure 23d).602,603 Au film was thermally evaporated on
Ni) were applied to enhance the adhesion. Magda et al. a 2D material, and a photoresist was patterned on the Au film.
experimentally presented the use of a gold thin film as an A patterned Au film was obtained through wet etching by a
adhesion layer instead of the adhesive tape, or polymeric gel.600 KI/I2 solution, and the MC film was etched by CF4 plasma.
A 100-nm-thick Au (111) film was deposited on a mica The pattern was transferred onto a target substrate (SiO2/Si
substrate. When thick multilayer MoS2 flakes on a thermal wafer) by using the thermal release tape and preheating. Prior
release tape were placed onto the Au (111) thin film and to contact, the wafer was O2 plasma treated and heated to
thermally annealed at 90 °C, thin MoS2 flakes were released on enhance adhesion with the MC film. The photoresist, organic
the Au film (Figure 26a). Short ultrasonic treatment (70 W, residue, and the Au pattern were removed successively by
Chem. Rev. 2023, 123, 3329−3442
Figure 27. Wafer-scale mechanical exfoliation by controlled crack propagation. (a) Scheme of the layer-resolved splitting of 2D materials. (b)
Schematic representation of crack propagation for initial exfoliation of 2D materials from a sapphire. (c) Exfoliation of the bottom monolayer of the
2D material. Reprinted from permission from ref 604. Copyright 2018, American Association for the Advancement of Science.
acetone, O2 plasma, and KI/I2 etching, which provided scalable synthesis by liquid-phase exfoliation. Selection of
patterned monolayer MC films on the substrate. This intercalating molecules determines the interlayer space of the
technique could be used to fabricate patterned MC MCs nanocrystals. This section reviews exfoliation in liquid
heterojunction arrays.603 Nguyen et al. fabricated patterned phase, including solvent-assisted exfoliation,605−607 surfactant-
WS2/MoS2 heterostructure arrays by transferring a patterned assisted exfoliation,608−610 chemical intercalation-induced
WS2 array onto the pretransferred MoS2 patterned array. This exfoliation,611−613 and electrochemical intercalation-induced
pattern transfer was necessary to increase the yield of exfoliation.614−616
monolayer transfer since the current yield is about 50%. 5.2.1. Solvent-Assisted Exfoliation. Solvent-assisted
The layer-resolved splitting (LRS) technique was developed liquid-phase exfoliation (LPE) is simple and efficient way to
by controlled crack propagation using a Ni film as an atomic- produce mono-, or few-layer 2D MC crystals in colloidal
scale adhesive (Figure 27a).604 A 600-nm-thick Ni film was solutions. The general LPE process includes immersion and
deposited on a thick 2D material grown on the sapphire insertion of solvent molecules, then exfoliation and stabiliza-
substrate and peeled off with the 2D material. Another Ni film tion.111,617,618 Solvent molecules are adsorbed on the surface of
was deposited on the bottom side of the 2D material, and a bulk MC crystals and diffuse in the interlayer space of bulk MC
thermal release tape was adhered to the bottom Ni film. crystals, leading to the intercalated state. When the ultrasonic
Peeling off the top Ni layer separated the 2D material and left a wave propagates in the solution, jet cavitation is generated by
monolayer on the bottom Ni film. Repeating the cycle of Ni pressure fluctuation. Implosion of the jet cavitation on the
deposition and peeling-off produced a large number of surface of the intercalated flakes results in fragmentation and
monolayers on the bottom Ni film. The monolayer could be exfoliation. The exfoliated NSs are stabilized by the steric
transferred on a SiO2 substrate by annealing at above the effects.619−621 The choice of an appropriate solvent is critical
release temperature (110 °C) followed by FeCl3 etching. The to obtain high concentration and good stability against
LRS technique is based on differences in the interfacial aggregation. Initially, N-functionalized solvents such as N-
toughness (Γ), where Γ2D‑Ni (1.4 J m−2) is three times larger methylpyrrolidone and N-cyclohexylpyrrolidone have been
than Γ2D‑2D (0.45 J m−2), and five times larger than Γ2D‑Sapphire exploited for the solvent because they lead to highly
(0.26 J m−2). Upon lift-off of the Ni/2D material stack on the concentrated dispersions that are stable for months.622
sapphire, or on the bottom Ni film, a bending moment is However, both solvents are hazardous and have high boiling
applied to bring elastic strain energy to the interface with the points (202 °C for N-methylpyrrolidone and 284 °C for N-
weakest toughness. As a result, strain energy is selectively cyclohexylpyrrolidone), which limits their industrial uses.
released on the 2D/sapphire interface (Figure 27b) and the Along the trial-and-error-based solvent screening process,
2D/2D interface (Figure 27c). The LRS method successfully many solvents with low boiling points have been
transferred uniform wafer-scale MC monolayers (WS2, MoSe2, reported.622−628
WSe2, MoS2) onto a SiO2/Si wafer without macroscopic In the solubility theory, the free energy of mixing can be
defects, such as wrinkle, folding, or ripple. expressed as ΔGmix = ΔHmix − TΔSmix, where ΔHmix and ΔSmix
represent enthalpy of mixing and entropy of mixing, and T is
5.2. Liquid-Phase Exfoliation absolute temperature. Unlike the solutes of small molecules,
Liquid-phase exfoliation is a powerful route to produce single- rigid solutes have relatively small ΔSmix; hence, ΔHmix dictates
layer to few-layere MCs in large scale. A variety of the exfoliation process and governs the stability.628 Parameters
electrochemical and catalytic applications have driven the that can predict ΔHmix upon exfoliation are Hildebrand and
Chem. Rev. 2023, 123, 3329−3442
Figure 28. Solvent- and surfactant-assisted exfoliation. (a) Plot of the concentration of the exfoliated GeS NPs as a function of the dispersive δs,D,
polar δs,P, and hydrogen-bonding δs,H components of the Hansen solubility parameter. (b) Dispersibility of graphene, Bi2Te3, TaS2, Bi2Se3, Sb2Te3,
MoSe2, WSe2, MoS2, WS2, In2Se3, Sb2S3, SnS2, In2S3, SnS2, In2S3, and h-BN in IPA/water cosolvent with varied volume fractions. (c) Scheme
illustrating the interlayer distance change in TiS2 and corresponding side view in TEM images by intercalating alkylamine. (d) SEM image of TaSe3
threads after liquid-phase exfoliation in acetone. (e) HRTEM image of an ultrathin NbSe3 NW. (a) Reprinted from permission from ref 633.
Copyright 2020, American Chemical Society. (b) Reprinted from permission from ref 617. Copyright 2017, American Chemical Society. (c)
Reprinted with permission from ref 649. Copyright 2015, Rights Managed by Nature Publishing Group. (d) Reprinted with permission from ref
638. Copyright 2021, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. (e) Reprinted with permission from ref 637. Copyright 2021, Rights
Managed by Nature Publishing Group.
Hansen solubility parameters.629−631 From the theory of 2D MC material match those of the solvent. Schiettecatte et al.
Hansen solubility parameters (δ), the volumetric ΔHmix plotted the concentration versus Hildebrand solubility
(ΔHmix/V) is expressed as follows: parameter of solvents (Figure 28a),633 and they revealed that
2 2
the Hildebrand solubility parameter of ReS2 NPs is ∼25
Hmix /V [( D,MC D,Sol) +( P,MC P,Sol) MPa1/2 from the maximum concentration (0.84 mg mL−1) of
+( 2 the exfoliated ReS2 NPs in NMP.
H,MC H,Sol) ] (1 )
Besides the solubility parameters, Shen et al. suggested that
where δD,MC (δD,Sol), δP,MC (δP,Sol), and δH,MC (δH,Sol) represent solvent can be screened on the basis of surface tension.111,618
dispersive, polar, and hydrogen-bonding Hansen solubility From the OWRK theory developed by Owen, Wendt, Rabel,
parameters of the 2D MC NSs (solvent), respectively.632 On and Kaelble, the interfacial tension can be separated into the
the basis of the theory, a maximum concentration can be polar and dispersive part.634 Assuming the surface tension
achieved when all three Hansen solubility parameters of the components can be independently treated and the polar-
Chem. Rev. 2023, 123, 3329−3442
dispersive interactions can be neglected, Fowkes developed the flakes.642 It was found that all processing parameters (MoS2
interfacial thermodynamics theory as shown in the below concentration, mixing time, liquid volume, rotor speed)
equation. affected the exfoliation yield. Under optimal conditions, the
exfoliation yield and exfoliating rate achieved levels as high as
= + 2( d d p p 0.5 mg mL−1 and ∼1 mg min−1, respectively. The surfactant
sl s l s · l + s· l )
concentration was a key parameter determining the maximum
d p d p d d p p
= s + s + l + l 2( s· l + s· l ) values in exfoliation yield, lateral dimension, thickness, and
zeta potential when the surfactant concentration increased.
where σs and σl represent the surface tension of the solid and The authors correlated the exfoliation yield to the critical
liquid, respectively, and p and d indicate polar and dispersive micelle concentration (CMC) of the sodium cholate surfactant
components, respectively. Maximum exfoliation efficiency can (∼6 mg mL−1). At above the CMC, the surfactant was
be achieved with minimized σsl, which infers that (1) σpl /σdl and consumed to form the micelles rather than be adsorbed on the
σps /σds , (2) σds and σdl , and (3) σps and σpl should be as close as nanoflakes, resulting in the saturation of both the exfoliation
possible.111 They obtained the σps /σds value for graphene, h-BN, yield and zeta potential. The effects of surfactant concentration
MoS2, MoSe2, WS2, Bi2Se3, SnS2, and TaS2 by contact angle on lateral size and thickness of the nanoflakes were tentatively
measurement and Young’s equation. They successfully attributed to the difference in surfactant packing density at
exfoliated various kinds of 2D MCs in low-boiling point edges from that on the basal plane. The existence of optimum
solvent mixtures (water, acetone, isopropyl alcohol (IPA), values depending on surfactant concentration was similarly
tetrahydrofuran (THF)), which enabled a low temperature observed in other surfactants of P-123,643 bovine serum
exfoliation process.111,618 The yield of exfoliated MoS2 and albumin (BSA),644 PVP,645 and other polymers.646−648
WS2 nanoflakes using a mixture of water and IPA was over 84% Exfoliation under ultrasonication or in harsh conditions
compared to NMP which is known as the best solvent for produced nanoflakes of submicron scale. Jeong et al. suggested
MoS2 and WS2. Wang et al. further extended the solvent tandem molecular intercalation which prevented occasional
screening process based on the surface tension to additional degradation of 2D MCs.649 A variety of 2D MCs (TiS2, ZrS2,
2D MCs including Bi2Te3, Sb2Te3, WSe2, In2Se3, Sb2S3, and NbS2, WSe2, and MoS2) acted as Lewis acids; hence, they were
In2 S 3 , and successfully exfoliated them in IPA/water exfoliated by using an organic Lewis base such as alkylamines
cosolvent.617 The dispersibility of 2D MCs with respect to and alkoxides under mild stirring conditions. When TiS2 was
volume fraction of IPA was plotted in Figure 28b. σps /σds was exfoliated by propylamine, butylamine, and hexylamine, the
scaled from 0.179 to 2.292 as the volume fraction of IPA interlayer distance was expanded from 5.7 Å to 9.5, 10.5, and
increased. The best exfoliation was found when σps /σds was 14.3 Å with increasing alkyl chain length of the primary amines
similar to σp2D/σd2D of the 2D MCs. (propyl, butyl, and hexyl), respectively (Figure 28c). The mild
Various quasi 1D structured MCs including TiS3,635 exfoliation produced micron-sized monolayer MoS2 NSs.
Nb2Se9,636 NbSe3,637 and TaSe3638,639 with NBs and atomic 5.2.3. Chemical Intercalation-Induced Exfoliation. To
threads have been obtained via solvent-assisted exfoliation overcome the dispersive force between the layers of 2D MCs,
using ethanol, isopropyl alcohol, acetone, and dimethylforma- species that can react to generate gases inside the vdW gaps are
mide as solvents. Barani et al. recently exfoliated TaSe3 atomic preferred to intercalate. Among alkali metals, Li has been
threads ranging from 50 to 100 nm while their length was in widely employed as an intercalant to improve the exfoliation
the range of several hundred micrometers (Figure 28d).638 yield due to the low diffusion barrier from the small atomic
The obtained TaSe3 atomic threads were mixed with UV-cured (1.34 Å) and ionic radii (0.90 Å).650 For lithium intercalation,
polymer, sodium alginate, and epoxy to fabricate electrically n-butyllithium (n-BuLi) and tert-butyllithium (t-BuLi) were
insulating flexible films as electromagnetic shields (Figure 28d, found to be more effective than the relatively smaller
inset). Yang et al. exfoliated NbSe3 NWs with diameters down organolithium such as methyllithium (MeLi).651,652 The
to 6.8 nm in reagent alcohol and measured the thermal chemical reaction between BuLi and 2D MCs originates
conductivity of single NWs.637 In Figure 28e, the obtained from the electron transfer from Bu− to 2D MCs, and then Li+
NbSe3 NWs demonstrate well-aligned molecular chains of a ions intercalate to balance the charge, which expands the
single crystalline nature. They found that thermal conductivity interlayer distance of 2D MCs in the c-axis and makes the
at room temperature followed the 1/3 power law with length, LixMCs compound according to the below equation.653,654
which provided experimental evidence of superdiffusive x
phonon transport. x n BuLi + MCs LixMCs + C8H18
2
5.2.2. Surfactant-Assisted Exfoliation. Water is a
desirable solvent to achieve environmentally benign manu- Exfoliation of LixMCs into dispersed nanoflakes is achieved
facturing processes; however, the exfoliation yield of MCs in through hydrolysis that is accompanied by generation of
pure water is inferior to organic solvents or cosol- hydrogen gas and LiOH, as expressed below.655
vents.618,622,640 Because the low exfoliation yield results from x
the mismatch of the solubility parameters between 2D MCs LixMCs + x H 2O MCs + H 2 + x LiOH
2
and water, the surfactant has been applied to modify the
surface energy of the 2D MCs.641 May et al. showed that the Fan et al. reported sonication-assisted lithium intercalation and
Hildebrand solubility parameters of a surfactant and solvent exfoliation which shortened the lengthy intercalation time (24
should be similar to obtain stable concentrated adsorption of h or days).656 With the aid of lithium intercalation, the yield of
the dispersant on the 2D MCs.640 Hu et al. investigated the MoS2 single sheets was over 95% with a dominant lateral size
relation between the concentration of the surfactant (sodium of about 300 nm. The X-ray photoelectron spectroscopy
cholate) versus the exfoliation yield, lateral dimension, (XPS) showed that both Mo 3d5/2 and Mo 3d3/2 peaks could
thickness, and zeta potential of the exfoliated MoS2 nano- be deconvoluted into two peaks indicating the phase transition
Chem. Rev. 2023, 123, 3329−3442
Figure 29. Chemical and electrochemical intercalation-induced liquid phase exfoliation. (a) Scheme for two-step expansion and Na+ intercalation.
Expansion of bulk MoS2 (left) and intercalation with A+ C10H8− (right). (b) Scheme of electrochemical exfoliation cell and for the mechanism of
electrochemical exfoliation. (a) Reprinted with permission from ref 612. Copyright 2014, Rights Managed by Nature Publishing Group. (b)
Reprinted from permission from ref 657. Copyright 2019, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
from the 2H to 1T phase. They found the exfoliated 1T-MoS2 between the layers (Figure 29b). Zhang et al. obtained a few
could be transformed again to the 2H phase by IR irradiation. layers (6−10 layers) of 2H-MoS2 NSs with a high exfoliation
Large ionic size alkali metals such as Na (1.16 Å) and K yield (70%) by cathodic exfoliation in organic electrolyte.657
(1.52 Å) have been less commonly used for intercalation due Tetra-n-butylammonium bisulfate (TBA·HSO4) and propylene
to the large ionic diffusion barrier although these ions can carbonate were used as the intercalant and solvent,
expand the interlayer distance to a larger extent. Na and K respectively. After electrochemical exfoliation, large volume
intercalation compounds can react more violently with water expansion was observed and the lateral dimension of the
than Li, implying that single-layer 2D MCs should be exfoliated MoS2 NSs was in the range 10−50 μm. The
exfoliated more efficiently. It was reported that the diffusion mechanism was suggested as the combined effect of cathodic
barrier of Na is comparable with Li once the interlayer distance reduction and gas evolution. At the initial state, when +5 V of
of 2H-MoS2 reached ∼17 Å.650 Zheng et al. realized Na and K bias were applied on MoS2 for 5 min, SO42− intercalated.
intercalation and exfoliation, and produced single layer MoS2 When the bias was reversed to −5 V, SO42− and H+ were
flakes with large sizes up to 400 μm2.612 They used a three-step reduced to gaseous SO2 and H2. In addition, the authors
process involving (i) lattice expansion by reacting with suggested that cathodic reduction of TBA+ was accompanied
hydrazine (N2H4) in hydrothermal condition, (ii) intercalation as in the following equation.658
by alkali naphthalenide solution, and finally (iii) exfoliation (n Butyl)4 N+ + e (n Butyl)4 N·
under mild ultrasonication (Figure 29a). In the first step
including the redox-rearrangement, part of N2H4 was oxidized (n Butyl)4 N· n Butyl ·+ (n Butyl)3 N
to N2H5+ during intercalation and decomposed to N2, NH3,
and H2 at high temperature conditions because of the thermal n Butyl ·+e n Butyl
instability of N2H5+. This step resulted in a more than 100
times expansion of MoS2 crystals. With the aid of more reactive
species (Na) and a mild sonication environment, an 80% yield 6. MODULATION OF ANISOTROPIC MC CRYSTALS
of the single-layer MoS2 sheets with the lateral dimension of 10 Recently, extensive studies have been reported on obtaining
μm was successfully obtained, while preserving the initial desired properties for various potential applications including
lateral size of the bulk flake. optoelectronics, magnetics, energy harvesting, storage devices,
5.2.4. Electrochemical Intercalation-Induced Exfolia- sensors, etc.659−665 The structures and compositions of
tion. To increase the lateral dimension and exfoliation yield, anisotropic MCs have been modulated for target applications
large-sized intercalating molecules are preferred. Applying and for finding new physical properties.666−670 The modu-
external electric potential not only enables the intercalation of lations include controls of dimensions, phases, compositions,
larger molecules in a short time (∼1 h) but also induces an heterostructures, and defects. This chapter discusses various
electrochemical reaction to overcome the vdW interactions mechanisms toward modulation of the anisotropic MC crystals
Chem. Rev. 2023, 123, 3329−3442
Figure 30. Size sorting of exfoliated NSs. (a) Scheme of the centrifugation cascade method. (b,c) Digital camera image of the MoS2 bands after the
first (b) and the second (c) iteration of density gradient ultracentrifugation. (a) Reprinted with permission from ref 674. Copyright 2016, American
Chemical Society. (b) Reprinted from permission from ref 673. Copyright 2014, Rights Managed by Nature Publishing Group.
and introduces recent representative experimental realizations heterogeneous mixture. In general, heavier nanoflakes precip-
by the mechanisms. itate during centrifugation while lighter (smaller, or thinner)
6.1. Dimension Control nanoflakes remain in the supernatant. Size sorting can be
achieved through the liquid cascade centrifugation which
Dimensions of MCs (diameter, length, thickness, lateral size) repeats the cycles of centrifuging-and-discarding. Backes et al.
of anisotropic MC crystals are of pivotal importance to found that mean length (⟨L⟩) and mean thickness (⟨N⟩) of the
modulate the electronic properties such as the quantum exfoliated WS2 nanoflakes follow the scaling laws of ⟨L⟩ ∼ (g-
confinement effect, indirect-to-direct bandgap transition, grain force)−0.5 and ⟨N⟩ ∼(g-force)−0.4 (Figure 30a).674 The density-
boundary-related properties, and exposed surface area. Uni- gradient centrifugation is another technique to separate
form dimension is critical to fabricate reliable device nanoflakes with specific dimension based on different buoyant
performance. Size sorting of top-down exfoliated NSs, densities. It achieves a high degree of monodispersity in
bottom-up synthesis of dimension-controlled MCs including thickness because the buoyant density is strongly dependent
both solution- and vapor-phase synthesis will be described in on the thickness but negligibly dependent on the lateral
this section. dimension of the 2D MCs.671 During centrifugation, each 2D
6.1.1. Size Sorting. The physical and chemical properties MCs NSs sediment at the point where their buoyant density
of nanocrystals are highly dependent on the dimensions of the matches with the medium density. Kang et al. demonstrated
nanocrystals (lateral dimension, thickness, diameter, length); the thickness sorting of the MoS2 nanoflakes by using iodixanol
therefore, size sorting is an essential process for their practical as a density gradient medium (Figure 30b).673 After the first
applications. The liquid phase-exfoliated nanoflakes (or NSs) density gradient centrifugation, multiple bands were created.
are polydispersed in the lateral dimension and thickness. Two The well-defined bands (f7, f17, and f27) and the relatively
strategies used for sorting exfoliated 2D MCs nanoflakes (or wider bands (f9, f13, and f23) were used for the second
NSs) are differential centrifugation and density-gradient iteration. After the second iteration of density-gradient
centrifugation.671−675 The differential centrifugation can isolate centrifugation, well-defined bands (f7, f17, and f27) which
specific particles with varying size, shape, and density from a corresponded to 1.0, 1.84, and 2.52 nm of MoS2 nanoflakes
Chem. Rev. 2023, 123, 3329−3442
Figure 31. Surface energy control in synthesis. (a) Scheme of the growth of Te NRs, encapsulation with Se, and regrowth of Te. (b) TEM image of
Bi2Te3 transformed from the Te NRs. (c) TEM image of diameter-controlled CdTe NWs. (d) Scheme of thickness-controlled 2D MC growth by
controlling the flux of precursor source. (e,f) TEM image of multilayer NPs of ZrS2 and single-layer ZrS2 NSs. (g) TEM images of lateral
dimension-controlled and thickness-controlled WSe2 NSs by using different capping agents. (a,b) Reprinted with permission from ref 682.
Copyright 2015, The Royal Society of Chemistry. (c) Reprinted from permission from ref 48. Copyright 2008, American Chemical Society. (d−f)
Reprinted from permission from ref 112. Copyright 2014, American Chemical Society. (g) Reprinted from permission from ref 383. Copyright
were successfully separated. It is notable that the topmost band growth of NRs was stopped upon Se introduction. The growth
was enriched in single-layer MoS2, capturing 30.8% of the was restarted when excessive Te source was added. The length
single-layer MoS2 nanoflakes (Figure 30c). could be controlled in the range 400−800 nm, and the
6.1.2. Surface Energy Adjustment. For the synthesis of thickness was adjusted within 20−80 nm. Chemical trans-
controlled dimensions of 1D crystals, chemical transformation formation of the Te NRs to Bi2Te3 or PbTe NRs was
from chalcogen (Se, Te) to MCs has been extensively studied completed with slightly roughened surfaces which was caused
owing to the thermodynamically preferred 1D growth of by volume expansion during the compound formation. In the
chalcogens.676−679 Se and Te inherently grow into 1D crystals solid-solution-solid growth process, it has been demonstrated
because of the covalent bond in the helical chain along the c- that the diameter of MC NWs was tuned via size control over
axis and the vdW interaction among the helical chains.680,681 catalytic nanoparticles.47,48,683 Catalytic Bi nanoparticles with
Kwak et al. demonstrated the length and thickness control over diameters of 5−17 nm were synthesized, followed by the
Te NRs with passivation of the growth tip by Se (Figure growth of CdTe NWs using Cd(ODPA) and the TOPTe
31a).682 Due to energy stabilization of c-axis facet by Se, complex in trioctylphosphine oxide (TOPO) at 300−330 °C
Chem. Rev. 2023, 123, 3329−3442
(Figure 31b).48 The diameter of CdTe ranged from 7.3 to 10.2 Surfactants binding to a specific facet can modify the surface
nm and was tuned in nanometer scale (∼0.5 nm). They found energy, hence controlling the thickness and lateral dimension
that the initial diameters of Bi nanoparticles (dBi) and the of the synthesized anisotropic crystals. In the synthesis of WSe2
diameters of CdTe NWs (dCdTe) had a good linear relationship NSs through the reaction with tungsten hexacarbonyl (W-
(dCdTe = (0.54 ± 0.06)dBi + (1.92 ± 0.68)). Laocharoensuk et (CO)6) and diphenyl diselenide (Ph2Se2), the thickness was
al. succeeded in controlling the length and diameter of CdSe controlled layer-by-layer by using different functional groups in
and ZnSe NWs directly grown on a solid substrate in a the surfactant (oleylamine, oleyl alcohol, and oleic acid)
microfluidic system (Figure 31c).683 Bi thin films (2, 5, or 10 (Figure 31g).383 WSe2 nanohseets with 4−8 layers and a lateral
nm) evaporated on a HF-cleaned Si wafer was melted and dimension of ∼5 nm were obtained with oleylamine, whereas
formed droplets of varying sizes while it was heated to the the number of layers decreased to 2 or 3 and the lateral size
reaction temperature (∼330 °C), followed by the growth of increased to ∼21 nm when oleyl alcohol was used. Monolayer
semiconducting NWs. Thicker films produced thicker NWs WSe2 NSs with a lateral size of 200−400 nm were synthesized
because they resulted in larger droplets than the thinner films; with the use of oleic acid. The binding energy on (101̅0) edge
CdSe NWs of 16.0, 21.4, and 37.6 nm in diameter were was calculated to be −1.475, −1.161, and −0.848 eV for
obtained from films of 2, 5, and 10 nm, respectively. Xing et al. methylamine, methyl alcohol, and formic acid, respectively.383
demonstrated magic-sized ZnS NWs with controlled diameter The tendency of the binding energies on the (112̅0) edge was
and length, and surprisingly the diameter could be lowered to consistent with the one observed for the (101̅0) edge: −1.421,
1.0 nm which was close to the size of one hexagonal unit cell of −0.978, and −0.780 eV for methylamine, methyl alcohol, and
wurtzite ZnS.684 Magic-sized ZnS NWs were synthesized by formic acid, respectively. These results indicate that oleylamine
reacting various amounts of Zn(ethylxanthate)2 dissolved in selectively stabilizes the edge facets and inhibits the lateral
octylamine and hot hexadecylamine (150 °C) at 120 °C for growth so that vertical growth of NSs takes place
several hours. Diameters of ZnS NWs were tuned by changing competitively. On the other hand, oleic acid with less edge-
the ratio of Zn(ethylxanthate)2 to octylamine. The diameter stabilizing effect promotes the lateral anisotropic growth which
increased from 1.0 to 2.4 nm as the ratio increased. The length leads to the synthesis of monolayer NSs. When molybdenum
of the NWs could be varied with reaction time while hexacarbonyl (Mo(CO)6) was used instead of W(CO)6,
maintaining the diameter. For 1.5-nm-thick NWs, the length monolayer MoSe2 NSs with a lateral dimension of 200−500
increased from 60, 90, to 168 nm as the reaction time nm were formed with oleic acid.383 The aspect ratio of the
increased from 45, 90, to 180 min. To further increase the anisotropic MCs nanocrystals can be adjusted by varying the
molar ratio between the precursor and capping ligand. In the
aspect ratio, an additional precursor was injected to the
synthesis of WSe2 NSs with TOPO which acts as a solvent and
suspension of the 1.0-nm-thick NWs. After three additional
a capping ligand, the diameters of WSe2 NSs increased from
injections of Zn(ethylxanthate)2, ZnS NWs grew up to 330
2.5 to 9.7 nm, and the thickness became thinner as the molar
nm. PbS NWs with a diameter of 1.8 nm were also achieved by
ratio of TOPO to W(CO)6 was reduced from 100 to 5.388
a similar experimental procedure by using lead hexadecylxan-
As well as transition metal chalcogenides, syntheses of
thate and trioctylamine instead of using zinc ethylxanthalate, colloidal post transition metal chalcogenides have been
octylamine, and hexadecylamine.685 In addition, the chalcogen- reported. When SnSe NSs were synthesized by reacting
to-metal precursor ratio had influence on the dimension of SnCl 2 and the TOP-Se complex in oleylamine with
anisotropic 1D MCs. During the reaction between SbCl3 and hexamethyldisilazane (HMDS), the opposite trend was
elemental S in oleylamine, increasing the ratio of the found.11 With fixed amounts of oleylamine and HMDS, lesser
chalcogen-to-metal facilitated the growth in the length amounts of SnCl2 and TOP-Se (larger molar ratio of the
direction, resulting in thinner Sb2S3 NRBs.686 When the S- capping ligands to the precursors) produced thinner SnSe NSs
to-Sb ratio was 2.25, NRBs with an average width of 2.3 nm, a with a similar lateral dimension. The thickness of SnSe NSs
thickness of 1.8 nm, and a length of 10 μm were obtained. As decreased from 35 to 8 nm when the SnCl2 amount was
the ratio decreased to 2.0 and 1.75, the width increased to 17.5 reduced from 40 mg to 10 mg. Monolayer single-crystalline
and 32.6 nm and the length decreased to 500−1 μm and 100− SnSe NSs with a lateral dimension of 300 nm were produced
300 nm, respectively. by reacting SnCl4·5H2O and SeO2 dissolved in oleylamine in
In situ control over dimensions of anisotropic nanocrystals the presence of phenanthroline that acted as a morphology
can be accomplished by controlling the reactivity of precursors control agent.319 The thickness was 1 nm, which was close to
and surfactants.316,687 It has been reported that continuous the value of monolayer SnSe. The neighboring distance
influx of diluted chalcogen can prepare single-layer ZrS2, HfS2, between each layer in the bumps in HR-TEM was around
and TiS2 NSs (Figure 31d).112 When CS2 was used as a sulfur 2.8 nm, which was consistent with single layer SnSe with long
precursor, multilayered ZrS2 nanodiscs with a lateral dimension chain oleylamine as a ligand. It is notable that, in the absence
of ∼20 nm was obtained (Figure 31e). By contrast, when 1- of phenanthroline, uniform nanoflowers with a monodisperse
dodecanethiol was reacted with metal chloride in oleylamine at diameter of 1.2 μm were obtained, indicating phenanthroline
245 °C (230 °C for TiS2), single-layer NSs with a lateral acted as a morphology control agent. Almeida et al.
dimension of 200−1000 nm were synthesized (Figure 31f). synthesized monolayer β-In2Se3 NSs with a tunable lateral
The authors found that 1-dodecanethiol provided a dilute and size from 300 to 900 nm, using short aminonitriles which acted
continuous H2S influx, while CS2 caused a burst influx. The as a morphology control agent.688 Without aminonitriles, only
dilute and continuous influx of H2S satisfied the kinetic growth 5 nm In2Se3 nanoparticles were formed instead of monolayer
window for preferential 2D lateral growth; however, the burst NSs. The lateral dimension could be tuned by changing the
influx generated excessively concentrated monomers and ratio of oleylamine to 1-octadecene. For instance, as the
caused simultaneous growth in both the lateral and vertical volume fraction of oleylamine increased from 20% to 60%, the
directions. lateral dimension of In2Se3 NSs decreased from 900 to 300 nm.
Chem. Rev. 2023, 123, 3329−3442
Figure 32. Salt-assisted CVD. (a,b). Scheme of the reaction between metal precursor and added salt, which decreases the melting point of the
precursor by the formation of low-melting metal oxychlorides and increases the reaction rate to produce a large-grain single crystalline monolayer in
growth time of less than 3 min (1−3 and 5−7). SEM images of the Nb nucleus with (4, left) and without (4, right) addition of the salt. (b)
Schematic comparison of the growth mechanism in “standard ” MOCVD (top) and growth-etch MOCVD (bottom). (a) Reprinted with
permission from ref 445. Copyright 2018, Rights Managed by Nature Publishing Group. (b) Reprinted with permission from ref 558. Copyright
2021 American Chemical Society.
6.1.3. Salt-Assisted CVD. In conventional CVD growth of quaternary alloys, and heterostructured compounds.445 NaCl
MCs, the vapor phase precursors are converted into solid or KI reacts with metal oxides and forms low melting
products via surface adsorption, surface diffusion, and bond intermediate products (e.g., Na2Mo2O7 of Tm = 605 °C),
formation.114 The shape of the final product crystal is primarily which facilitates easy sublimation of the metal precursor and
determined by their inherent free energy of crystal facets and increases the growth rate along the in-plane direction by
the kinetics of the surface diffusion process. 689 The accelerating the nucleation process and increasing the lateral
sublimation and diffusion rate of the solid phase metal oxide dimension of the single grains up to millimeter scale (Figure
precursors (e.g., MoO3, WO3, ReO3, etc.) used for the 32a).6
conventional CVD process plays an important role in Li et al. demonstrated NaCl assisted vapor−liquid−solid
determining the grain size, thickness, and morphology of the (VLS) growth of MoS2 ribbons. The process started with the
as-grown MCs crystals. Due to the high melting point of metal formation of Na−Mo−O droplets; next, the droplets become
oxides (e.g., 795 °C for MoO3), it is challenging to control the saturated with sulfur (S) vapor. Regular lateral displacement of
sublimation rate (or vapor pressure) of the metal precursor the S-saturated droplets triggers the anisotropic growth of the
and its diffusion rate. Since the uniformity in grain size and MoS2 ribbons.6 Moreover, the alkali metal ions can act as an
thickness of the product is not readily controllable, Zhou et al. efficient catalyst to reduce the growth energy barrier and
has recently introduced molten salt-based metal precursors by facilitate the off-equilibrium kinetic growth of 2D MCs. Huang
mixing metal oxides with alkali metal halides (such as NaCl et al. demonstrated the KCl-catalyzed growth of MoS2 via the
and KI) and synthesized a library of 47 MC compounds, vapor−liquid−adatom−solid (VLAS) growth mechanism. The
including binary transition metal compounds, ternary and vapor phase molecules are captured by the catalyst particles on
Chem. Rev. 2023, 123, 3329−3442
Figure 33. Crystallographic phase control. (a) Scheme of the precursor-conversion chemistry. The correlated liquid and solid characteristics of the
catalyst nanoparticles, and the SLS and SSS growth of quantum wires are described. (b,c) HRTEM images of polytypic (b) (Zinc-blende and
wurtzite) and wurtzite CdTe quantum wires (c). (d) Scheme explaining the selective formation of the metastable 1T-WS2 and the stable 2H-WS2
phase in the presence of and in the absence of HMDS. (e) TEM images of corresponding 1T-WS2 (left) and 2H-WS2 (right). (a) Reprinted with
permission from ref 709. Copyright 2017, American Chemical Society. (b,c) Reprinted from permission from ref 708. Copyright 2016, American
Chemical Society. (d,e) Reprinted from permission from ref 104. Copyright 2021, American Chemical Society.
the corners of the growing hexagon. The kinetic mass transport increment compared to the conventional process (Figure 32b).
along the edges becomes the growth rate limiting process.690 The process included H2O vapor-etched and re-evaporate
The local height, surface tension, atomic mobility, and adatom small/defective WS2 or WSe2 nuclei, and effectively reduced
concentration are the control variables in determining the net the nucleation density during the growth process. The process
atomic flux.691,692 While the mass flux determines the amount enabled efficient grain growth through the repeated cycles of
of precursor involved in the nucleation and domain growth, the nucleation−etch−growth. H2O vapor also effectively elimi-
growth rate determines the grain size in the product MC films. nated the carbon impurities which generally act as nucleation
Zhou et al. has demonstrated that a continuous monolayer film centers and produce defective nuclei. Employing a reverse flow
having mm-size grains was formed under high mass flux thus at chemical vapor epitaxy, Zhang et al. achieved epitaxial growth
high growth rates, whereas small-grain polycrystalline films of the second monolayer from the first monolayer and
were obtained at low growth rates.445 Kim et al. used KI as produced large-size TMDC bilayer crystals with a high yield
growth promoter to synthesize large-area uniform films of and good reliability.443 They applied reverse carrier gas (N2/
MoSe2, WS2, and WSe2.693 They spin-coated ammonium H2) flow to prevent the generation of unintended nucleation
orthomolybdate ((NH4)2MoO4) and the KI mixture on a centers on the as-grown first layer, and used H2 to etch away
growth substrate, followed by selenization under an Ar/H2 the emerging nucleation points on the growth substrate.
atmosphere. Following the principle of the salt-assisted Consequently, the second monolayer was deposited preferen-
enhanced mass transport, different types of 2D MCs such as tially on the as-grown monolayer surface. Zhang et al. also
semimetallic WS2,694 Mo/WTe2,454 magnetic MTe2 (M = V, employed a similar idea of the reverse gas flow from the
Nb, Ta),536,695 and doped MoS2696,697 have recently been substrate to the source and prevented uncontrolled homoge-
reported. neous nucleation, thus enabling highly robust epitaxial growth
6.1.4. Growth-Etch Interplay. Cohen et al. recently of various heterostructures.183
demonstrated a growth-etch MOCVD approach to produce 6.1.5. Thickness Control. Due to the thickness-dependent
large-grain (∼12 μm) WS2 and WSe2 films with wafer-scale optical and electronic properties, controllability over the layer
uniformity.558 Upon introducing a small amount of H2O vapor number or thickness of 2D MCs over a large area is an
during the growth process, they achieved a significant grain size essential requirement for practical applications. Wang et al.
Chem. Rev. 2023, 123, 3329−3442
demonstrated a layer-by-layer sulfurization of MoO2 micro- with foreign ions, use of capping ligands, and solvent molecules
crystals for layer-controlled growth of MoS2 microcrystals with adsorbed to the MC surfaces.
a domain size of ∼10 μm.499 Yu et al. demonstrated precise 6.2.1. Thermodynamic Lattice Mixing. In semiconduct-
control in the MoS2 layer number over a large area by precisely ing 1D NWs, nearly equivalent amounts of ZB and WZ were
controlling the amounts of MoCl5 and S powders, flow rate in found in a mixed phase due to the interplay of the lower lattice
the growth environment, and total pressure in the CVD growth energy of ZB nuclei and WZ nuclei.704−707 Wang and Buhro
chamber.473 In the synthesis, the suggested self-limiting nature performed systematic studies on phase control of CdTe NWs
of the layer-by-layer process was controlled by the total by varying the reactivity of Cd precursors and the molar ratio
pressure of the system and flow rate of the precursors. The between Cd and Te (Figure 33a).708,709 Two main precursor
thickness of the resulting film increased with increasing the conversions of TOPTe exist, either the formation of CdTe
flow rate and total pressure of the system. Park et al. (process I) or decomposition into Te (process II). Under
demonstrated large-area thickness modulation of MoS2 films conditions where process I was predominant and Bi nano-
by controlling the Mo deposition time period to control the particles were used, initial incorporation of CdTe and the
Mo film thickness on the (100) Si substrate, such as 4 s for 1- limited solubility of CdTe in the Bi nanoparticles generated
layer MoS2, 10 s for 2-layer MoS2, and 30 s for 3-layer MoS2. liquid catalysts promoting the SLS growth of polytypic NWs.
Subsequent vapor phase sulfurization of Mo films was carried In contrast, when an excess amount of Te existed in the
out in an LPCVD system.698 Samad et al. demonstrated a CVD reaction mixtures (process II), primary intake of Te into Bi
based process to grow 1 layer to 6 layer MoS2 films through nanoparticles rendered solid catalysts, resulting in nearly
precise tuning of the partial pressure of MoCl5 and elemental S phase-pure WZ phase grown via the SSS mechanism. The
precursors. They used the vdW epitaxy on SnS2, TaS2, and fraction of the WZ phase could be manipulated to be a mixed
graphene and carefully controlled the ambient humidity during phase (Figure 33b) and a pure crystal phase (Figures 33c),
the growth process.699 Layer-by-layer epitaxial growth of a with a varying molar ratio of Cd:Te and varying reactivity of
scalable WSe2 film on the Al2O3 (sapphire) (001) substrate Cd precursors of Cd-oleate (Cd(OLT)2), Cd-di-n-octylphos-
was also achieved by MBE, where the atomically flat hexagonal phinate (Cd(DOPT)2), and Cd-n-tetradecylphosphonate (Cd-
lattice of Al2O3 favored c-axis orientation of WSe2.476 Serna et (TDPT)).
al. demonstrated in situ thickness control growth of MoS2 films 6.2.2. Intercalation. Phase transformation by intercalating
on a wide range of substrates by employing the pulsed laser with foreign ions such as Li+ and NH4+ has been proposed for
deposition (PLD) method, in which the thickness control was the 2H-1T-dT (distorted 1T phase) phase transition of 2D
achieved by manipulating the repetition rate (frequency) and MCs.710 Nudged elastic band (NEB) calculation revealed that
energy of the laser as well as the deposition pressure. The intercalating Li+ can largely reduce the transformation energy
MoS2 target used for film deposition was carefully designed barrier of MoS2 from 2H to 1T, and result in spontaneous
with an excessive amount of sulfur.700 By a polymer assisted phase transition from 1T to dT. In the liquid phase exfoliation
deposition method and subsequent thermolysis of a single process, organolithium (typically n-BuLi) chemically interca-
source precursor film of MoS2 (ammonium tetrathiomolyb- lated and stabilized the 1T phase of MoS2 and WS2 NSs,
date), Yang et al. achieved precise thickness tuning of wafer- reaching a phase fraction up to 70% and 80%, respec-
scale MoS2 films from ∼2 nm to ∼30 nm. This process relies tively.29,702
mainly on the formation of uniform precursor film with precise In the direct synthesis by the hydrothermal method, the 1T
thickness control.116 Thickness modulation of MCs (WSe2, phase NSs of MoS2, MoSe2, and WS2 were obtained with a
MoTe2, WTe2) was also achieved through a quick solution- similar strategy except using ammonium ion (NH4+) as an
based microwave assisted deposition process on doped Si intercalant instead of Li+.414,420,421,711 Liu et al. demonstrated
(100) wafers. In the synthesis, the precursor concentration, that the NH4+ ion plays a paramount role in stabilizing the 1T
volume, and microwave irradiation time were the critical phase of MoS2.420 The 1T-MoS2 NSs were obtained by
factors in controlling the MC layer numbers.15,294 Jung et al. reacting ammonium molybdate ((NH4)6Mo7O24·4H2O) and
used a colloidal synthesis to achieve precise tuning in the thiourea (Mo:S = 7:15). As control experiments, sodium
number of layers of MSe2 (M = Mo, W) nanosheets by the molybdate (Na2MoO4·2H2O) was used instead of ammonium
choice of appropriate capping ligands during 2D anisotropic molybdate. When excess thiourea was used (Mo:S = 1:30), the
growth.383 Since the binding affinity of the capping ligands at 1T-MoS2 NSs were formed because NH4+ ions were supplied
the edge facets of the NSs was varied with the functional by protonation of excess thiourea. The intercalation of NH3
groups in the capping ligand, the ligands dictated the formation and NH4+ ions was confirmed by two endothermic peaks at
of multi or single layer MSe2 NSs. 100 and 240 °C. The fraction of 1T phase was 61.6%, which
was lower than that of the Li+ intercalated one. The 1T-MoS2
6.2. Crystallographic Phase Control
intercalated by NH4+ showed enhanced long-term stability up
MCs adopt one of several polymorphs that differ slightly in to half-year which is comparable to the one intercalated by
crystal structures. This polymorphism leads to phase-specific Li+.712,713 Recently, Zhou et al. synthesized the 1T-rich MoSe2
properties and applications. The semiconducting 2H-type MCs by reacting sodium molybdate and selenium oxide in the
can be applied in efficient photocatalysts.701 1T-type MCs are presence of ethylenediamine. The 1T-MoSe2 fraction reached
metallic or semimetallic; hence, they can function as hydrogen up to 53.7%.711 They found ethylenediamine acts not only as
evolution catalysts and supercapacitor electrodes due to the the NH4+ ion source by thermal decomposition but also as a
enhanced charge transfer.3,702 Phase transition of the MCs reductant converting SeO2 to Se2−. When polyvinylpyrrolidone
polymorphs may be thermodynamically possible at high (PVP) and hexadecyltrimethylammonium bromide (CTAB)
temperatures,703 and also morphological stabilization through were used instead of ethylenediamine, only Se was obtained
surface energy modulation can be achieved by intercalation after the hydrothermal reaction.
Chem. Rev. 2023, 123, 3329−3442
Figure 34. Crystallographic phase control. (a) Tellurization rate-dependent metallic-semiconducting-metallic phase evolution in CVD growth of a
large-area few-layer MoTe2. (b) Scheme of the alternating triangular pattern formed by 1H phase (blue) and 1T phase (yellow) of PtSe2. STM
image of the 1H/1T patterned structure in a monolayer PtSe2 (right). (c) Scheme of the 1T′ phase polycrystalline MoTe2 film with Te vacancies
(left). OM image of the 1T′-MoTe2 film grown in 5 min of growth times (right). (d) As Te atoms occupy the vacancies in the 1T′ phase film,
recrystallization induces phase transformation to 2H-MoTe2 (left). The corresponding OM image of the 2H-MoTe2 grown in 30 min of growth
time (right). (e) Scheme explaining the in-plane 2D-epitaxy synthesis of wafer-scale single-crystalline 2H-MoTe2 thin film. The 1T′-MoTe2 film on
a Si wafer was converted gradually to the 2H-MoTe2, starting from the hole to the entire area. (a) Reprinted with permission from ref 723.
Copyright 2017 American Chemical Society. (b) Reprinted with permission from ref 502. Copyright 2017, Rights Managed by Nature Publishing
Group. (c, d) Reprinted with permission from ref 726. Copyright 2019 American Chemical Society. (e) Reprinted with permission from ref 727.
Copyright 2021 American Association for the Advancement of Science.
Heterostructuring anisotropic MC nanocrystals with carbo- MoSe2 and P-doped carbon. These binding energy shifts reflect
naceous materials (carbon, rGO, CNT, etc.) has been widely effective electron transfer from MoSe2 to the P-doped carbon,
investigated, successfully producing nanobox, yolk−shell, which is caused by the change in the d-orbital electron density
core−shell, and NTs. The target application of the carbona- of the transition metal.
ceous coating has been for electrochemical uses. The 6.2.3. Ligand Coordination. Ligand coordination modi-
carbonaceous coating contributes in reducing the strain in fies the geometry and reactivity of the metal precursors, and it
the 2D MC nanocrystals during multiple charge/discharge is also useful to tune the phase of 2D MCs nanocrystals. In the
cycles in the Li-ion battery.714,715 Maintenance of the diffusion hot-injection synthesis, hexamethyldisilazane (HMDS) was
mean free path for electrons and ions stabilized the electrical demonstrated to be an effective phase control ligand. Mahler et
conductivity. A carbon matrix can also induce a structural al. synthesized phase-controlled WS2 NSs by reacting WCl6
change in MC nanocrystals. Recently, Chen et al. found that P- and CS2 in oleylamine with a small amount of oleic acid
doped carbon can induce a phase transition of MoSe2 NSs (Figure 33d). Flower-like 2H-WS2 NSs were obtained in the
from 2H to 3R.716 MoSe2 NSs with a mixed phase of 2H and presence of HMDS, whereas monodisperse round-shaped 1T-
3R (2H/3R MoSe2) were synthesized under solvothermal WS2 NSs with a diameter of 100 nm were produced without
conditions by reacting molybdenyl acetylacetonate and Se HMDS (Figure 33e).701 The synthetic procedure was
powder in N,N-dimethylformamide in the presence of extended to 1T′-WSe2 NSs and 2H/2H′-WTe2 NSs. Reaction
hydrazine and phytic acid. During reaction, phytic acid was between W(CO)6 (or WCl6) and the TOP-Se (Te) complex
carbonized to form P-doped carbon and intercalated in the produced 1T′-WSe2 NSs (without HMDS) and 2H/2H′-
MoSe2 layers to expand interlayer spacing from 0.65 nm (2H- WTe2 (with HMDS).384,387 With a similar synthetic procedure,
MoSe2) to 0.70 nm (2H/3R MoSe2). The binding energies of 1T′-MoTe2 NSs were obtained by reacting MoCl5 and the
both Mo 3d and Se 3d shifted to a higher value compared to TOP-Te complex with HMDS.389 While stable 2H-MoTe2
2H-MoSe2, indicating stronger electronic interaction between nanocrystals were synthesized with HMDS, metastable 1T′-
Chem. Rev. 2023, 123, 3329−3442
MoTe2 nanocrystals were formed with HMDS. The DFT gradual temperature decrease. By changing Te flux controlled
calculation suggested that the energy difference between 1T′- by reaction temperature, Yoo et al. obtained few-layer 2H-
MoTe2 and 2H-MoTe2 is small, which renders both phases MoTe2 at a high Te flux and few-layer 1T′-MoTe2 at a low Te
potentially achievable.717 The activation energy barrier from flux, and 2H-1T′ MoTe2 homojunctions at a medium flux.725
1T′-MoTe2 to 2H-MoTe2 is much larger than that from 1T′ to Starting from 1T′-MoTe2, through lithographic masking and
2H phases of MoS2 and MoSe2. The 1T′-to-2H transition in subsequent tellurization of the unmasked area under high Te
MoTe2 is accompanied with significant lattice constant change. flux, they have obtained few-layer 2H-1T′ MoTe2 patterns. By
It is also known that the 1T′-MoTe2 is relatively stable and the controlling the annealing temperature and the amount of
1T′-to-2H transition is inhibited by a grain boundary pinning deposited Se, Lin et al. demonstrated formation of intrinsically
effect. patterned monolayer PtSe2 on a Pt substrate, showing a
The production yield of the 1T phase 2D MCs obtained by periodic triangular structure of alternating 1H and 1T phases
the in situ intercalation or selective use of ligands is limited to (Figure 34b).502 By tuning the kinetic rates of nucleation and
60−80%, causing inhomogeneous phase distribution and crystal growth, Xu et al. demonstrated the growth of MoTe2
nonreliable performance.718 With a two-step process combin- films with different phases by tellurizing the Mo film at 620 °C
ing the above approaches, the yield of 1T phase 2D MCs was under different growth times.726 When a short growth time of
enhanced to ∼100%. Stoichiometric AMS2 (A = Li, Na, K, M = 5 min was applied, the metastable 1T′-MoTe2 phase was
Mo, Nb, Ta, Ti) crystals were synthesized by solid state formed (Figure 34c). According to DFT calculations, this is
reaction between metal (M), sulfur (S), and alkali sulfide the most stable phase when Te deficiency exceeds 2%.
(A2S), followed by exfoliation in an aqueous HCl solution719 However, at a growth time of 30 min, randomly distributed
or distilled water.720 Atomic structures of monolayer MoS2 circular 2H-MoTe2 phase emerged (Figure 34d), which was
NSs exfoliated from LiMoS2 by HCl solution and from MoS2 eventually grown and merged with each other to form a
by in situ intercalation were characterized by HAADF-STEM. uniform single-crystalline 2H-MoTe2 film upon a prolonged
While the MoS2 NSs exfoliated by n-BuLi were composed of growth time of 180 min.
the mixed phases (1H, 1T, and 1T′), the MoS2 NSs exfoliated In a recent study, starting from a 1T′-MoTe2 film, Xu et al.
from LiMoS2 crystals showed the pure 1T′ phase. In addition, has employed a seeded epitaxial growth to produce a 1-in.
enhanced long-term stability of the 1T′-MoS2 exfoliated from wafer scale single-crystalline 2H-MoTe2 film via the solid-to-
LiMoS2 was obtained. This method could be generalized to solid phase transition and recrystallization process.727 The
various monolayer 2D MCs NSs including NbS2, TaS2, and process was composed of both vertical epitaxy and in-plane
TiS2. epitaxy. An exfoliated single-crystalline 2H-MoTe2 NS was
6.2.4. Vapor-Phase Transition. In case of vapor phase placed in the middle of a 1T′-MoTe2 film. A small punch was
deposition of 2D MCs, various approaches have been made on the 2H-MoTe2 NS. Supply of Te filled the Te-
implemented for phase-controlled growth, interconversion vacancies of 1T′-MoTe2 and induced the 1T′-to-2H phase
between different phases, and phase patterning. For instance, transition. The in-plane 2D-epitaxial growth was triggered from
using controlled tellurization of MoO 3 , Zhou et al. the punched area of the 2H-MoTe2 film and extended to
demonstrated selective formation of 2H-MoTe2 (under produce wafer-scale single-crystalline 2H-MoTe2 film (Figure
sufficient Te source) and 1T′-MoTe2 (under insufficient Te) 34e). Apart from the phase control by the growth
in large-area homogeneous thin films.721 They prepared a conditions,167,728,729 several recent approaches have also been
MoO3 film by fully oxidizing a 1-nm-thick Mo film evaporated proposed using the external electric field,730 electrostatic
on a SiO2/Si wafer and converted the film into MoTe2 by doping effect,731 electrostatic gating effect,732 pressure,733
controlled tellurization. They observed that 2H-MoTe2 was thermal strain,728 defect-induced phase programming,734,735
preferred at the sublimation temperature (∼600 °C), whereas gate-tunable phase transition,736 laser-induced phase pattern-
1T′-MoTe2 was prepared at 700 °C.496 By controlling the ing,737 etc. Different phases of various MCs and experimental
growth temperature, Kang et al. has recently achieved phase parameters for phase-controlled growth have been summarized
controlled growth of ultrathin 2D-layered tetragonal FeTe NPs well in the recent review article by Wang et al.738
and nonlayered hexagonal FeTe NPs.722 The formation energy
6.3. Chemical Composition Control
difference between the hexagonal and tetragonal phase was the
key driving force for the temperature-sensitive phase tunability. Recently, a variety of efforts have been focused on tuning the
It is observed that hexagonal FeTe was the dominant phase at native properties of anisotropic MCs to improve their
a relatively high temperature, whereas the tetragonal FeTe electronic and photonic properties. Several strategies such as
phase was dominant at the decreasing temperature. In a similar doping, compound formation, and heterostructure formation
study, Cheng et al. has also demonstrated controlled growth of have been applied to control the chemical composition of these
hexagonal and tetragonal FeTe NSs by controlling the growth materials and effectively tune their intrinsic properties. This
temperature.554 Yang et al. has developed phase modulation of section summarizes the strategies for property modulation.
MoTe2 2D film which was sensitive to the tellurization rate.723 6.3.1. Thermodynamic Solid Solutions. Precise tuning
Carrier gas flow rate and tellurization temperature was varied of the chemical composition is essential in achieving desired
to control the tellurization velocity and reaction coefficient. properties of the anisotropic MCs nanocrystals. The metal or
Pure 2H-MoTe2 was obtained at a fast tellurization rate, while chalcogen atoms in a parent MC crystals can be substituted by
pure 1T′ phase was reliably produced at a fast tellurization other metal or chalcogen atoms to achieve desired proper-
velocity (Figure 34a). Empante et al. has synthesized three ties.739 In the wet chemical synthesis, various 1D and 2D MC
distinct structural phases of MoTe2 (2H, 1T′, and 1T) only by NSs were successfully synthesized by simple mixing of
varying the cooling kinetics after the growth step.724 Pure 1T- precursors.317,384,740−743 Sun et al. synthesized 2D MCs
MoTe2 was obtained when the growth process was quenched nanocrystals with a wide range of compositions of metals
rapidly; meanwhile, 1T′ was thermodynamically stable under and chalcogens in MoSe2−WSe2 and WS2−WSe2 nanocrystals
Chem. Rev. 2023, 123, 3329−3442
Figure 35. Chemical composition control. (a) Photograph of MoxW1−xSe2 and WS2ySe2(1−y) samples suspended in ethanol. (b) Raman spectra of
the pristine MoS2 NSs and the Dy-doped MoS2 NSs. (c) M-H loops of the pristine MoS2 sheets and Dy-doped MoS2 sheets at room temperature.
(a) Reprinted with permission from ref 744. Copyright 2017, American Chemical Society. (b,c) Reprinted from permission from ref 745. Copyright
(Figure 35a). 744 The MoSe 2 −WSe 2 solid solution 4H2O) and Dy(COOCH3)2 with H2S gas, followed by
(MoxW1−xSe2) was synthesized at 300 °C by introducing annealing at 500 °C for 2 h in the N2 environment. The
dropwise metal precursors (MoCl5, WCl6) dissolved in oleic Raman peaks for E12g and A1g shifted to lower wavelengths from
acid in a mixed solution containing oleylamine, HMDS, and 377.3 to 373.3 cm−1 and from 401.3 to 398.6 cm−1,
diphenyl diselenide. For reliable composition control, similar respectively, as the Dy doping concentration increased (Figure
reactivities of the precursors are desired. Since the metal 35b). After Dy doping (1.37 at%) in MoS2 NSs, room-
precursors (MoCl5, WCl6) had similar reactivities in the temperature ferromagnetic properties were observed with
solution, the composition control was readily achieved. A full maximum remnant magnetization of 0.0034 emu/g and
range of WS2−WSe2 solid solutions (WS2ySe2(1‑y)) were saturation magnetization of 0.023 emu/g (Figure 35c).
produced by the combination of CS2 and diphenyl diselenide Tuning the chemical composition of vapor phase grown MC
for sulfur-rich solid solutions (y > 0.5) and from the nanocrystals has been achieved mainly by means of surface
combination of diphenyl disulfide and diphenyl diselenide for chemical doping and lattice doping. Spatially controlled lattice
selenium-rich nanocrystals (y < 0.5). With the precise doping has also been implemented recently by intercalating
composition variation, the excitonic transition of the colloidal metal atoms in the vdW gap of bilayer MC single crystal NSs.
MoxW1−xSe2 and WS2ySe2(1‑y) nanocrystals was readily tunable For instance, Zhang et al. chemically doped the exposed
from 1.51 to 1.93 eV in UV−vis adsorption spectra. surface of MoS2, WS2, MoSe2, and WSe2 nanocrystals by
6.3.2. Surface Doping. As well as the substitution of the exposing them to the reducing solutions of pentamethylrho-
same group elements, other group elements can be doped in docene dimer (n-dopant) and oxidizing solution of “Magic
parent 2D MCs.176−181 Xin et al. prepared P-doped MoS2 NSs Blue,” [N(C6H4-p-Br)3]+[SbCl6]− (p-dopant).277 The n-
with the hydrothermal method by using Na2MoO4·2H2O, L- dopant reacted with the MCs via electron-transfer pathways
cysteine (C 3 H 7 NO 2 S), and monosodium phosphate and released two electrons to the MCs, whereas the p-dopant
(NaH2PO2·H2O) as Mo, S, and P sources, respectively.182 extracted one electron from the MCs to form an anion that is
Compared to the undoped MoS2, interlayer spacing increased electrostatically attached to the MC surface (Figure 36a). They
from 0.62 to 0.65 nm due to the larger atom size of the doped found that all four MC nanocrystals could be used as either p-
P (1.23 Å) compared to the substituted S atom (1.04 Å). or n-channel materials when appropriately doped, irrespective
Meanwhile, P-doping induced a shift of the A1g peak to a lower of their initial transport polarity. The extent of doping could be
wavelength, indicating the presence of tensile stress in the P- controlled by varying the dopant concentration and treatment
doped MoS2. Zhao et al. reported Dy-doped MoS2 NSs to time. The band alignments of MoS2, MoSe2, WS2, and WSe2
acquire room-temperature ferromagnetic properties.745 The were calculated with the effective ionization energy of n-dopant
Dy-doped MoS2 NSs were obtained by reacting a mixed and electron affinity of the p-dopant (Figure 36b). The band
aqueous solution of ammonium molybdate ((NH4)6Mo7O24· alignment suggested that n-dopants could easily contribute
Chem. Rev. 2023, 123, 3329−3442
Figure 36. Surface doping of 2D MCs. (a) Scheme of the charge transfer process for n- and p-doping. Monomeric RhCp*Cp+ is the expected
product by n-doping. Treatment with MB is expected to form neutral tris(4-bromophenyl) amine and leave SbCl6− anions on the surface. (b)
Calculated band alignment of MoS2, MoSe2, WS2, and WSe2. The effective ionization energy of the n-dopant and the electron affinity (EA) of the
p-dopant are estimated from electrochemistry. (a,b) Reprinted with permission from ref 277. Copyright 2018 Wiley-VCH Verlag GmbH & Co.
KGaA, Weinheim.
electrons to the conduction band of all four MCs, whereas 6.3.3. Lattice Doping. Lattice doping in the form of either
electron transfer from the valence band of MoS2 and WS2 to substitutional doping or interstitial doping has been used to
the p-dopant was marginally feasible. Ji et al. also demonstrated tailor materials characteristics and add new functionalities into
chemical doping of monolayer WSe2 to tune its electrical MC nanocrystals. Using DFT calculations, Karthikeyan et al.
polarity.288 4-Nitrobenzenediazonium tetrafluoroborate was demonstrated that most transition metal atoms can be
used as the p-type dopant, and diethylenetriamine was used to incorporated as either interstitial or substitutional dopants in
induce the n-type doping effect. Interestingly, both p- and n- the crystal lattice of a MoTe2 thin film through atomic
type WSe2 field effect transistors (FETs) showed much higher deposition at a moderate temperature.748 The transition metals
effective carrier mobilities than the pristine WSe2 ambipolar land as adatoms on the MoTe2 surface, and then either form
atomic clusters by self-agglomeration or diffuse inside the
FETs. Similarly, Yarali et al. also demonstrated the chemical
crystal lattice (Figure 37a). Two stable adatom positions were
doping of monolayer MoS2 by using 4,4′-bipyridine as an identified as (i) on top of the middle of the hexagon (hollow or
organic electron donor.746 They have achieved the highest “h-Top” position) or on top of the Mo site (“Mo-Top”). The
doping levels to date, in the range 0.63 to 1.26 electrons per positions on top of Te atoms were found to be unstable. Once
dopant molecule. Using Lewis acid−base chemistry, Lei et al. diffused inside the MoTe2 lattice, the atoms can either occupy
demonstrated that the lone pair electrons on the surface of the interstitial site (Int) or chalcogen (X) site with the
many 2D MCs (such as MoS2, MoSe2, InSe) can be used as a chalcogen atom displaced to the adatom. The formation
Lewis base to form coordination complexes with other Lewis energies (Ef) of all transition metal adatoms in the “h-Top”,
acids such as B3+, Al3+, and Sn4+, which in turn can control the “Mo-Top” positions on MoS2 are determined, along with the
electronic surface states of the materials.747 energies for interstitial (Int) and substitutional (X-sub) site
Chem. Rev. 2023, 123, 3329−3442
Figure 37. Lattice doping of 2D MCs. (a) Scheme of transition metal (TM) atom deposition on MoX2 layers, and the atomic structures of TM
adatoms and the atoms embedded in MoX2. The green, ochre, and red balls represent host Mo, chalcogen, and TM atoms, respectively. (b)
Magnified STEM-ADF image revealing a single Fe dopant atom (left), corresponding simulated image of the same (middle), and corresponding
atomic model (right). (a) Reprinted with permission from ref 748. Copyright 2019 American Chemical Society. (b) Reprinted with permission
from ref 752. Copyright 2020 American Chemical Society.
occupancy of the adatoms. This formation energy calculation MoS2, in situ substitutional doping of Fe atoms into a MoS2
indicates that most transition metal atoms prefer to stay on the monolayer was employed, where the Fe atoms substituted Mo
surface of MoS2 in the form of atomic clusters. This theoretical sites in the MoS2 crystal lattice.760 Similarly, V-doping was
prediction is in good agreement with experimental observa- used to achieve tunable ferromagnetism of the WSe 2
tions, where lattice doping of MoS2 by Co, Mn, and Au was monolayer at room temperature.761 Catalytic activity of the
unsuccessful and the dopants predominately remained at inactive basal plane of the MoS2 monolayers was induced by
adatoms sites, flake edges, or domain boundaries.749−751 means of Re doping with a high concentration (larger than
Through the CVD growth process, Li et al. recently 50%) and formation of RexMo1−xS2 alloy monolayers.275 Luo
demonstrated the formation of an Fe-doped MoS2 monolayer, et al. has recently summarized very well a variety of doping
where the Fe atom occupies a substitutional position at the Mo engineering and related functionalization for 2D MCs.762
site (FeMo) (Figure 37b).752 Gao et al. demonstrated 6.4. Formation of Heterostructures
substitutional doping of Nb and Re on a wafer-scale When anisotropic nanocrystals form heterostructures with
continuous monolayer of MoS2.753 With varying concen- other materials, unique properties that are not achievable from
trations of Nb and Re in the MoS2 or WS2 monolayer, the the pristine structures can be obtained. Owing to extensive
sheet conductance was tunable.754,755 The electronic and research efforts, the synthesis of anisotropic MC nanocrystals
photonic properties were also engineered by in situ substitu- with multicomponent heterostructures has significantly
tional doping of Re, Co, Cr, and O during the CVD growth flourished and enabled a variety of interesting studies in
process.276,756−758 Heteroatom-substitution (such as yttrium catalysis, electrochemical energy storages, thermoelectrics, and
and phosphorus) has also been utilized for phase selected optoelectronic devices.763−767 Through chemical transforma-
growth (2H phase or 1T phase) of various 2D MC NSs.759 To tion, epitaxial growth, and multistep growth, various
induce room temperature ferromagnetism in a monolayer anisotropic MC heterostructures coupled with
Chem. Rev. 2023, 123, 3329−3442
Figure 38. Formation of heterostructures. (a) Dark-field STEM image and EDS element mapping of 3CdS-4ZnS quantum-dot-in-NW. (b) ADF-
STEM image of Ag5%/1T′-MoTe2. (c) Scheme of the bilayer pristine SnS2 with a vdW gap (1), native vacancy-dominated defect (2), Cu
intercalation-induced p-type doping (3), and Co intercalation-induced metallic doping (4). Schemes corresponding to (2), (3), and (4) show that
spatially controlled intercalation realized these three doping types. (d) Scheme of the spatially controlled intercalation for SnS2. (e) OM image of
various spatially controlled intercalation of a SnS2 single crystal to obtain an in-plane p−n junction (Cu-SnS2 and SnS2), S-shaped SnS2 with Cu-
SnS2, half SnS2 and half Co-SnS2, and in-plane metal−semiconductor junction (Co-SnS2 and Cu-SnS2). (a) Reprinted with permission from ref
796. Copyright 2018, Rights Managed by Nature Publishing Group. (b) Reprinted from new permission from ref 798. Copyright 2020, Rights
Managed by Nature Publishing Group. (c−e) Reprinted with permission from ref 799. Copyright 2018, Rights Managed by Nature Publishing
Group.
MCs,385,768−774 metal oxides,775−781 noble metals,616,782−784 growth of seeds on overgrown materials is explained by their
and carbon-based materials785−795 have been prepared. wettability.295 To selectively grow Fe3O4 only at one end of
6.4.1. Sequential Reaction. In catalyzed growth of 1D NRs, double buffer layers consisting of Ag2S and Au were
NWs, a semiconductor MC starts to grow from the catalyst introduced to gradually modify the interfacial energies.797 The
when the concentration in the catalyst reaches supersaturation. resultant heterostructure presented impressive optical chiral
The relative intercalation energy in the host catalyst varies with activities in the absence of other chiral sources, and the optical
each element. Adding an active precursor with a lower activities could be further enhanced when an external magnetic
intercalation energy in a reacting solution medium can field was directionally applied.
substitute the less active precursor dissolved in the catalyst, Heterostructure formation between MC nanocrystals and
hence creating a heterostructure. Once the more active noble metal nanocrystals has been realized by an appropriate
precursor is consumed, the less active precursor starts to reduction process including chemical, photochemical, or
grow. Density functional theory revealed that incorporation of electroless deposition with the precursor of K 2 PtCl4 ,
Cd in Ag2S catalyst is energetically preferred over Zn.796 K2PdCl4, HAuCl4, or AgNO3.616,782−784 Recently, Sun et al.
Therefore, when a small amount of a Cd precursor was added reported spontaneous reduction-deposition of Ag and Au
in growing ZnS NWs, the growth of ZnS NWs switched to nanoparticles on 2D MC nanocrystals (1T-WS2, 2H-WS2, 2H-
epitaxial growth of CdS quantum dots, and then re-epitaxy of MoSe 2, 2H-WSe2 , 1T′-MoTe 2, and Td-WTe2 ).798 The
ZnS took place after the Cd precursor was consumed (Figure deposition of Au on all six MC nanocrystals produced uniform
38a).796 By varying the reaction time after Cd precursor Au nanoparticles. However, large-sized Au nanoparticles were
injection, the lattice spacing and the heterostructure could be generated on the surface of metallic ditellurides (1T′-MoTe2
adjusted. Zhuang et al. tuned the chemical composition of and Td-WTe2). This preferred lateral growth suggests stronger
ZnxCd1−xS NRs (0 ≤ x ≤ 1) with a small Ag2S apex at one end electron-donating capabilities of metallic ditellurides that are
of the NRs.797 With a varying Zn/Cd ratio, the semi- attributed to their higher Fermi levels. Ag nanoparticles were
conducting NRs exhibited a broadened excitonic absorption created on metal disulfides and diselenides during deposition.
in the ultraviolet and visible regime. The authors fabricated a Ag nanoparticles readily moved, coalesced, and became larger
quaternary heterostructure with Fe3O4 with the aid of Au nanoparticles, resulting in a bimodal distribution of Ag
(ZnxCd1−xS−Ag2S/Au@Fe3O4). Generally, heterogeneous nanoparticles on 1T-WS2, 2H-WS2, 2H-MoSe2, and 2H-
Chem. Rev. 2023, 123, 3329−3442
Figure 39. Heterostructure formation of MCs. (a) OM image of three-junction lateral heterostructures made of MoSe2 and WSe2. Magnified OM
image in the inset was taken from the area within the dashed box. The dark-contrast regions correspond to MoSe2, the bright-contrast regions to
WSe2. (b) Corresponding Raman (left) and photoluminescence (PL) spectra (right) of the heterostructure at positions 1, 2, 3, and 4, as marked in
the inset of (a). (c) Scheme of the fabrication process of 2D vdW heterostructure (vdWH). The laser patterned arrays are obtained in forms of
large-area monolayer or bilayer of WSe2, MoS2, and WS2 (top). (d) AFM image of a VSe2/WSe2 vdWH array, and corresponding Raman (at 257
cm−1 for WSe20, and at 206 cm−1 for VSe2) and PL (at 776 nm for WSe2) mapping images. (a,b) Reprinted with permission from ref 185.
Copyright 2018, Rights Managed by Nature Publishing Group. (c,d) Reprinted with permission from ref 130. Copyright 2020, Rights Managed by
Nature Publishing Group.
WSe2. Atomically thin Ag layers were deposited on 1T′-MoTe2 tional lithographic patterning, spatial control of the inter-
and Td-WTe2 and generated a unique 2D-2D heterostructure calation was achieved (Figure 38d). The process relies on
on the basal plane of the metal ditellurides (Figure 38b). deposition of Zn and Al with a predefined pattern on the
Spectroscopic analysis revealed that the formation of interfacial pristine SnS2. Cu was intercalated into the exposed SnS2 areas,
Ag−Te bond resulted in a partial positive charge; therefore, the followed by etching of Zn metal. Co was intercalated into the
growth was self-limiting to form a single atomic layer of Ag on earlier Zn-deposited areas, and then Al was removed to
the metal ditellurides. produce Cu-SnS2, Co-SnS2, and SnS2 in-plane heterostructures
6.4.2. Intercalated Patterning. Gong et al. devised a such as SnS2@Cu-SnS2, SnS2@Co-SnS2, and Co-SnS2@Cu-
controlled solvent-based intercalation method to achieve p- SnS2 (Figure 38e) that are difficult to achieve with mechanical
type, n-type, and degenerately doped semiconducting behav- transfer or other traditional methods.
iors in the same CVD grown bilayer 2D SnS2 single crystal NS 6.4.3. Vertical Heterostructure in CVD. CVD-based
(Figure 38c). 799 When the n-type pristine SnS2 was vapor phase deposition offers great advantages for the reliable
intercalated by Cu and Co atoms, it turned out to be a p- construction of 2D MC heterostructures and superlattices with
type semiconductor (Cu-SnS2) and metallic conductive (Co- precisely defined spatial modulation of chemical compositions
SnS2). By combining the intercalation method and conven- and electronic structures. To date several 2D lateral
Chem. Rev. 2023, 123, 3329−3442
Figure 40. Growth-induced intrinsic defects of MCs. (a) Histograms of various point defects (left) and their densities (right) in physical vapor
deposition (PVD), CVD and mechanically exfoliated (ME) MoS2 monolayers. (b) Top and side view schematic illustration of MoS2 lattice
structure, with a sulfur monovacancy (Vs). (c) Scheme of the band structure representing the vacancy-induced formation of midgap states. (d)
Schematic stability diagram of the charge states in monolayer MoS2, as a function of Fermi energy (EF). (e) Schematic energy diagram of different
charge states of VS (top) and electronic configurations (VS), in the 0, −1, and −2 charge states. (a) Reprinted with permission from ref 815.
Copyright 2015, Rights Managed by Nature Publishing Group. (b−e) Reprinted with permission from ref 838. Copyright 2021, Rights Managed by
Nature Publishing Group.
heterostructures (e.g., WS2−MoS2,185,187,550,800,801 MoSe2− expose the edges of the seed 2D crystals to ambient
WSe2,548,802 ReS2−WS2,803 NbS2−MoS2,551 NbS2−WS2,804 contaminations, which in effect restricts the flexibility to
WS2−WSe2, and WS2−MoSe2),183,459 multiheterostructures control the periodic homogeneity of the domain size. Using a
(e.g., WS2−WSe2−MoS2 and WS2−MoSe2−WSe2),183 and single heterogeneous solid source, Sahoo et al. recently
superlattices (e.g., WS2−WSe2−WS2−WSe2−WS2)183,553 have reported a one-pot continuous growth approach for lateral
been reported. Several studies of the vertical heterostructure multijunction heterostructures.185 Simply by changing the
formation have also been reported recently using the CVD composition of the relative gas environment in the presence of
process. However, controlled fabrication of vertical multi- H2O vapor, the sequential formation of heterojunctions was
heterostructures by the CVD approach are rare,187,805−807 and achieved through edge-epitaxy (Figure 39a). They succeeded
generally those heterostructures have been achieved by in forming a seven-junction heterostructure with variable
mechanical exfoliation and the layer-by-layer stacking transfer domain width. The number of junctions and the lateral size of
process.184,189 For experimental realization of these hetero- each domain were controlled by the number of gas-switching
structures and superlattices through stepwise edge epitaxy, the cycles, and varying the growth time of each individual cycle,
nucleating block must be robust enough to survive the respectively. In Figure 39b, Raman (in the left) and PL spectra
temperature and environmental swing between the growth (in the right) of the samples marked in Figure 39a, at positions
steps. In addition, the growth conditions must ensure exclusive 1 (MoSe2), 2 (WSe2), 3 (MoSe2), and 4 (WSe2), confirmed
heterogeneous epitaxial nucleation of the new crystal seeds at the spatial distribution of the MoSe2 and WSe2 domains.
the edge of the existing 2D crystals, and undesired Zhang et al. employed a reverse gas flow technique during the
homogeneous nucleation of the new crystal seeds must be temperature swing stage in sequential growth steps to produce
minimized.183 diverse heterostructures (e.g., WS2−WSe2 and WS2−MoSe2),
To date, one-step,187,802,808 two-step,548,549 or multistep183 multiheterostructures (e.g., WS2−Se2−MoS2, and WS2−
growth processes have been implemented to produce metal MoSe2−WSe2), and superlattices (WS2−WSe2−WS2−WSe2−
dichalcogenide lateral heterostructures. These stepwise pro- WS2).183 The use of reverse gas flow cools the existing 2D seed
cesses require alternating use of precursors and reactors, which crystals and prevents undesired thermal degradation, environ-
Chem. Rev. 2023, 123, 3329−3442
mental contamination, and uncontrolled homogeneous In a comprehensive joint experiment−theory study, Hong et
nucleation, which enables highly robust growth. Using a one- al. investigated various point defects in monolayer MoS2,
step synthesis method, Fu et al. recently demonstrated the prepared by mechanical exfoliation (ME), PVD, and CVD
vertical heterostructure formation between NbS2 (metallic) processes.815Figure 40a shows the total counts and defect
and MoS2 (semiconductor).551 Initially, MoS2 was grown into density of different point defects obtained from 70 atomically
a triangular single-crystal form, and then NbS2 was nucleated resolved ADF-STEM images for each growth type. They found
only on the top corners of MoS2 triangles, followed by growth that the VS vacancy type of point defect is dominant for the
and eventual merging of NbS2 at the edge sides and then ME and CVD process, whereas VMo (one Mo atom missing)
covering the entire MoS2 layer. and SMo (one S atom replacing Mo site) defects were observed
Li et al. has recently demonstrated a general strategy to at very low concentrations. In PVD samples, however, the
produce a patterned vertical heterostructure array by selective antisite defects such as MoS2 and MoS were the dominant type.
nucleation at the predesignated spatial locations (Figure A time-domain ab initio analysis by Li et al. also demonstrated
39c).130 The process started with laser patterning of monolayer that PVD samples contain many antisite defects, which greatly
or bilayer MCs (e.g., WSe2, WS2, MoS2) to create periodic decrease charge-carrier lifetimes and mobilities. Because the
arrays of selective nucleation sites for the epilayer. With precise CVD-grown samples mainly contain vacancy defects, they
control over the crystal nucleation and growth of the epilayer, mainly influence the transport of the holes and have less effect
various periodic arrays of the vdW heterostructures were on electron lifetime.258
reproducibly achieved, such as VSe2/WSe2, NiTe2/WSe2, 6.5.2. Point Defects. Point defects in monolayer 2D MCs
CoTe2/WSe2, NbTe2/WSe2, VS2/WSe2, VSe2/MoS2, and can significantly influence their electronic structure819,820 and
VSe2/WS2. The uniformity of the VSe2/WSe2 heterostructure electrical carrier transport properties by determining the
was clearly characterized by AFM, Raman spectroscopy, and majority carrier,819−821 as well as modulate the work
PL mapping images of WSe2 and VSe2 (Figure 39d). Islam et function822,823 and many other aspects of the materials starting
al. demonstrated a direct integration process for large-area (4 from magnetism to catalysis.824−826 Localized point defects can
cm2) vdW heterostructures of MoS2 and WS2. They deposited also work as a highly efficient single photon source by
Mo and W seed layers and sulfurized in a low-pressure CVD confining the excitons.827−829 In addition, Han et al. recently
chamber to produce the few-layer MoS2/WS2 heterostruc- fabricated a high performance piezoelectric nanogenerator by
ture.495 It is worth noting that Zhang et al. recently reported an passivating the point defects in MoS2 NSs.825 S vacancies and
in-depth review on the construction of 2D multiheteros- Mo−S antisite defects have also been demonstrated to enhance
tructures emphasizing the growth parameters, choice of the interlayer electron transport in the bilayer MoS 2
catalysts, mechanism, and their applications.809 homojunction by intervalley scattering.830 By investigating
the formation and stability of point defects in monolayer ReS2,
6.5. Defect Engineering
Horzum et al. demonstrated that Re-containing point defects
2D MCs may contain several structural defects in their crystal lead to spin polarized ground states with localized magnetic
lattices which can significantly alter their electrical and optical moments of 1−3 μB, while S-containing defects result in a
properties. The presence of defects in MCs can be either nonmagnetic semiconducting ground state.831 Through a
beneficial or detrimental, depending on the target application. comparative theoretical study of intrinsic point defects in
According to their geometry and shape, lattice defects and 1T′-MoS2 and 2H-MoS2, Pizzochero et al. demonstrated that,
imperfections can be considered under four main categories: under thermodynamic equilibrium, the 1T′-MoS2 phase is
point defects (vacancies, interstitial defects, substitution more prone to host additional defects than the 2H phase.832
defects), line defects or dislocations (screw dislocation, edge Due to the structural relaxation that plays a major role in
dislocation), planar defects or interfacial or grain boundary lowering the defect formation energy, Mo vacancies in 1T′-
defects, and volume defects. In this section, the origin, MoS2 are the abundant defect in contrast to the 2H phase.
structure, effects, and rational control of different types of Scanning tunneling microscope/spectroscopy (STM/S) and
defects are discussed. STEM are the mostly used tools to study these defects at the
6.5.1. Growth-Induced Intrinsic Defects. Defect mor- atomic scale, which can distinguish a sulfur monovacancy from
phology plays a crucial role in determining the properties of a divacancy or an antisite defect.585,833−836 For instance, Zhang
the system and can harness new functionalities.810,811 et al. engineered the W vacancy in a monolayer WSe2 by single
Structural inhomogeneities at the nanoscale in the forms of K atom decoration and proved that K decoration alters the
point defects, line defects, grain boundaries, dislocations, and energy states.585 Very recently, Calderon et al. employed
ripples have significant influence on the mechanical, optical, differential phase contrast (DPC) STEM techniques for atomic
thermal, and electrical properties of the material.254,812−815 For electrostatic mapping of point defects in a monolayer MoS2,
instance, sulfur vacancies were predominant in the mechan- providing information about the local chemical state in the
ically exfoliated and PVD-processed samples,816,817 whereas presence of S vacancies.837 Through noise nanospectroscopy,
antisite defects (Mo replacing S in case of MoS2) were main Song et al. recently probed the ionization dynamics of S
defects in the CVD-grown samples.815 Sharona et al. recently monovacancy (VS) defects in a monolayer MoS2.838 It is
reported various types of cross-sectional defects and two types observed that S monovacancy defects exhibit distinct
of grain boundary defects in a pulsed laser deposited (PLD) ionization configurations of 0, −1, and −2.839 The neutral
MoS2 film.817 Edelberg et al. investigated the intrinsic point VS(0) vacancy is occupied by two electrons, corresponding to
defects found in WSe2 single crystals prepared by chemical the valence of the missing S2− atom (Figure 40b). The energy
vapor transport (CVT) and the self-flux growth approach.818 band diagram showing the mid gap states (a1 and e) appears in
Once the CVT-grown MoSe2 sample was thermally annealed between EC and EV due to the presence of VS (−1) in MoS2
under the thermal gradient (t-CVT), the defect density (Figure 40c).253 The relative stability of the VS charge states is
dramatically reduced to 0.2% of the unit cells. shown in the energy diagram in Figure 40d. It is observed that
Chem. Rev. 2023, 123, 3329−3442
Figure 41. Point defects of MCs. (a) Raman spectra of MoS2 thin films after Au ion irradiation at various ion fluences (LD) to create point defects.
(b) Intensity of the defect peak LA(M) at ∼227 cm−1 increases with the increase of Au ion fluence. (c) Raman mapping images of the sample for
defect peak LA(M) in the gray shadow area in (b). Reprinted with permission from ref 850. Copyright 2018 American Chemical Society.
Figure 42. One-dimensional defects (dislocation, grain boundary) of MC. (a) Perspective view of the typical grain morphology (shown in different
color) in a polycrystalline 2D MCs. (b) Top-view of the as-formed grain boundaries (GBs, marked with gray color atoms). (c) Distribution of von
Mises stress field of a grain-textured polycrystal. (d and e) Typical loop and Y-shaped GBs captured from the polycrystal, respectively. Typical
dislocation cores captured from GBs in polycrystal are shown in the right side, where they are named accordingly to the constituent ring-pairs.
Reprinted with permission from ref 854. Copyright 2018 American Chemical Society.
the switching between two stable vacancy states (VS (0) and VS metastable VS (−2) configuration is relatively lower, so the
(−1)) is more likely since they are separated by a relatively switching between VS (−1) and VS (−2) is less likely (Figure
high kinetic barrier. However, the kinetic barrier for the 40e).
Chem. Rev. 2023, 123, 3329−3442
Figure 43. Grain boundary healing of MCs. (a) Scheme of MoSe2 grain growth via GB migration, directional gliding, and ultimate annihilation of
GBs upon thermal annealing. (b) High resolution STEM-ADF images of the pinned GBs by defects in 2D ReS2. The immobile dislocations are
marked by yellow dotted lines. Low-index GBs are highly mobile and can actively participate in the lattice reconstructions in 2D ReS2. (c) Atomic
model presenting the reconstruction process to form 8-member-ring arrays in VSe2. (a) Reprinted with permission from ref 874. Copyright 2019
Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. (b) Reprinted with permission from ref 875. Copyright 2020 Wiley-VCH Verlag GmbH &
Co. KGaA, Weinheim. (c) Reprinted with permission from ref 876. Copyright 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Manipulating the defect types, positions, and their respective vacancies, the intensity of the disorder-induced Raman
densities is an effective way to obtain novel functionalities and scattering peak (LA phonon mode, at ∼227 cm−1) also
superior device performance.667,840−842 For instance, weak increased (Figure 41b). The Raman mapping images for this
ferromagnetism with a variable magnetic easy axis was LA phonon mode reflected direct correlation with the increase
observed in pristine MoS2 single crystals upon formation of in ion fluence and consequent increase of S defect density
single vacancies and vacancy clusters by hydrogenation (out- (Figure 41c). It is noteworthy to specify that Zhao et al.
of-plane magnetic easy axis) and proton irradiation (in-plane reported a detailed summary of the recent progress on
easy axis).843 The gas sensitivity of monolayer MoS2 increased irradiation-induced defect engineering of the 2H-MoS2 few
significantly due to electronic structure modifications upon layers.852
incorporation of excessive defects.844 Electron beam irradi- 6.5.3. Grain Boundary. Large area 2D MC thin film
ation,253,255,844 ion beam irradiation,845−847 plasma treat- synthesis almost produces polycrystalline films with grain
ment,848 thermal annealing,842 and chemical functionaliza- boundaries (GBs). Engineering the structure and/or the
tion849 are the often-used defect generation technique reported density of GBs is crucial to tailor the performance of
to date for MoS2. Among them, ion beam irradiation has mechanical properties, 853,854 photovoltaics, 855,856 elec-
shown better controllability over the defect type and defect tronics,857,858 and catalysis.859−861 GBs are the one-dimen-
density. For instance, He et al. demonstrated defect engineer- sional (1D) interfaces between randomly oriented crystal
ing of a monolayer MoS2 with a controlled density of S domains.107,254,812,862Figure 42a,b exhibit the perspective side-
vacancies, by 500 keV Au ion irradiation (Figure 41).850 and top-viewed structures of an annealed polycrystalline MoS2
Raman spectroscopy systematically used with respect to ion thin film with an average grain size of 12 nm. Depending on
fluences (Figure 41a). At a low ion fluence (LD > 10 nm, LD the tilt angles and the relative translation between neighboring
stands for average distance between neighboring ion impact grains, a variety of topological dislocation cores with different
sites), both A1′ and E′ peaks shifted toward a lower polygonal ring numbers (e.g., 5|7, 4|4, 4|6, 4|8, and 6|8) are
wavenumber, indicating the presence of compressive strain generated at the GBs. The topology and polarity of these
generated due to the creation of S vacancies.851 Meanwhile, dislocation cores dictate the mechanical strength of 2D MCs.
with increasing ion fluence (LD < 10 nm), the E′ peak shifted Even the presence of a single dislocation core can alter the
toward a lower wavenumber and the A1′ peak shifted more structural characteristics and rise in polar stress−concentration
toward a higher wavenumber, and both the peaks became in a monolayer MoS2.863 Stress concentrates locally at the GBs
broad. This result indicates that, with increasing ion fluence, because the local lattice becomes distorted due to the presence
the Mo−S bond progressively dissociateed to create a greater of dislocation cores at the grain boundaries.854 The typical
number of S vacancies. With the increasing number of S distribution of von Mises stress in a polycrystalline MoS2
Chem. Rev. 2023, 123, 3329−3442
Figure 44. (a) OM image of a WSe2/MoSe2 heterobilayer prepared by mechanical stacking. (b) Scheme of the hBN-encapsulated WSe2/MoSe2
heterobilayer. (c) Moiré superlattice formation by vertical stacking of WSe2 and MoSe2 monolayers with a twist angel of θ. (d) SEM images of
laterally integrated three monolayer WS2/WSe2 superlattices. (e) False-color SEM images of superlattices (I to V) with decreasing width ratio
between WS2 and WSe2. (f) Normalized PL spectra of intrinsic WS2 (dashed line) and WS2 in the superlattices I to V. Inset shows the
representative PL spectrum of the WS2/WSe2 superlattice, showing the shift in their respective peak upon superlattice formation with respect to
their intrinsic PL peak position. (a−c) Reprinted with permission from ref 890. Copyright 2020 American Association for the Advancement of
Science. (d−f) Reprinted with permission from ref 553. Copyright 2018 American Association for the Advancement of Science.
shows heterogeneous atomic-level stress in the vicinity of GBs phases into thermodynamically stable phases along its trace
(Figure 42c), which is different from the bulk grains having (Figure 43a).874 Zheng et al. found that twinning is much
uniform atomic-level stress. Figure 42d,e present the magnified easier than a dislocation slip in 2D ReS2 and concluded that
microstructures of the GB loop (Figure 42d) and a double Y- the highly mobile GBs are inversely pinned by the relatively
shaped GB junction (Figure 42d). The GBs with a high tilt immobile dislocations (Figure 43b).875 The effects of GBs on
angle (60°, between grain 1 and 4 in Figure 42d) consisted of the properties of 2D MCs are complex and diverse, providing
the dense 5|7 and 6|8 dislocations; however, the GBs with a exciting opportunities to realize new functionalities by
low tilt angle primarily consisted of the isolated 5|7 manipulating the local structure and properties. For instance,
dislocations.854 Analysis of the GBs have recently made Chua et al. has recently demonstrated that an atomically
remarkable progress, including Raman,107 ADF-STEM,275 reconstructed VSe2 monolayer with Se-deficient 1D defects has
multiphoton microscopy technique for rapid visualization,864 room-temperature ferromagnetism (Figure 43c).876 He et al.
photoluminescence imaging,865,866 second harmonic gener- recently synthesized wafer-scale MC thin films with an
ation,867 nonlinear optics,868 and other methods.869−871 The ultrahigh density of GBs (∼1012 cm−2), which shows an
third-harmonic generation microscopy provides excellent excellent hydrogen-evolution performance due to an intrinsi-
sensitivity and high speed for grain boundary visualization cally high activation of the MC GBs.877 Huang et al. reported
regardless of the degree of crystal axis rotation. an unexpected band gap tunability (as large as 0.85 ± 0.05 eV)
GBs have major effects on the physical, chemical, and with distance from the grain boundary in a single-layer MoS2,
electrical properties of low-dimensional MCs. For instance, the which also depends on the grain misorientation angle.878 GBs
degradation of transport properties via scattering of majority may also sometimes be optically hidden inside an apparently
carriers at the GBs in addition to the formation of electrostatic single-crystal triangular grain. For instance, Zhang et al.
barriers is amplified in 2D MCs compared to the traditional demonstrated a special 2D core−shell growth mode of a
mesoscopic semiconductors.872 Wang et al. has recently monolayer MoS2, which led to one kind of “pseudo” single-
employed a direct laser writing technology to engineer the crystal triangles containing triangular outline grain boundaries
GBs of a monolayer MoS2. The engineered GBs exhibited (TO-GBs). It was artfully hidden inside the monolayer MoS2
short- and long-term plasticity that enables them to respond triangle and was unidentified by OM.879
simultaneously to electrical and light-based stimuli.873
Through in situ annealing experiments, Zhao et al. have 6.6. Moiré Superlattice Formation
shown that stacking faults and rotational disorders in Spatially periodic structures with a long-range period can be
multilayered 2D MoSe2 crystals can be healed by GB sliding, obtained in vdW MC bilayers in the presence of a small
which works like a “wiper blade” to correct all metastable rotational misalignment (stacking angle) or of a lattice
Chem. Rev. 2023, 123, 3329−3442
Figure 45. Electronic switching devices. (a) Scheme of the transistor using a metallic SWCNT as the gate electrode that enabled 1 nm gate length
(Lg). (b) Structure of the transistor using 0.34 nm side-wall MoS2 grown on the edge of graphene. (c) Up-to-date achievements in the scaling down
of gate length by using different channel conditions. (d) Scheme of the high performance MoS2-based backplane on a 4-in. carrier glass substrate for
fabricating an active-matrix full-color flexible and wearable display. (e) OM image of the back-gated WSe2 transistors with neighboring VSe2 NPs
acted as the vdW contacts and the channel length defined by edge-to-edge gap. (f) The devices with vdW contacts showing improved carrier
mobility and narrower mobility distribution compared to the devices with conventional metal contacts. (g) Drain current (ID)−drain voltage (VD)
curve of a MoS2 memtransistor at gate bias VG = 10 V. The direction of the drain bias (VD) sweep (1 to 4) is indicated by colored arrows. (h) ID−
VD curves for ten consecutive sweeps at each gate bias VG for the same device. (i) Statistical distribution of the set/reset voltages for 73 MoS2
memristor devices on a 2-in. wafer. Inset shows MoS2 memristors. (j) Accuracy comparison of the fabricated 3-layer convolutional neural network
executed in-memory with a conventional graphics processing unit (GPU)-based neural network. (k) Stable and bipolar resistive switching
characteristics of 3D stacked MoS2 memristors. (l) Schematic presentation of the 3D memristor array with buried metal interconnections and logic
circuits. (a−c) Reprinted with permission from ref 3. Copyright 2022, Rights Managed by Nature Publishing Group. (d) Reprinted with permission
from ref 913. Copyright 2020 American Association for the Advancement of Science. (e−f) Reprinted with permission from ref 130. Copyright
2020, Rights Managed by Nature Publishing Group. (g, h) Reprinted with permission from ref 4. Copyright 2018, Rights Managed by Nature
Publishing Group. (i−l) Reprinted with permission from ref 931. Copyright 2022, Rights Managed by Nature Publishing Group.
mismatch between the monolayers, referred to as a moiré introducing a tensile strain in the bilayer MoS2 film through a
pattern or in-plane moiré superlattice.880 For instance, water bath.886 The formation of a moiré superlattice reduces
Schouteden et al. demonstrated the formation of a moiré the interlayer potential barrier and thereby significantly
superlattice for the bulk single crystal Bi2Te3 by in-plane enhances the catalytic performance. Instead of a bilayer of
rotation of the topmost quintuple layer (QL) of Bi2Te3.881 the same material, Moiré superlattices have also been created
Moiré superlattice formation can modulate the electronic band by stacking and twisting of two different materials, such as a
structure of the material and lead to emergent properties such MoSe2 monolayer on a WSe2 monolayer,887 a GaSe monolayer
as superconductivity,882 magnetism,883 topological edge on a MoSe2 monolayer,888 a MoS2 monolayer on a WSe2
states,884 etc., which are not obtainable with individual monolayer,880 and a SnS2 monolayers on a WSe2 mono-
layers.885 The twisted angle also plays a crucial role in the layers.889 Only vertical stacking of MC monolayers does not
formation of moiré superlattices and the properties of 2D necessarily yield a moiré superlattice. As the lattice constants of
MCs. For instance, Jiang et al. demonstrated the trans- MCs having common chalcogen atoms typically exhibit a small
formation of a planar MoS2 film to a twisted MoS2 scroll lattice mismatch, they are the ideal candidates for moiré
(twisted angle of θ ≈ 7.3°) with a moiré superlattice, by superlattice formation. For instance, Tran et al. demonstrated
Chem. Rev. 2023, 123, 3329−3442
the formation of a heterobilayer moiré superlattice by stacking applied to suppress such movements. This type of carrier
the MoSe2 monolayer on the WSe2 monolayer with a small movement increases the off-state current of the devices,
twist angle of ∼1°. When the MoSe2/WSe2 heterobilayer was produces static power, and causes heat generation. Silicon
encapsulated inside high quality hBN, an equally spaced transistors approach their physical limitations; hence, alter-
interlayer exciton resonance was observed at low temper- native materials that can outperform silicon are required.
ature.887 However, in an hBN-encapsulated WSe2/MoSe2 Atomically thin semiconducting 2D MCs having band gaps
heterobilayer (Figure 44a−c), Choi et al. have demonstrated larger than silicon, specifically MoS2, WS2, and WSe2, have
that the moiré period decreased as the twist angle increased, emerged as attractive materials due to their large switching
and the excitons tunneled between supercells and diffused over ratios and suppressed source-to-drain tunneling current (i.e.,
a longer lifetime. In the case of commensurate hetero- lower static power) at the scaling limit.894,895 Since the
structures, the moiré superlattice was absent and the exciton growing demand for nanosized device fabrication asked for
diffusion was the longest.890 Due to the minor lattice distortion thinner channel materials, atomically thin monolayer semi-
in each layer during the CVD growth of rotationally aligned conductors are in the forefront of device innovation.896
heterobilayer MCs (e.g., WSe2/MoSe2), commensurate atomic Additionally, their tunability of electronic band structure
alignment was usually observed instead of a moiré pattern.891 adjusted by variation of thickness, doping concentration, and
Superlattice formation has also been achieved in the case of defects provides a broad range of band gaps and semi-
dislocation-free laterally integrated MC monolayers. For conductor-to-metallic transitions.246
instance, Xie et al. demonstrated WS 2/WSe2 laterally Currently, it is difficult to achieve a gate length (Lg) of less
integrated superlattices grown by an omnidirectional epi- than 5 nm by using standard electron beam lithography (EBL).
taxy.553 The superlattices possessed fully matched lattice Gate lengths of 3 nm for state-of-the-art Si transistors were
constants across the hetero interfaces; thus, the isotropic fabricated on a silicon-on-insulator substrate utilizing atomi-
lattice structure and triangular symmetry were maintained over cally sharp V-shaped grooves produced by anisotropic wet
the entire crystal (Figure 44d,e). As shown in Figure 44f, due etching.897 Approaching the ultimate Lg scaling limits, Desai et
to the presence of epitaxial strain at the interfaces, the PL peak al. demonstrated MoS2 transistors with a 1 nm Lg using a
of MCs shifted significantly to as high as 0.25 eV. metallic single-walled carbon nanotube (SWCNT) as the gate
electrode (Figure 45a).127 These ultrashort devices exhibited
7. APPLICATIONS excellent switching characteristics and a high on−off ratio of
106. Wu et al. demonstrated side-wall MoS2 transistors with an
The potential applicability of the anisotropic MCs including
1D (NWs, NTs, and NRs) and 2D (NPs, NSs, thin films) has atomically thin channel and an Lg of 0.34 nm using the edge of
been proven in a variety of research areas due to their a graphene layer as the gate electrode (Figure 45b).3Figure 45c
outstanding optical, electronic, physical, and chemical proper- demonstrates the up-to-date achievements in the scaling down
ties. Since their intrinsic properties can be further tailored of gate length by using different channel conditions. Wu et al.
through modulation of dimension, phase, composition, defects, also demonstrated the wafer-scale (2-in.) fabrication capability
and heterostructures, they are expected to further widen the of the side-wall MoS2 transistors, where the Lg of 0.34 nm
possible applications. This section reviews recent advances in approaches the ultimate scaling limits. The side-wall transistors
applications of the anisotropic MCs. showed good switching characteristics with the on/off ratio up
to 1.02 × 105. Jiang et al. recently succeeded in fabrication of
7.1. Electronic Devices short vertical channel FETs (channel length = ∼10 nm) of
Anisotropic MCs have been emerging as an exciting material MoS2 and MoTe2, which shows a large on-current density of
system for a wide range of electronic applications due to their 70 μA μm−1 nm−1 at a source−drain voltage of 0.5 V and a
unique optical and electronic properties. Most importantly, 2D high on/off current ratio of 107−109.898 Sarkar et al. also
MC semiconductors have attracted intensive interest because reported MoS2-based novel band-to-band subthermionic
atomically thin active channels can facilitate continuation of tunnel FETs with a vertical source-channel junction, which
the transistor scaling. Despite many proof-of-concept demon- exhibited steep turn-on and a minimum subthreshold swing of
strations, the full potential of anisotropic MCs as next 3.9 mV per decade.5
generation switching devices has yet to be determined. This Compared to the electron mobility of Si (1400 cm2 V−1 s−1)
section reviews the current status of anisotropic MCs for and GaAs (8500 cm2 V−1 s−1), monolayer TMDCs have low
electronic switching devices and their state-of-the-art large-area carrier mobility (typically <300 cm2 V−1 s−1 at room
fabrication process. temperature), which also varies with experimental measure-
7.1.1. Transistors. In typical field-effect transistors (FETs), ment conditions.457,899−907 Cheng et al. proposed theoretical
the current flow in the semiconductor channel is associated predictions on the intrinsic mobilities of 774 cm2 V−1 s−1 and
with the source−drain voltage (VDS) and can be modulated by 395 cm2 V−1 s−1 for H-WS2 and H-MoS2, respectively;124,908
the electric field through the applied gate voltage (VG). High the experimental results achieved similar values.29,31,32 In the
charge carrier mobility, high on-state current, high on/off InSe FETs, Li et al. achieved an unprecedented high electron
current ratio, and low leakage current at the off-state are the mobility up to 3700 cm2 V−1 s−1 at room temperature and a
necessary conditions to achieve effective switching and low high Ion/Ioff ratio of 107.909 They used the surface charge
power consumption during transistor operation.892,893 Follow- doping strategy induced by indium encapsulation. Bandurin et
ing Moore’s prediction regarding density of transistors in a al. also reported the hBN-encapsulated InSe FETs showing
chip, aggressive scaling down of the channel length (currently carrier mobilities exceeding 103 cm2 V−1 s−1 at room
<10 nm) in 3D Si based FETs has been made over the past five temperature and 104 cm2 V−1 s−1 under a liquid-helium
decades. However, with decreasing channel length, the atmosphere.208 Interface engineering between semiconducting
tunneling current between the source and drain electrodes is MCs and the dielectric layer has been employed to enhance
inevitable even in the presence of gate voltage specifically the efficiency of FETs. For instance, Zou et al. utilized an
Chem. Rev. 2023, 123, 3329−3442
ultrathin metal oxide (MgO, Al2O3, and Y2O3) buffer layer perception in which memory and computation for motion
inserted between the HfO2 and MoS2 channel to minimize the detection and recognition are possible.925 Individual mono-
interface defect density, which improved room temperature layers of 2D MCs can also be used as LEGO-like building
mobility (63.7 cm2 V−1 s−1) and the on/off current ratio blocks to create a variety of other heterostructures for use in
(>108).910 Using an atomically thin h-BN as a tunneling layer the light-emitting memristors for optoelectronic artificial
for reducing the contact resistance between metal and MoS2, efferent nerve systems.926,927 Sangwan et al. fabricated a
Wang et al. fabricated a high mobility (73 cm2 V−1 s−1) MoS2 multiterminal hybrid device of a memristor and transistor (i.e.,
transistor with a Schottky barrier height of 31 meV (improved memtransistor) using polycrystalline MoS2.4Figure 45g shows
from 158 meV) and a contact resistance of 1.8 kΩ·μm the ID−VD curve of the MoS2 memtransistor at a gate bias of
(improved from 5.1 kΩ·μm).905 Due to their intrinsic high VG = 10 V, where the direction of the applied drain bias (VD)
mobility and good Ion/Ioff ratio, MC-based semiconductors are sweep is indicated by colored arrows. The device was in a high-
one of the most promising candidates for backplane transistors resistance state (HRS) in the pristine state, and gradually
of next generation display, in which high spatial resolution and changed to a low-resistance state (LRS) during the VD sweep
charge mobility of pixel transistors are simultaneously from 0 to 80 V (sweep 1) and maintained the LRS state during
mandatory.911,912 Choi et al. recently fabricated a wearable sweep 2 (80 V to 0 V). It was reset to the HRS state during
full-color organic light-emitting diodes (OLEDs) display sweep 3 (0 V to −80 V) and maintained the HRS state during
integrated with a wafer-scale MoS2-based backplane transistor sweep 4 (−80 V to 0 V), acting as LRS-HRS memtransistors.
array.913 In the demonstration, the backplane transistors were Figure 45h presents the ID−VD characteristics of the device for
specifically designed as a driving and switching component for ten consecutive sweeps at different gate biases (VG, varied from
each color pixel made of different organic materials (Figure 50 V to −50 V), showing an LRS and HRS resistance change
45d). of 104 and a switching ratio (ILRS/IHRS at VD= 0.5 V) change
The atomically clean interface of vdW metal/semiconductor from 300 to 8. The device showed a field-effect mobility of 0.6
heterostructures such as VSe2/WSe2, NiTe2/WSe2 enabled the cm2 V−1 s−1 in the HRS and 0.3 cm2 V−1 s−1 in LRS. Through
construction of high-performance electronic devices with Li+ ion migration under an electric field, reversible local 2H-
persistent performance and high on-current density. For 1T′ phase transition of MoS2 was achieved, where the
instance, Li et al. fabricated (VSe2/WSe2)-WSe2-(VSe2/ memristive behavior of the device can be directly correlated
WSe2) transistors, where the neighboring VSe2 NPs function with local ion exchange, similar to synaptic competition and
as the vdW source and drain electrodes (Figure 45e).130 The synaptic cooperation effects observed in biology.928 In addition
vertical heterostructure showed Ohmic contact and a typical p- to the conventional neural learning behavior of long-term
type-transistor behavior with Ion/Ioff = 107. The mobility potentiation and depression, the memtransistors showed gate
distribution of this vdW vertical heterostructure device tunability in individual resistance states, as well as large
indicates that vdW contacts improve the carrier mobility switching ratios, high cycling endurance, and long-term
significantly (137 cm2 V−1 s−1) and show a much narrower retention of states. Zhang et al. has reported a MoTe2 and
mobility distribution (Figure 45f). In contrast to the vdW Mo1−xWxTe2 based resistive random-access memory (RRAM)
vertical heterostructure devices, the devices with deposited device showing an Ion/Ioff = 106. The switching mechanism
metal contacts showed inferior performance and broader relies on electric-field-induced structural transition from the
mobility distribution, which can be attributed to the induced semiconducting phase to a distorted transient structure (2Hd)
contamination at the contacting interface during lithography or and orthorhombic Td conducting phase in vertical device made
metal deposition.914 of 2H-MoTe2 and Mo1−xWxTe2.730,929 Generation of S and W
7.1.2. Memtransistors. The emerging technology of vacancies in WS2 and electron hopping between vacancies have
neuromorphic computing, inspired by the energy efficient also been observed to be responsible for the resistance
neural networks of the human brain, is capable of massive switching performance and facilitate realization of low-power
parallel computing and is expected to overcome the consumption for neuromorphic computing application.930
fundamental limitations of current computing architec- Tang et al. recently demonstrated wafer-scale integration of
tures.4,915,916 The large connectivity between the neurons the solution-processed 2D MoS2 memristor arrays for next-
and precise adjustment of the ionic flow through synapse is the generation information storage and neuromorphic computing
key to the highly efficient parallel processing of the biological (Figure 45i−l).931 The reproducibility of the devices was
systems. The memristor is a two-terminal electronic device obtained by measuring the distributions of Vset and Vreset of 73
whose conductance can be reversibly regulated by electric devices over the entire wafer, showing the variation of only
stimuli.917 Memristors have been developed for use in 19.7% and 18.5%, respectively (Figure 45i). The wafer-scale
nonvolatile resistive random-access memory and may also be RRAM array also showed a high recognition accuracy of
useful in neuromorphic computing.918−920 Anisotropic MCs 98.02% when trained with 50,000 images by using the in-
exhibit several unique properties such as rich polymorphism, memory computation technique (Figure 45j). 3D stacking of
stacking polytypes, phase transformation, interfacial charge the three-layer MoS2 memory cells was also fabricated by
trapping, and ferroelectric/ferromagnetic properties. Such sequential deposition of Ti, MoS2, and Pt. Each memory stack
unique properties can be used to create futuristic memristive (Ti−MoS2−Pt) was programmed independently and exhibited
and artificial synaptic devices,921−923 because the operational stable bipolar switching characteristics (Figure 45k,l).
mechanism of the 2D MC-based memristive and synaptic
devices also includes interfacial electrostatic modulations, 7.2. Optoelectronic Devices
charge transfer, phase transformation, and gate-tunable energy Giant anisotropic optical properties and large emission
band shift. 924 Moreover, the availability of numerous intensities of 1D MC NWs have been achieved by controlling
combinations of 2D MC heterostructures allows the the diameter, length, and chemical compositions for use in
fabrication of retinomorphic devices with an all-in-one efficient optoelectronic devices. Their band gap tunability is
Chem. Rev. 2023, 123, 3329−3442
Figure 46. Optoelectronic devices. (a) Wavelength-dependent photoresponsivity curve of the MoS2 thin film photodetector. (b) Partial electron
density of the grain line-type defect structure in MoS2, which is responsible for its near-infrared (NIR) optical absorption. Mo atom and S atom are
depicted in gray and yellow sphere, respectively. (c) Scheme of the WSe2−MoS2 (p−n) vdW heterojunction device under laser irradiation. (d)
Energy band diagram of the p-n heterojunction with photogenerated carriers under laser beam irradiation. (e) Photoresponsivity of the transistor
based on the WSe2−MoS2 vdW heterojunction. (f) Scheme of the MoS2-based phototransistors with an out-of-plane p−n homojunction. (g)
Transfer characteristics of the pure n-doped MoS2 detector and a surface-doped device with an out-of-plane p−n junction. (h) Comparative energy
band diagram of the out-of-plane p−n junction at the interface (top panel) and the n-doped MoS2 transport channel (bottom panel) with different
applied bias voltage. (a,b) Reprinted with permission from ref 15. Copyright 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. (c−e)
Reprinted with permission from ref 15. Copyright 2020 American Chemical Society. (f−h) Reprinted with permission from ref 938. Copyright
2017, Rights Managed by Nature Publishing Group.
promising for light generation, and the high aspect ratio is 7.2.1. Photodetectors. The photodetector is a key
beneficial in guiding the propagation of the light.932 The component of many devices in state-of-the-art technologies,
thickness-dependent band gap variation and the indirect-to- ranging from autonomous vehicles, environmental monitoring
direct band gap crossover of 2D MCs (e.g., the indirect band systems, security systems, mobile phone cameras, and
gap of 1.3 eV in MoS2 bulk increases to a direct band gap of telecommunications systems.20,185,933 Photodetector perform-
1.8 eV in a single layer MoS2) open the possibility of ance indicators are responsivity (R), response time (τ), specific
optoelectronic devices.1 Moreover, their unique optical detection rate (D*), and spectral selectivity. Despite
introductions of many new 2D vdW materials, 2D MoS2 still
properties such as strong light−matter interaction and large
remains a promising semiconductor for optoelectronic
exciton binding energy, and the strong light emission and
applications. In particular, MoS2 phototransistors have been
absorption in the visible to near-infrared wavelength range,
investigated with respect to various structures and mecha-
make them attractive for unconventional optoelectronic nisms.16,133,134,934−941 The first monolayer MoS2 photo-
applications. They have become increasingly important in transistor exhibited a responsivity of 7.5 mA/W,134 and the
optoelectronic applications such as photodetectors, light multilayer MoS2 phototransistor showed over 100 mA/W,935
emitting diodes (LEDs), solar cells, lasers, and optical switches. with a response time of ∼50 ms. Lopez-Sanchez et al.
Optoelectronic devices that are flexible and transparent are demonstrated a monolayer MoS2 phototransistor with a high
also expected to extend the applications in solar arrays, responsivity of 880 A/W;941 however, the observed response
wearable electronics, and transparent displays. time was in the range of several seconds due to the trap states
Chem. Rev. 2023, 123, 3329−3442
around the channel. Driven by poly(vinylidene fluoride- energy band diagram of the out-of-plane PN junction at the
trifluoroethylene) (PVDF) ferroelectrics, the detectivity and interface (top panel) and pristine N-MoS2 transport channel
responsivity of a multilayer MoS2 photodetector reached 1012 (bottom panel) with different applied bias of VG < VT and VG
Jones and 2570 A/W.16 Lee et al. demonstrated a high- > VT, respectively is shown in Figure 46h. Zhang et al.
performance MoS2 phototransistor that exhibited photo- demonstrated a monolayer MoS2 lateral p−n homojunction
response in the 400−700 nm range with a maximum photodiode, where the piezo-photonic effect was used to
responsivity of over 1 × 104 A/W.942 However, the CVD achieve the broadening of the depletion zone at the p−n
grown large-area MoS2 monolayer film photodetectors showed junction interface, and hence the significant enhancement in
a relatively lower responsivity of 0.8 mA/W.943 Giri et al. photoresponsivity and detectivity was observed compared with
synthesized a microwave-assisted MoS2 thin film and fabricated the strain-free state.956 Simultaneously, several other photo-
an array of photodetectors over a HfO2 dielectric layer.15 The active 2D MCs have also been studied, such as III−VI MCs
photodetector showed high photoresponsivity over a wide (e.g., InSe, 957−961 α-In 2 Se 3 , 962−965 GaSe, 966−968 and
range and a fast response time (124 μs): 100 mA/W at λ = 375 GaTe969,970) and IV−VI MCs (e.g., SnS,971−973 SnS2,974−977
nm, 315 mA/W at λ = 610 nm, and 140 mA/W at λ = 1000 and SnSe2933,978). Quantum-confined colloidal II−VI semi-
nm (Figure 46a). Their photodetector showed excellent near- conductor NWs, NRs, and NPs exhibiting size-controlled band
IR photoresponsivity as well, which was attributed to the small gaps and electronic structures also offer great promise for
grain size (∼4.5 nm) of the microwave-assisted synthesized potential applications in optoelectronics and sensors.53,979−982
MoS2 thin films (Figure 46b).15 For instances, Shalev et al. demonstrated a fast photodetector
In order to improve the performance of MoS2 photo- (response time of 2 μs and a large gain of 102) by using single-
detectors, many research groups have implemented hetero- crystal CdSe NWs.979 Penner et al. reported a photodetector
junction formation with graphene, p−n heterojunction array based on nanocrystalline CdSe NWs.983 A UV−visible
formation with TiO2, and environmental protection of MoS2 photodetector made of a single CdS NR exhibited a high
by the Al2O3, HfO2, or hBN layer.17,944−947 For instance, De responsivity of 1.23 × 104 AW−1 at a bias voltage of 2 V.980
Fazio et al. demonstrated a high responsivity, with large-area ZnS, a well-known wide band gap semiconductor, is a suitable
graphene/MoS2 flexible photodetectors having an external candidate for UV detection. Fang et al. demonstrated a UV
responsivity of 45.5 A/W and an internal responsivity of 570 detector made of single-crystalline ZnS NBs that exhibited
A/W at 642 nm.948 Paul et al. fabricated a broad-band ultrafast switching performance.984 Various doped ZnS nano-
photodetector from monolayer MoS2 CVD-grown on a TiO2 crystals and their solid solutions have been developed to obtain
nanostructure.949 This heterojunction photodetector exhibits a the hole conductivity while maintaining good optical trans-
high responsivity and detectivity of 18.5 A/W and 1.09 × 1013 parency in visible light.53
Jones, respectively, in the visible region. Kufer et al. has shown 7.2.2. Light Emitting and Light Harvesting Devices.
that a simple encapsulation by HfO2 on MoS2 can significantly The strong light−matter interaction and direct band gap
improve the photodetector performance by preventing the property of MCs make the heterostructure of MCs promising
strong current drifting and environmental degradation.934 candidates for the construction of next-generation photo-
Band engineering based on the vdW heterostructure of 2D diodes128,985 as well as light-emitting986,987 and light-harvesting
MCs allowed for the realization of high-performance devices.988,989 The structure of the active light emitting layer
optoelectronic devices by providing an ultrathin and spatially can be either single-layer MCs990−992 or lateral p−n
uniform PN heterojunction with sharp band edges and low junctions.808,987,989,993 For instance, Ye et al. fabricated an
trap states.184,950−955 For instance, Shin et al. fabricated a WSe2 electroluminescence diode of a monolayer MoS2 on a heavily
and MoS2 heterostructure device (Figure 46c), where MoS2 doped silicon substrate.994 Jo et al. investigated optoelectronic
was utilized as the channel for a phototransistor, whereas the properties of atomically thin light-emitting transistors that were
WSe2−MoS2 PN junction in the out-of-plane was utilized as a gated through an ionic liquid on a WS2 monolayer and
charge transfer layer.15 As shown in the energy band diagram bilayer.995 Ponomarev et al. fabricated an ambipolar light-
of the PN junction under laser beam irradiation (Figure 46d), emitting transistor based on a monolayer MoS2, where the
the vertical built-in electric field in the PN junction separated observed electroluminescence originated from the exciton
the photogenerated carriers; hence, the electrons moved from recombination in MoS2 at the region close to the hole-injection
WSe2 to MoS2, whereas the holes in MoS2 moved to WSe2. contact.996 It has also been demonstrated that vertically
This charge movement led to the modulation of the stacked vdW heterostructures can also lead to more efficient
conductance of the MoS2 channel by photogenerated charges and large area light emission.986,997,998 For instance, Withers et
(photogating effect). The device shows a high photo- al. fabricated light emitting quantum wells (LEQWs) with a
responsivity of 2700 A/W under laser illumination of variable low-temperature external quantum efficiency (EQE) of 1% by
power (Figure 46e), specific detectivity of 5 × 1011 Jones, and forming vdW heterostructures consisting of monolayers of
response time of 17 ms. MoS2 sandwiched between atomically thin hBN and graphene
Konstantatos et al. fabricated an ultrasensitive MoS2 electrodes.992 Xu et al. has shown vertically stacked bilayer
phototransistor enabled by an out-of-plane MoS2 p−n heterostructures of WS2/MoSe2 that exhibited a correlated
homojunction (Figure 46f).938 By facile chemical doping, a blinking effect. The device comprised randomly switching
vertical built-in field is introduced in the transport channel of bright, neutral, and dark states, in which the bright state
the MoS2 phototransistors, which efficiently separates the occurring in one monolayer simultaneously led to a dark state
photoexcited carriers. The device shows a responsivity of 7 × in the other monolayer due to an intermittent interlayer carrier
104 A/W and a photoresponse time on the order of 10 ms. The transfer process.128 Using spatial and spectral confinement of
p−n junction device showed a dramatic shift in the threshold light, emission from MCs can be further enhanced. Initial
voltage (VT) from −3 V to 30 V due to the depletion of experiments with cavity integrated MCs have shown operation
charges across the PN junction (Figure 46g). A comparative of strongly coupled exciton-polaritons at room temper-
Chem. Rev. 2023, 123, 3329−3442
Figure 47. Light emitting and light harvesting devices. (a) Scheme of the cavity coupled electroluminescence (EL) measurement setup and device
structure. (b) I−V characteristics of the light-emitting heterojunction device. Inset shows the SEM image of the photonic crystal cavity. (c) EL
spectrum measured from the cavity area (blue line) and away from the cavity area (red line). (d) Optical image of 4-in. and 2-in. (in the inset)
wafer-scale μ-LEDs driven by MoS2 TFTs on GaN/silicon and GaN/sapphire wafers, respectively. (e) Brightness control in each pixel of the MoS2-
TFT-integrated μ-LEDs on both silicon wafer (top) and sapphire wafer (bottom), by applying gate-source voltage (VGS) and data voltage (VDD).
(f) Energy level diagram for MoS2, SnO2, and TiO2 as electron transport layer (ETL) used in perovskite solar cell (PSC) fabrication. (g) Current
density−voltage (J−V) characteristics of the PSC under one sun condition. (h) Comparative incident photon to electron conversion efficiency
(IPCE) spectra for the PSC device fabricated with different ETLs. (a−c) Reprinted with permission from ref 1004. Copyright 2017 American
Chemical Society. (d,e) Reprinted with permission from ref 1005. Copyright 2022, Rights Managed by Nature Publishing Group. (f−h) Reprinted
with permission from ref 1016. Copyright 2019 Royal Society Chemistry.
ature,999,1000 and optically pumped nanolasers.1001−1003 In was single mode and linearly polarized (84%) along the cavity
order to integrate monolayer LEDs with the nanocavity, Liu et mode. Large-scale integration of 2D MCs with other
al. fabricated a tunneling diode with a photonic crystal compound semiconductors is essential for their implementa-
nanocavity based on a vdW vertical heterostructure.1004 They tion as active matrix displays or optical sensors. In a recent
sandwiched a monolayer WSe2 (light emitter) between study, Hwangbo et al. demonstrated fabrication of a MoS2 thin
graphene and hBN electrodes. (Figure 47a). Upon applying film transistor array on a 4-in. GaN-based epitaxial wafer, and
a bias voltage across two graphene layers, the injected electrons subsequent monolithic integration with μ-LEDs (Figure
and holes tunnel from the top and bottom graphene layers into 47d).1005 The brightness of each pixel was controlled by
WSe2, leading to I−V characteristics as shown in Figure 47b. gate-source voltage (VGS) and data voltage (VDD) values, and
The injected electrons and holes from top and bottom the observed emission area ratio of the μ-LEDs was 26% and
electrodes form excitons in WSe2. The radiative recombination 100% on the Si and sapphire wafer, respectively (Figure 47e).
of the excitons gives rise to electroluminescence (EL). Locally The photoluminescence of the colloidal II−VI NPs and NBs
enhanced electroluminescence has been observed due to the has also been investigated extensively as promising emissive
nanocavity formation (Figure 47c), and the observed emission materials for solution processed optoelectronic devices such as
Chem. Rev. 2023, 123, 3329−3442
LEDs and lasers.1006−1009 For instance, van der Bok et al. conversion efficiency (IPCE) spectra (Figure 47h) are shown
recently demonstrated the fabrication of white LEDs by using for the perovskite solar cell devices fabricated with standard
CdSe NPs, which exhibited a narrow spectral width of exciton ETLs. Therefore, the result clearly indicates highly efficient
emission.1010 Wen et al. demonstrated a pure green (521.5 electron transport ability, similar to standard ETLs, of the
nm) LED based on CdSe/CdS core/crown colloidal NPs, in directly grown MoS2 on glass/FTO substrate. Nazif et al.
which nonradiative recombination during the charge injection recently demonstrated flexible WSe2 solar cells, where a
process was successfully suppressed. Thereby the devices transparent graphene contact was used to mitigate Fermi-level
showed a peak EQE of 2.16%, which is a 6-fold enhancement pinning and MoOx capping was used for doping, passivation,
comparing to the stacked NP LEDs. 1008 She et al. and antireflextion coating.1021 The flexible WSe2 solar cells
demonstrated an amplified spontaneous emission and lasing device showed a record specific power of 4.4 W g−1, which was
by using colloidal CdSe NPs of different thickness. The a remarkable increase in PCE (5.1%) for the flexible WSe2
multiexciton recombination in the NPs was found to be largely solar cell (previously reported value of <0.7%).1022 The PEC
independent of lateral dimensions, in contrast to the quantum increase was due to the defect state created at the Au−WSe2
dots and quantum rods.1011 Using colloidal CdS NPs as the interface during electron beam evaporation of Au which
gain medium, lasing has also been observed in a linear optical pinned the Au Fermi level toward the charge neutrality level of
cavity, which improved spectral tunability as well as elevated WSe2.
multiexciton lifetimes.1006 7.3. Catalysts
The importance of photovoltaic devices has been continually
increasing in the world’s renewable energy mix. Bernardi et al. Among various kinds of catalysts, MCs have been extensively
showed that the monolayers of MoS2, MoSe2, and WS2 can studied in electrocatalytic hydrogen evolution reactions
absorb up to 5−10% incident sunlight, which is 1 order of (HERs). Hydrogen possesses a relatively high energy density
magnitude higher than GaAs and Si.1012 The Schottky barrier (142 MJ kg−1) compared to other chemical fuels, and shows
solar cell (based on MoS2 and graphene) and an excitonic solar promise as a substitute for fossil energy. Among the various H2
cell (based on MoS2−WS2 bilayer heterostructure) could production methods there are the following: photocatalytic
attain power conversion efficiencies (PCE) of up to ∼1%. Tsai water splitting, electrolysis of water, steam reforming, natural
et al. demonstrated photovoltaic operation with a power gas oxidation, biomass electrolysis, etc. Electrocatalytic hydro-
conversion efficiency of 5.23% in large-scale MoS2 monolayers, gen production from water is considered as the cleanest
by the formation of a type-II heterojunction with p-Si. The method. Due to the high cost and scarcity of Pt, MCs with a
built-in electric field, generated near the interface between large surface area and high chemical stability have drawn
MoS2 and p-Si, helps the photogenerated carriers to be attention because they are cheap, earth-abundant, and
separated easily.140 The trilayer graphene/MoS2/n-Si solar cell intrinsically active catalysts that can potentially match the
devices exhibit a power-conversion efficiency of 11.1%, where HER performance of Pt. The high surface-to-volume ratio of
the MoS2 thin film was used for passivation as well as a hole- the anisotropic MCs is beneficial for maximizing the exposed
transporting layer.1013 Hao et al. demonstrated a remarkable catalytically active sites. The Sabatier principle indicates that
increase in the PCE of MoS2/Si hybrid solar cells by the interaction between catalysts and reactants should be
employing Pd atoms as a chemical dopant within the MoS2 neither too strong nor too weak. Binding of reactants is not
film.1014 For the MoS2/h-BN/GaAs heterostructure solar cells, favorable when the free energy of adsorption (ΔGH) is too
a PCE of 9.03% has been achieved after electrical gating and high, whereas conversion and desorption are delayed when
chemical doping.1014 ΔGH is too low. The best catalytic performance is regarded to
The ultrathin h-BN layer was inserted between the MoS2/ have been achieved under thermo-neutral conditions (ΔGH =
GaAs heterostructure, in order to suppress the static charge 0). It has been revealed that ΔGH on the MoS2 edge is close to
transfer. Layered MoS2 has also been used as the hole- the thermo-neutral conditions,1023 making MoS2 a promising
transport layer (HTL),1015 power-per-weight of 23 W g−1 layer HER catalyst. Tsai et al. calculated ΔGH on the edges and basal
(ETL),1016 interfacial layer, and protective layer in fabricating planes for 26 different MCs.1024 They found that basal planes
heterojunction solar cells. The highest PCEs in thin-film single- of metallic MCs can be catalytically activated with ΔGH, for
junction MCs were 2.8% in plasma-doped MoS2 and 6.3% in instance as low as 0.05 eV for 1T-VS2, while semiconducting
electrostatically doped MoSe2 solar cells.1017,1018 According to MCs are known to be catalytically inactive. Many studies have
realistic detailed balance models,1019 a PCE of ∼27% can be endeavored to create heterostructures to activate edge sites
achieved in ultrathin single-junction MCs solar cells, leading to through facile electron transfer, modify the morphologies to
extremely high power-per-weight of 23 W g -1 once increase the edge-to-basal plane ratio, and change electronic
implemented on lightweight flexible substrates.1020 Singh et structures by heteroatom doping.
al. reported the use of a MoS2 thin layer as the electron 7.3.1. Heterostructure Control. Enhanced HER perform-
transport layer (ETL) for perovskite solar cells (PSCs) with a ance can be achieved by heterostructure formation. To achieve
device configuration of FTO/MoS2 (ETL)/perovskite layer/ high conductivity to improve electrical contact to active sites,
po-spiro-MeOTAD/Au, exhibiting a power conversion effi- high-conductivity carbonaceous materials are brought into
ciency (PCE) of 13.1%,1016 where the MoS2 transparent thin contact with MCs.1025−1031 Pramoda et al. fabricated
film was directly synthesized on the glass/fluorine-doped tin heterostructures of MoS 2 and MoSe 2 with poly-
oxide (FTO) substrate by using microwave irradiation. On the (diallyldimethylammonium chloride) (PDDA)-functionalized
basis of the measured work function of different standard ETL reduced graphene oxide (rGO) and borocarbonitride
materials (MoS2, SnO2, and TiO2) used in PSC fabrication, the (BC6N).1032 After functionalization of PDDA on rGO and
energy level diagram is shown in Figure 47f. The comparative BC6N, the zeta potential became positive (56.4 mV for rGO
current density−voltage (J−V) characteristics under one sun and 51.3 mV for BC6N). The exfoliated MoS2 and MoSe2 by
condition (Figure 47g) and incident photon to current lithium intercalation showed negative potentials of −48.3 mV
Chem. Rev. 2023, 123, 3329−3442
Figure 48. Catalysts. (a) Scheme of the synthesis route to the hierarchical MoS2/CoS2 NT arrays on carbon cloth. (b) Calculated ΔG of H on
MoS2/CoS2 and MoS2. (c) Mass activity of metal-MoS2 composites and 20 wt % Pt/C catalysts for HER at −0.25 V. (d) The schematic illustration
of the feasible HER mechanism for the 5.2 wt % Rh-MoS2 catalyst. (e) Linear sweep voltammetry spectra for HER performance of a pure and
metal-doped MoSe2 thin films. (f) Gibbs free energy diagram for the pure and metal-doped MoSe2. (a,b) Reprinted with permission from ref 1041.
Copyright 2019, The Royal Society of Chemistry. (c,d) Reprinted with permission from ref 1046. Copyright 2017, Wiley-VCH Verlag GmbH &
Co. KGaA, Weinheim. (e,f) Reprinted with permission from ref 1068. Copyright 2019, American Chemical Society.
and −46.8 mV, respectively. With opposite surface charges of exhibits a high catalytic activity of 225 mA cm−2 at −250 mV
PDDA-functionalized carbonaceous materials and MoS2/ vs RHE, and a Tafel slope of 38 mV dec−1.
MoSe2, simple mixing can form heterostructures between Besides carbonaceous materials, MCs with good electrical
MoS2/MoSe2 and PDDA-functionalized carbonaceous materi- conductivity such as cobalt sulfides and nickel sulfides have
als. HER activities were investigated with varying ratios of MCs been employed as supporting materials for MoS2 and
to carbonaceous materials. With increasing amounts of MoS2 WS2.10−15,1034−1039 Cao et al. synthesized one-dimensional
and MoSe2, HER activity increased, indicating MoS2 and MoS2/Ni3S2 nanoarrays directly grown on a three-dimensional
MoSe2 are active components in H2 evolution. The authors Ni form by one-step hydrothermal synthesis.290 During
insisted that charge transfer from electrostatically attached synthesis, Ni substrate acted as a Ni source to produce Ni3S2
PDDA-functionalized carbonaceous materials to the active NRs. MoS2 grew onto the Ni3S2 NRs to form the MoS2/Ni3S2
sites may assist the catalytic activity. The outstanding NR array. Due to highly exposed MoS2 active edge sites, the
electrocatalytic HER activity of the PDDA-functionalized composite has an onset overpotential as low as 13 mV in 1 M
BC6N-MoS2 (1:5) was found with an activity of 8593 μmol KOH, which is comparable to the Pt-based electrocatalyst for
h−1 g−1 and an onset potential of −50 mV (vs RHE), which is HER. Sun et al. fabricated mace-like MoS 2 /NiCo 2 S 4
comparable to that of Pt. Ko et al. synthesized few-layered hierarchical structure directly grown carbon fiber paper via
MoS2 vertically aligned on 3D interconnected porous carbon the hydrothermal process.1040 The authors used NiCo2S4
NSs for maximizing the exposed edge site of MoS2, which is because of its good electrical conductivity at least 2 orders of
known as active sites of 2H-MoS2.1033 3D interconnected magnitude higher than the individual Ni sulfides and Co
porous carbon NSs acted as not only a conductive support but sulfides. The MoS2/NiCo2S4/carbon fiber paper composites
also an anchoring support to induce horizontal growth of exhibited a HER current density of 10 mA cm−2 with a low
MoS2. Benefiting from exposure of MoS2 edges, the composite overpotential of 139 mV and a small Tafel slope of 37 mV
Chem. Rev. 2023, 123, 3329−3442
dec−1. The electrocatalytic properties changed little after 5000 catalysts for HER.1068 The metal-doped MoSe2 atomic layers
CV cycles and continual electrolysis for 12 h without obvious were prepared by the solution bath process, followed by
decay. The MC/MC heterostructure not only gives high annealing under a Se atmosphere to improve crystallinity.
conductivity to active sites but also enhances kinetics by Overpotential occurred at −86, −87, −88, and −35 mV vs
altering reaction barriers. Tang et al. synthesized MoS2/CoS2 RHE at 10 mA cm−2 for Cu-, Mn-, and Fe-doped MoSe2, and
NT arrays on carbon cloth via the templated-hydrothermal commercial Pt wires, respectively. The onset potential
reaction.1041 The Co-based metal-organic framework (MOF) occurred at −317, −277, and −289 mV vs RHE at 300, 277,
functioned as both a precursor and a sacrificial template. and 289 mA cm−2 for Cu-, Mn-, and Fe-doped MoSe2,
During growth of MoS2, excess S reacted with the MOF to respectively (Figure 48e). First-principles density functional
form CoS2, followed by etching the MOF to produce hollow theory approximations showed that charge transfer between
NT arrays (Figure 48a). The Gibbs free energy of H (ΔGH) on the doped metal and MoSe2 increases the density of states near
the ideal basal planes of MoS2 is 2.1 eV uphill, indicating that the Fermi level, which increases the carrier concentration as
the basal planes of MoS2 are catalytically inert. The ΔGH for well as electron mobility with dopant metal atoms. The Gibbs
MoS2/CoS2 heterostructures dramatically decreases to 60 free energy (ΔGH) for a hydrogen atom adsorbed on pristine
meV, which is very close to being thermoneutral (Figure 48b). and metal-doped MoSe2 is 2.03, 0.98, 0.72, and 0.13 eV for the
The MoS2/CoS2 heterostructured NTs exhibited a current pristine MoSe2, and the Mn-, Fe-, and Cu-doped MoSe2,
density of 10 mA cm−2 at low overpotentials of 90 mV in acidic respectively (Figure 48f). As a result, the Cu-doped MoSe2
media and 85 mV in alkaline media. The Tafel slope was small, exhibited an 86 mV overpotential with a small Tafel slope (44
which was 30 mV dec−1 in acidic media and 34 mV dec−1 in mV dec−1) and an outstanding robustness was observed in an
alkaline media. acidic medium with a constant HER over 20 h. Zhu et al.
Metal nanoparticle decoration has been reported to be reported that nonmetal elements, P/Se codoped MoS2
another effective method to minimize the use of precious noble combined with CNTs exhibited an HER electrocatalyst
metals.1042,1043 Shi et al. revealed that the plasmonic Au NR/ performance of a low overpotential of 110 mV at 10 mA
MoS2 NSs increase the current 3-fold under excitation of Au cm−2 and a small Tafel slope of 49 mV dec−1, close to the
localized surface plasmon resonance (LSPR).1044 Hot electrons commercial Pt/C.1063 P and Se were doped by N-(n-
from SPR excitation of the Au NR were injected to active butyl)thiophosphoramide and sodium selenite during solvo-
MoS2, resulting in an increase of charge density of MoS2, thermal synthesis. The co-doped catalyst exhibited excellent
enhancing electrocatalytic activity for HER activity. Zhao et al. electrochemical stability over 15 days.
fabricated WSe2 NSs decorated with ultrafine Ru nano- 7.4. Batteries
particles.1045 With increasing amount of Ru from 0 to 4.25
wt %, the overpotential reached 87 mV at a current density of Li ion batteries have been the major power source for portable
10 mA cm−2 for 1.93 wt % Ru-decorated WSe2, which is electronic devices to electric vehicles. While graphite has been
comparable to the commercial Pt/C (40 mV) and out- the most applied anode due to its low potential profile and
performing those of WSe2 (308 mV) and Ru NRs (104 mV). stable cycling performance, the theoretical capacity of graphite
The 1.93 wt % Ru-WSe2 was observed to have a fast reaction (372 mA h g−1)1069 is not sufficient to meet the energy density
rate and showed superior long-term stability without significant of high-rate Li ion batteries for high power applications.
loss of overpotential at 10 mA cm−2 when a 75 000 s test was Therefore, finding a new anode with high performance for Li
conducted. Cheng et al. demonstrated that Rh-decorated MoS2 ion batteries is highly required. Due to the limited Li resource,
nanocomposites exhibit Pt-like catalytic activity.1046 Rh was Na ion batteries and K ion batteries have been also developed.
deposited on exfoliated MoS2 NSs with a thickness of 1.9 nm Na or K ion batteries are still far from practical use because the
by lithium intercalation. In addition to Rh, various metals larger ionic radius of Na+ (1.02 Å) and K+ (1.38 Å) compared
including Ag, Au, Re, Ru, Pd, and Pt with similar concentration to Li+ (0.76 Å) results in a large volume during charge/
of 5 wt % were also compared. Among the various noble discharge, slow ion diffusion, and sluggish electrode kinetics.
metals, Rh exhibited the best HER activity with an over- Among some alternative anode materials including carbona-
potential of 47 mV at the current density 10 mA cm−2. ceous materials,1070,1071 Si,1072 metal oxides,1073 and Li
Notably, the current density of the 5.2 wt % Rh-decorated metal,1074,1075 MCs have drawn considerable attention owing
MoS2 catalysts surpassed that of the commercial 20 wt % Pt/C to their prominent advantages such as high specific capacity
when the potential reached −0.18 V, resulting in a 26.3% larger and better structural stability. A number of metal sulfides1076
hydrogen yield (13.87 A mgmetal−1) than that of commercial 20 and selenides1077−1083 have been developed for rechargeable
wt % Pt/C under an overpotential of 0.25 V (Figure 48c). The batteries. So far, the major obstacles of MCs for rechargeable
reaction proposed mechanism involves three steps (Figure batteries include their low electrical conductivity and the
48d): (i) a hydrogen ion adsorbed on the Rh surface combines structural instability associated with the large volume change
an electron to become an adsorbed H atom, (ii) the neutral during the charge/discharge process.
adsorbed-H atom migrates to the MoS2 surface due to the It has been accepted that there are three main types of Li+/
spillover effect, and (iii) this H atom combines a hydrogen ion Na+/K+ accommodation mechanisms for the MC-based
and an electron to release hydrogen gas. anode: insertion, conversion, alloying, and their combinations.
7.3.2. Heteroatom Doping. Elemental doping, such as Generally, MCs with electrochemically active elements (i.e.,
metals including Zn, 1047−1049 V, 1050 Pt, 1051 Sn, 1052 As, Bi, Si, Ge, Sn, Pb, and Zn) that can react with Li+/Na+/K+
Co,1053−1055 Cr,1056 Ru,1057 and Ni1058 and nonmetals follow the alloying mechanism or a combination of the other
including N,1059−1061 P,1062−1064 Se,1065,1066 and B1067 have two mechanisms. On the other hand, insertion or insertion
been explored as a measure to regulate the morphologies and along with a conversion reaction occurs for electrochemically
electronic structures of electrocatalysts. Vikraman et al. inactive elements including Cu, Co, Nb, Fe, Ni, Mo, V, etc.
proposed Cu-, Fe-, and Mn-doped MoSe2 nanostripe electro- While the alloying and conversion process can produce a
Chem. Rev. 2023, 123, 3329−3442
Figure 49. Batteries. (a) Scheme of the 1D synthesis of MnS-MoS2. (b) Cycle stability of MnS-MoS2 heterostructure, pure MnS, and pure MoS2 at
1 A g−1. (c) Scheme explaining the synthesis process and crystal structure of expanded VS2. (d) Long-term cycling performance of VS2@S/N-
doped electrode at 8 A g−1. (a,b) Reprinted with permission from ref 1102. Copyright 2021, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
(c,d) Reprinted with permission from ref 1123. Copyright 2019, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
higher theoretical capacity than the insertion process, large capacity of 675 mAh g−1 at 50 mA g−1, a good rate capacity,
volume changes and hysteresis take place during charge/ and cycling stability.1085 Electrospun VSe1.5/carbon nanofibers
discharge cycles, which hinders long cycle stability. Many proved to be efficient anode materials for all Li+, Na+, and K+
efforts have been devoted to addressing these issues by batteries with a high capacity of 932 mAh g−1 after 400
controlling the heterostructure and interlayer spacing. cycles.1086 In addition, Fe,1087 Ni,1088,1089 Zn,1090 Co,1091,1092
7.4.1. Heterostructure Control. To ameliorate the low V,1093,1094 and Mo1095−1097 sulfides and selenides have been
conductivity and structural instability, incorporation with other widely studied. Guo et al. synthesized an Fe7S8 NW/SiOx/N-
materials and rendering heterostructures has been widely doped carbon matrix by a hydrothermal method, followed by
explored. Carbonaceous materials have been extensively sulfidation derived by bamboo leaves. The Fe7S8 NW/SiOx/N-
exploited to form the heterostructures with MCs because doped C electrode for a Li-ion battery shows a discharge
they can reduce the volume expansion/shrinkage during capacity of 1060.2 mA h g−1 at 200 mA g−1 with a good long
charge/discharge and increase the charge transport. MnS cycling performance of 415.8 mA h g−1 at 1000 cycles at 5 A
nanoparticles/S-doped mesoporous C frameworks showed g−1.1087 Wang et al. fabricated petal-like Ni3S2 NSs on three-
outstanding Li storage performance, with a specific capacity dimensional CNT foams (Ni3S2@3D-CNTF) via the solvo-
of 1383 mAh g−1 at 200 mA g−1 in the 300th cycle.1084 A thermal method. The electrode for the Li-ion battery exhibits a
Co9S8 NR encapsulated by a N-doped C shell exhibited a high reversible capacity of 968.2 mAh g−1 at 0.2 A g−1, good rate
Chem. Rev. 2023, 123, 3329−3442
performance of 524.1 mAh g−1 at 8 A g−1, and long life cycling g−1), excellent rate performance, and long-term cycling stability
stability of 93.6% after 900 cycles at 4 A g−1.1088 Xu et al. (397.2 mAh g−1 after 3000 cycles) (Figure 49b). Cui et al.
obtained a yolk−shell ZnSe@C anode from C-coated prepared SnS/MoS 2/N, S-doped C NSs for Na+ ion
Zn2GeO4@C NRs. For a K-ion battery, the electrode shows batteries.1101 Na2SnO3, Na2MoO4, thiourea, ammonium
a discharge/charge performance of 360 mA h g−1 at 0.2 A g−1 citrate, and NaCl were dissolved in water and freeze-dried.
after 60 cycles and 204 mA h g−1 at 2.0 A g−1 over 100 cycles, Then, calcination under an inert atmosphere and washing with
with a rate capacity of 167.5 mA h g−1 at 4.0 A g−1.1090 Wang water resulted in the composite. In this process, NaCl was used
et al. synthesized C-coated CoSe microrods and evaluated the as a template to promote the growth of NSs and ammonium
performance of a Na-ion battery.1091 C-coated CoSe exhibits a citrate was used as the carbon. The produced composites
discharge capacity of 485 mA h g−1 after 60 cycles at 0.1 A g−1 exhibited improved electrochemical performances with a high
and rate performance of 315 mA h g−1 at 0.5 A g−1. Li et al. capacity (570.4 mAh g−1 at 0.2 A g−1) and long cycle life
investigated a hollow C-templated few-layered V5S8 NSs for K- (287.2 mAh g−1 at 1.0 A g−1 after 800 cycles).
ion battery.1093 The obtained V5S8@C electrode showed a TiO2 coating on solution-processed CoSe2 NRs make
specific capacity of 645 mAh g−1 at 50 mA g−1, long cycling uniform TiO2@CoSe2 core−shell structures that can improve
stability at a high rate of 360 mAh g−1 and 190 mAh g−1 after cyclic stability.1098 The discharge capacity was 999.2 mAh g−1
500 and 1000 cycles at 500 and 2000 mA g−1, respectively. after 300 cycles at 200 mA g−1 and 723.7 mAh g−1 after 430
Individual 2D MoS2 layers vertically grown on top of the cycles even at a high current density of 500 mA g−1.1098 As a
basal plane of graphene were obtained by direct growth of comparison, bare CoSe2 showed only 145.4 mAh g−1 after 220
MoS2 on graphene oxide, followed by annealing in an inert cycles at 200 mA g−1. The enhanced cyclability resulted from
atmosphere.1095 Oxalic acid played an important role as a the NR structure that shortened the Li+ diffusion distance and
surface charge modifier in the synthesis, where protons from facilitated the charge transport kinetics. In addition, the TiO2
oxalic acid mediated electrostatic interaction between graphene layers coated on the CoSe2 NRs efficiently buffered the volume
oxide and Mo7O246−. As a result, vertical growth of MoS2 on changes during cycling, alleviating the pulverization problem of
graphene was induced as well as a stable bond through C−O− the electrodes. Xing et al. fabricated a three-layered
Mo. The vertical MoS2/graphene heterostructure exhibited a heterostructure with porous metallic TiNb2O6 as the core
high capacity of 1077 mAh g−1 at 100 mA g−1 up to 150 cycles. and a carbon-encapsulated MoS2 microsphere as the shell.1100
The improvement was attributed to the presence of C−O−Mo TiNb2O6@MoS2/C composites were formed by the two-step
bonds that made the carriers transport easier and guaranteed hydrothermal process, followed by thermal annealing under a
free volumes between the vertical 2D MoS2 layers, which H2 atmosphere to make oxygen-deficient TiNb2O6 from
reduced mechanical stress during charge/discharge. Liu et al. TiNb2O7. TiNb2O6 with unsaturated oxygen atoms has a
synthesized a MoSe2/C heterostructure through the templated metallic conducting behavior, which can significantly enhance
growth of MoO2 on SiO2 templates, followed by etching of the electronic mobility of both inner and outer parts of the
SiO2 and then hydrothermal selenization to convert to core. As well as the mobility, MoS2 NSs were epitaxially grown
MoSe2.1097 Synergetic effects between 2D MoSe2 and 3D on the surface of TiNb2O6, inhibiting the agglomeration of the
ordered macroporous carbon provides an expanded interlayer ultrathin MoS2 NSs and maintaining the large contact area
spacing (0.76 nm for a single layer) which facilitates Na+ between active material and electrolyte. As a result, impressive
insertion/extractions. The strong electronic coupling of Mo−C electrochemical behavior with a high capacity (424 mAh g−1 at
bonding led to the fast electron/ion transfer, and the ordered 0.1 A g−1 after 50 cycles) and high cycling stability (175 mAh
stereoscopic cavity accommodating the volume expansion g−1 at 1.0 A g−1 after 300 cycles) were achieved.
prevented the stacking of MoS2 NSs upon cycling. As a result, 7.4.2. Interlayer Spacing Control. Interlayer expansion
the MoSe2@C composite delivered high capacity (410 mAh has been considered to be an effective strategy to enhance the
g−1 at 0.5 A g−1 after 100 cycles), superior rate capability (279 discharge capacity and reaction kinetics of layered 2D
mAh g−1 at 10 A g−1), and long-term cycling stability (384 materials, as the ion diffusion energy barriers can be
mAh g−1 at 5 A g−1 after 2000 cycles). significantly decreased.422,650,655,1114,1115 While the interlayer
As well as carbonaceous materials, extensive research on MC spacing of bulk MoSe2 is 0.646 nm, intercalation of foreign
heterostructures with metal oxides1098−1100 and other atoms (typically, ammonium ion or amines) can induce
MCs1101−1113 has been conducted to improve the battery interlayer expansion.1116 MoSe2 intercalated with octylamine in
performance. Recently, Chen et al. prepared a MnS-MoS2 solvothermal conditions exhibited a large interlayer spacing of
heterostructure by hydrothermal sulfurization of MnMoO4 1.00 nm, which resulted in fast Na+ insertion/extraction with a
rods prepared by reaction between (NH4)2MoO4 and high capacity (228 mAh g−1 after 1500 cycles at a high current
Mn(acetate)2. MnMoO4 acted as self-sacrified template density of 1.0 A g−1).1083 Ethylenediamine-intercalated MoSe2
controlling the agglomeration of MoS2, which further acted synthesized under hydrothermal conditions had an interlayer
as a template for heterogeneous growth of MnS onto MoS2 spacing of 1.02 nm, which matches the Na+ ionic radius.1096 As
(Figure 49a). A built-in electric field at the interface was a result, excellent rate capabilities and a long cycling life with
developed owing to the intimate contact from p-type MnS and exceptional Coulombic efficiency were obtained even at high
n-type MoS2, which accelerated the ion migration and the current density, maintaining 501 and 471 mAh g−1 over 1000
charge transport between MnS and MoS2 in charge/discharge cycles at 1 and 3 A g−1. Even at high current density at 10 A
cycles. The authors found phase transitions from α-MnS to γ- g−1, capacity retention was achieved. As well as MoSe2, VS2-
MnS and from 2H-MoS2 to 3R-MoS2 after the first cycle. They based materials have been extensively investigated in various
insisted that it was beneficial to enhance the structural stability rechargeable batteries1117−1121 due to not only the inherit
and reformation of the heterostructure preserved the built-in layered structure but also the metallic conductivity.1122 Yang et
electric filed. As a result, the MnS-MoS2 heterostructure al. synthesized interlayer-expanded rose-like VS2@S/N co-
exhibited outstanding specific capacity (1246.2 mAh g−1 at 1 A doped carbon with a 0.92 nm d-spacing of the (001) plane
Chem. Rev. 2023, 123, 3329−3442
Figure 50. Application in supercapacitors. (a) Schematic crystal structure of the O-incorporated MoS2. (b) Cycle performance at a current density
of 10 A g−1 during 10,000 cycles. (c) Scheme of the intercalated 1T-MoS2 enabled by fluorine free radicals and polymer fragments. (d) HRTEM
image of the 1T/2H MoS2. (e) Photograph of LED operation using the all-solid-state stretchable supercapacitor connected in series. (f) Scheme of
the working mechanism of the Ag-decorated (Ni,Fe)Te NRs/Ni foam electrode. (g) Cyclic voltammetry curves of (Ni,Fe)Te NRs/Ni foam and
Ag-decorated (Ni,Fe)Te NRs/Ni foam electrodes. (a,b) Reprinted with permission from ref 1134. Copyright 2021, Elsevier. Ltd. (c−e) Reprinted
with permission from ref 1136. Copyright 2021, American Chemical Society. (f,g) Reprinted with permission from ref 1150. Copyright 2021,
American Chemical Society.
(Figure 49c).1123 The reaction between vanadyl acetylaceto- cycling stability up to 600 cycles of 8 A g−1 with a capacity of
nate and thioacetamide results in VS2. During the solvothermal 684.5 mAh g−1 (Figure 49d).
reaction, ammonium molecules released from thioacetamide 7.5. Supercapacitors
and melam induced a synergistic effect to expand the interlayer Supercapacitors are considered as a class of next generation
spacing to 1.26 nm. After subsequent thermal annealing, energy storage devices due to the prolonged cycle life, high
melam was thermally decomposed to NH3 gas and the rest charge/discharge rates, and wide thermal operating
served as the source of the S/N-doped carbon, which acted as range.1124−1126 The electrochemical reaction in supercapaci-
a gas generator to keep d-spacing expanded to 0.92 nm. tors includes both surface faradaic and nonfaradaic reactions.
In the nonfaradaic reaction, charges are stored in the electric
Introduction of melamine during the solvothermal reaction double layer without charge transfer and redox reactions. A
significantly enhanced electrochemical properties, such as a faradaic reaction containing a surface redox reaction and
large reversible capacity of 971.6 mAh g−1 at 0.2 A g−1, a high intercalation occurs in pseudocapacitors, which provides
rate capability of 772.1 mAh g−1 at 10 A g−1, and a remarkable additional capacitance. Most MC-based supercapacitors are
Chem. Rev. 2023, 123, 3329−3442
classified as pseudocapacitors.1127,1128 Among the various stacking of the layered materials. The interlayer spacing was
supercapacitor electrodes such as carbon-derived materials, 11.8 Å, in which a bilayer of water molecules could be
conducting polymers, metal oxides, and MCs, increasing contained. When Na+ and Li+ are used as the transport cations,
attention has been focused toward anisotropic MCs because a higher capacitive performance is observed with Li+ due to the
they exhibit a high surface area, high theoretical capacitance, bigger sizes of Na+. A control experiment measuring specific
and good electrical conductivity. The major drawbacks that capacitances was conducted with 1T-MoS2, 2H-MoS2, and
hinder the practical uses of the MC supercapacitors are low mixture-MoS2 (1T-MoS2/2H-MoS2 = 1:1 by weight). The
energy density and poor cycle stability.28,1129,1130 result revealed that the specific capacitance by using Na+ was
7.5.1. Doping Control. Doping of foreign atoms can tune enhanced with increasing amount of 1T-MoS2, that is, 1T-
the morphology, interlayer spacing, faradaic reaction, and MoS2 (183.7 F g−1) > mixture-MoS2 (61 F g−1) > 2H-MoS2 (7
electronic conductivity. Co doping (1.8 at%) in 1D NiSe2 NWs F g−1). The supercapacitor retained their capacitance up to
improved the specific capacitance by increasing the surface 88% after 10000 cycles. Very recently, Thiyagarajan et al.
area.1131 The Co-doped NiSe2 NWs were directly grown on fabricated stretchable solid-state supercapacitors. They used
nickel foam by using the hydrothermal process. After Co- polymeric molecules to produce 1T-MoS2. The stretchability
doping, the NW diameter was reduced from 50 to 20 nm, the was obtained by adding a fluoroelastomer (FE) in the 1T-
active surface area increased from 54.6 m2 g−1 to 135.2 m2 g−1, MoS2 solution.1136 F radicals in the FE were generated by
and thus the specific capacitances were enhanced from 1091.3 high-power ultrasonication (200 W). They found that 1T-
F g−1 to 3167.6 F g−1. Guo et al. fabricated Co-doped NiSe MoS2 was bound to the fluoroelastomer through the defective
NWs that were 40−50 nm in diameter and up to several S vacancy in 1T-MoS2 and the F radicals (Figure 50c). The
micrometers in length on a Ni foam by stepwise chemical interlayer distance increased to 0.98−1.08 nm, and interest-
transformation.1132 First, the Ni foam was reacted with NaHSe ingly, 1T-MoS2/FE exhibited unconventional crystal structures
to create NiSe NWs, and then the Co2+ ion replaced Ni2+ in in which the stable cubic 1T and distorted 2H structures were
NiSe NWs. With varying cation replacement time, the amount mixed (Figure 50d).1136 The specific capacitance was 28 mF
of Co can be adjusted. Among various compositions of cm−2 at a current density of 0.2 mA cm−2, and the energy
NixCo1−xSe NWs, Ni0.8Co0.2Se displayed the highest specific density showed 3.15 mWh cm−3. The resistance of super-
capacitance of 86 F g−1 (NiSe: 42 F g−1, Ni0.6Co0.4Se: 39 F g−1, capacitor was stable after 1000 cycles at 40% uniaxial strain.
and Co9Se8: 66 F g−1) and good cycling stability (>95% over The capacity remained 100% up to 3000 cycles and decreased
2000 cycles). Ni0.8Co0.2Se exhibited the smallest Rs (0.72 Ω to 87% after 6000 cycles. The supercapacitor with the series
cm2), Rct (0.82 Ω cm2), and Zw (0.0012 Ω s−1/2 cm2) obtained connection was able to light up a light-emitting diode for 5 min
by analyzing Nyquist plots, which contributed to the superior under the stretched state at 40% strain (Figure 50e).
electrochemical performances. As well as cations, anions such 7.5.3. Heterostructure Control. Much research has been
as oxygen, phosphor, nitrogen, and fluorine have been widely reported on heterostructured anisotropic MCs explored for
applied as a dopant. Zhou et al. synthesized oxygen- improving supercapacitor performances, which is typically
incorporated MoS2 (MoS2‑xOx) NSs with expanded interlayers attributed to decreased electrical resistance and/or increased
by a reaction between molybdenum oxide and potassium active surface area.1137−1141 Metal nanoparticles with high
thiocyanate dissolved in ethanol.1133 The interlayer spacing conductivity such as Cu, Ag, Au, and Pt have been exploited to
(d002) of MoS2‑xOx was ∼8.4 Å larger than that of MoS2 NSs enhance the surface area and electrical conductivity of MC-
(∼6.4 Å). based supercapacitor devices.1142−1149 It has been demon-
7.5.2. Interlayer Spacing Control. Another method to strated in the study that CoS NSs decorated with Ag
increase interlayer spacing to facile allocation of ions is nanoparticles (14−25 nm) have better supercapacitive
intercalation. The intercalated structure led to the increase in performance with a stable specific capacitance of 370 F g−1
the specific capacitance of MoS2‑xOx to 227 F g−1 from 145 F at 1 A g−1 compared to pure CdS NSs having almost no
g−1 of the pristine MoS2 at 0.5 A g−1 and current density of 1 A capacitance after 1000 cycles. Very recently, Jayababu et al.
g−1. Very recently, the interlayer distance further increased to synthesized Ag-decorated mixed metal (Ni/Fe) telluride NRs
9.8 Å in 1T/2H MoS2‑xOx by insufficient sulfidation of on a nickel foil (Figure 50f).1150 Ag-decorated Ni0.75Fe0.25Te
polymeric Mo-blue clusters and in situ intercalation of NH4+ NRs show a higher surface area (18.578 m2 g−1) and pore
ions (Figure 50a).1134 The specific capacitance further volume (0.026 cm3 g−1) than bare Ni0.75Fe0.25Te NRs (surface
increased to 280 F g−1 at 1 A g−1, and better capacitance area = 4.82 m2 g−1, pore volume = 0.0168 cm3 g−1). With
retention of 88% was achieved after 10000 cycles at 10 A g−1 varying composition between Ni and Fe, Ni0.75Fe0.25Te
(Figure 50b). In situ intercalation of ammonium ion in MoS2 exhibited the lowest internal resistance (Ri = 0.006 Ω) and
NSs by reacting ammonium molybdate and thiourea during charge transfer resistance (Rct = 2.30 Ω). The areal and the
the hydrothermal process increased the interlayer spacing to specific capacitances of the alloy were 187.5 μAh cm−2 and
0.99 nm.1135 Simultaneously, ammonium interaction in MoS2 156.3 mAh g−1 at 2 mA cm−2, respectively. The performance
induces phase transition from the 2H to 1T phase (60%). It is remained 92% after 2000 cycles at 15 mA cm−2. After
known that 1T-MoS2 is metallic with excellent electrical decorating Ag, the areal and the specific capacitance highly
conductivity, which would be greatly helpful for improving the increased to 1.12 μAh cm−2 and 699.58 mAh g−1 at 3 mA
performance of electrochemical capacitors. The specific cm−2, respectively (Figure 50g). The device showed 80.4%
capacitance was 346 F g−1 at 1 A g−1, and the retention ratio capacity retention after 3000 cycles.
after 2000 cycles was 95.4%. Geng et al. synthesized pure 2H- In addition to metal, heterostructures between metal oxides/
and 1T-MoS2 by hydrothermal synthesis, followed by chalcogenides and MCs have been demonstrated to have rich
annealing (200 °C for 1T phase, and 240 °C for 2H phase). redox reactions, good conductivity, and high electrochemical
In their previous work, they found that a bilayer of water was activity.1151−1157 Adhikari et al. synthesized CdS NR-CoFe2O4
attached on the surface of 1T-MoS2, which reduced the nanoparticle heterostructures on rGO.1158 The n-type and p-
Chem. Rev. 2023, 123, 3329−3442
Figure 51. Sensing platforms. (a) HRTEM image of ZnO@ZnS core−shell NW. Inset shows interfaces between Pd nanoparticles and ZnO NWs.
(b,c) H2S gas sensing performance of Pd-decorated ZnO@ZnS core−shell NWs under (b) positively bent surfaces and (c) negatively bent surfaces.
(d) Schematic illustration of light-enhanced NO2 sensing mechanisms in CdS/ZnO core/shell NWs-based optoelectronic NO2 gas sensor. (e)
Time-dependent photoresponse in air or in different NO2 concentration by periodically turning on and off. (a−c) Reprinted with permission from
ref 1177. Copyright 2019, American Chemical Society. (d,e) Reprinted with permission from ref 1186. Copyright 2014, Wiley-VCH Verlag GmbH
& Co. KGaA, Weinheim.
type nature of CdS and CoFe2O4 created a p−n junction removed from the semiconducting MCs. Among the various
diode, where the electrons in the valence band of CoFe2O4 MCs, CdS, ZnS, CdSe, MoS2, WS2, MoSe2, WSe2, MoTe2,
moved to the conduction band. The electrons from the ReS2, ReSe2, SnS2, GaSe have been intensively explored for
conduction band of CoFe2O4 moved to the conduction band sensing applications.1165−1175 Meanwhile metallic MCs such as
of CdS. rGO acted as an electron acceptor and transferrer. The NbS2 and VSe2 are not appropriate for sensors because of the
surface area was gradually increased from 30.05 m2 g−1 (CdS), low resistance. The common obstacles of the MC-based
91.13 m2 g−1 (CdS-CoFe2O4), to 230 m2 g−1 (CdS-CoFe2O4- sensors are inferior selectivity compared to the spectroscopy-
rGO). As well as surface area, charge transfer resistance (Rct) based sensors, interference from ambient temperature and
was decreased in the order CdS (28.78 Ω) > CdS-CoFe2O4 relative humidity, and durability issues resulting from oxidation
(5.31 Ω) > CdS-CoFe2O4-rGO (0.92 Ω), while maintaining of MCs at elevated working temperature.1176
electrolyte resistance (1−2 mΩ). As a consequence, the 7.6.1. Flexible Gas Sensors. Because most MC gas
highest specific capacitance of 1487 F g−1 was measured for sensors are based on the charge transfer mechanism,
CdS-CoFe2O4-rGO, and it showed 78% capacitance retention anisotropic nanomaterials including both 1D and 2D materials
after 5000 cycles. Recently, trimetal sulfide (Zn−Mn−Ni-S, are beneficial in making the conducting path. Yang et al.
ZMNS)@NiSe core−shell architectures have been proven to directly synthesized vertically aligned Pd-decorated ZnO/ZnS
be a superior supercapacitor compared to single-component NWs on flexible substrates and demonstrated flexible H2S gas
metal sulfides.1159 ZMNS@NiSe NWs with varying composi- sensors (Figure 51a).1177 ZnO/ZnS core−shell structured
tions were grown on Ni foil by a two-step hydrothermal NWs were critical in maintaining the sensing stability because
synthesis, followed by electrodeposition of NiSe to form the pristine ZnO gives unstable sensing conditions to H2S: ZnO(s)
core−shell structure. The NiSe NSs are believed to protect the + H2S(ads) → ZnS(s) + H2O(g). The sensor had exclusively
ZMNS core and provide numerous paths for the diffusion of high sensitivity to H2S gas (631%) among other gases of the
ions through the pore network in the electrode.
same concentration of CO (35%), acetone (5.7%), ethanol
7.6. Sensing Platforms (2%), and toluene (1.53%). After Pd nanoparticle decoration,
Gas sensors have been widely used in various applications the selectivity further increased to 4444% for H2S, while
including gas emission control, agricultural and industrial maintaining the similar sensitivity to other gases: CO
production, military defense, environmental safety, and (12.37%), acetone (39.68%), ethanol (4.3%) for toluene.
medical diagnostics.1160−1164 Gas sensors require high The sensor could endure mechanical bending due to strong
sensitivity, selectivity, and fast response/recovery time. adhesion between NWs and substrate, stably operating without
Among various gas sensing mechanisms including charge degradation of the performances up to 10 mm of positive
transfer, surface reaction, and proton conduction, the majority curvature radius (Figure 51b) and 8 mm of negative curvature
of MC-based gas sensors have used the charge transfer radius (Figure 51c). Cho et al. fabricated wearable, launder-
mechanism. Depending on whether gaseous species are able, and bendable gas sensors by the CVD method.1178
oxidizing or reducing, electrons (or holes) are injected to or Prepatterned WO3 and Nb2O5 were selenized to metallic
Chem. Rev. 2023, 123, 3329−3442
NbSe2 and semiconducting WSe2. During the CVD seleniza- MoS2-coated SiO2 NRs, more gas molecules could access,
tion process, the NbxW1−xSe2 compound layer was naturally through the pores, a larger number of edge sites. In the
formed at the metal−semiconductor interface by vertical previous report, the binding energies between NO2 molecules
diffusion of W and Nb transition metals. Natural formation of and basal plane, S edge, and Mo edge of MoS2 were revealed to
the NbxW1−xSe2 layer reduced the Schottky barrier height at be −0.248, −0.927, and −4.530 eV, respectively.1185
the interface, which made it easier to collect charges on 7.6.4. Heterostructure Control. Yang et al. demonstrated
channels induced by gas molecule adsorption. The NbSe2/ that core−shell structured NWs can improve the NO2 gas
WSe2 gas sensor detected subppm levels of NO2 and NH3 sensor performances.1186 CdS/ZnO core−shell NWs with the
gases even at a bending radius of 2 mm without degradation of core diameter being 20−60 nm and shell being 2−3 nm were
selectivity and sensitivity; further, it showed good cycle prepared by a two-step hydrothermal synthesis (Figure 51d).
performance (>10 000 bending cycles). The sensors were The authors explained three crucial factors in the core−shell
stitched on a T-shirt which operated after the conventional structure. First, the core−shell heterojunction structure
laundry process (washing with chemical detergent and improved the photoinduced charge separation, thus leading
cleaning) and being dried with a drying machine. to a 28 times enhancement in the photocurrent (143 nA under
7.6.2. Thickness Control. The energy levels of the 468 nm light illumination with 0.68 mW cm−2 at a bias of 4 V)
conduction and valence band of MCs change with the layer compared to bare CdS NWs. Second, the photoelectrons
thickness and likely alters the redox potential, which in turn transferred from the CdS core to the ZnO shell promoted the
affects the sensing capability. The thickness-dependent sensing interaction between ZnO and NO2, resulting in a remarkable
properties of MoS2, MoSe2, WSe2 have been intensively enhancement of the room temperature NO2 sensing proper-
investigated.1179,1180 Late et al. deposited MoS2 sheets of 1−5 ties: detection limit of 5 ppb, response time of 27−40 s, and
layers by mechanical exfoliation on a 300 nm SiO2/Si substrate recovery time of 53−227 s. Third, the thin thickness of the
and fabricated FETs.1181 They found that the current of the ZnO shell layer (<3 nm) brought NO2 to the proximity of the
single-layer MoS2 device was not stable over time. Interest-
CdS/ZnO interface. The sensors could be turned on and off
ingly, 5-layer MoS2 was the most sensitive upon exposure to
rapidly within tens of milliseconds and repeatably (Figure
various concentrations of NH3 and NO2 in the range 100−
51e). When the CdS/ZnO core/shell NW was exposed to NO2
1000 ppm without gate bias. When the back gate voltage (+15
under visible-light illumination, the adsorbed NO2 gas
V) was applied, the sensitivity for NO2 was increased while
that for NH3 was decreased. This is because electrons molecules capture the photoelectrons directly from the ZnO
accumulate at the interface of MoS2 and SiO2 under positive shell and generate NO species (2NO2 + e− → 2NO + O−2 ). As
gate voltage; hence, the signal of the electron-accepting NO2 a result, the surface electron-depletion layer expands, which
(oxidizing gas) increases and the signal of the electron- results in the increase of the overall resistance.
donating NH3 (reducing gas) decreases. When WS2 NSs Very recently, highly efficient H2 gas sensors based on
exfoliated by lithium intercalation and ultrasonication were MoS2/CsxWO3 nanocomposites have been reported.1187 An
used for NH3 gas sensing, the signal recovery time was aqueous solution of exfoliated MoS2 produced by ultra-
considerably shorter as the number of layers decreased.1182 sonication in DMF was mixed with WCl6 and CsOH·H2O in
The first-principles calculation revealed that the NH3 molecule ethanol/acetic acid solution, and then the mixed solution was
has stronger binding energy in the interlayer space (−0.356 reacted under hydrothermal conditions at 240 °C for 20 h. The
eV) than that on the surface of WS2 (−0.179 eV), which improved electrical conductivity of the nanocomposite
explains the relationship between recovery time and number of contributed to the enhancement in the H2 gas sensor response.
layers. When the CsxWO3/MoS2 composite was exposed to H2 gas,
7.6.3. Effective Surface Area Increase. The surface area the adsorbed oxygen species on CsxWO3 reacted with H2 gas
of active sites is an important parameter to improve sensor and produced extra electrons in the conduction band of
performance. Templated growth can increase the surface area CsxWO3, (2H2 + O−2 → 2H2O + e−), which decreased
of active sites. Hierarchical hollow spheres were produced by electrical resistance. The sensor detected the H2 concentration
heterogeneous growth of MoS2 on polystyrene (PS) micro- in the range 10−500 ppm, and the response and recovery
spheres by reacting sodium molybdate and thiourea under times were 60 and 120 s at 500 ppm of H2 gas.
hydrothermal conditions.1183 MoS2 nuclei were formed on the 7.7. Thermoelectric Devices
PS surface and covered the entire surface with a hierarchical
morphology. The PS microsphere template was removed to The performance of thermoelectric devices is determined by a
obtain the MoS2 hollow spheres. When the reaction was figure of merit, ZT, which can be expressed by ZT = S2σT/κ,
prolonged over 10 h, small spheres began to nucleate on the where S, σ, T, and κ represent the Seebeck coefficient,
surface of the MoS2 hollow spheres and grew up into solid electrical conductivity, absolute temperature, and thermal
spheres to reduce the surface energy. The authors reported conductivity. Anisotropic MC nanocrystals have been exten-
that the hollow spheres had considerably improved sensitivity sively explored as thermoelectric materials, inspired by the
and selectivity for NO2 gas compared to the solid spheres, seminal work by Dresselhaus et al. in 1993,1188 which
which was attributed to the increased surface area. Direct predicted that quantum confinement effects can enhance the
growth of MoS2 on SiO2 NRs induced numerous edge sites of thermoelectric power factor in low-dimensional materials.
MCs being exposed.1184 The SiO2 NRs were deposited using Filtering low energy carriers in heterostructure interfaces of
the glancing angle deposition with the e-beam evaporator. MC nanocrystals further increases the Seebeck coefficient.
Subsequently, MoS2 was grown via thermolysis of ammonium Thermal conductivity (κ) can be reduced by anisotropic
tetrathiomolybdate with an extra sulfur source in CVD. The nanomaterials/nanoprecipitates through phonon scattering at
NO2 gas response of SiO2 NRs encapsulated by MoS2 was ∼90 grain boundaries. Intensive research using MC nanostructures
times higher than that of MoS2 deposited on flat SiO2. In the has been focused on increasing S and σ with a low κ through
Chem. Rev. 2023, 123, 3329−3442
Figure 52. Application in thermoelectrics. (a) OM image of the as-grown 2D Te NSs. (b) Numerical modeling of temperature-rise per absorbed
laser power. (c) Extraction of the Seebeck coefficient from the voltage drop versus temperature gradient plot. (d,e) SEM image (d) and EDS
mapping (e) of the 11.8 at% Cu-doped SnSe. (f) Comparison of experimental ZTs with predicted plots for the Cu-doped SnSe. (g) Scheme and
corresponding TEM images of the evolution of Bi2Se3 seed to core−shell, double-shell, and multishell (Bi2Se3@Bi2Te3@Bi2Se3@Bi2Te3) NPs. (h)
ZT of the pellets made of Bi2Se3, (Bi2Se3)2(Bi2Te3)8, and (Bi2Se3)1(Bi2Te3)9. (a−c) Reprinted with permission from ref 1189. Copyright 2019,
American Chemical Society. (d−f) Reprinted with permission from ref 1211. Copyright 2018, The Royal Society of Chemistry. (g,h) Reprinted
with permission from ref 1228. Copyright 2015, American Chemical Society.
dimension control, doping, heterostructure formation, and thermoelectric devices with room-temperature ZT exceeding
phase control. 1.2. The high ZT value was attributed to the enhanced Seebeck
7.7.1. Dimension Control. While Te grows intrinsically coefficient (S = 1250 μV K−1) and the reduced cross-plane
into a 1D structure, Wang et al. synthesized 2D tellurene with thermal conductivity (κ = 0.088 ± 0.004 W m−1 K−1)
the aid of surfactant polyvinylpyrrolione (PVP) under compared to bulk SnSe single crystals (S = 809 μV K−1and
hydrothermal conditions (Figure 52a).1189,1190 Qiu et al. 0.23 ± 0.03 W m−1 K−1).1192 As well as 2D nanoflakes, 1D
evaluated the thermoelectric performance of the suspended 2D NWs including Bi2Te3 and PbTe were obtained by chemical
tellurene films.1189 The thermal conductivity was 1.5 W m−1 transformation from Te NWs.1193,1194 Uniform n-type Bi2Te3
K−1, which is lower than that of bulk Te, around 3 W m−1 K−1 NWs with the average diameter of 5 nm and p-type PbTe NWs
(Figure 52b). The Seebeck coefficient was high, 413 μV K−1 with a 12.1-nm diameter were consolidated to bulk pellets by
(Figure 52c), and the power factor (S2σ) was 31.7 μW cm−1 spark plasma sintering. The measured thermal conductivity of
K−2. The room-temperature ZT was 0.63, which is a significant the Bi2Te3 NWs was 0.92 W m−1 K−1 at 370 K which was
value from that of bulk Te (0.2−0.3). Reduction in dimension lower than commercial Bi2Te2.7Se0.3 single crystals (∼1.65 W
down to nanoscale increased ZT due to grain boundary m−1 K−1), leading to a 13% enhanced ZT value of 0.96 with
scattering and reduced thermal conductivity. Min et al. respect to the best n-type commercial Bi2Te2.7Se0.3 single
synthesized 2D Bi2Se3 and Bi2Te3 nanoflakes with a 4−20 crystals (∼0.85).
nm thickness and their composites.1191 They showed a 7.7.2. Phase Control. The properties of MCs vary
reduced thermal conductivity in the range of 0.55 to 0.68 W dramatically according to their polymorphs. Recently, gram-
m−1 K−1, compared to the thermal conductivity of the bulk scale synthesis of CuxS with specific compositions was
Bi2Te3 with microsized grains (∼1.5 W m−1 K−1). SnSe NS developed, and the thermoelectric performances corresponding
films allowed for fabrication of high-performance flexible to the crystal phases were reported.1195 The synthesis was
Chem. Rev. 2023, 123, 3329−3442
simple and straightforward. Stoichiometric amounts of Cu and 19 × 10−4 W m−1 K−2 at 440 K and the lowest κ (0.69 W m−1
S powders were reacted with hydrazine hydrate, and then CuS, K−1).
Cu1.75S, Cu1.80S, and Cu2S were formed with different 7.7.4. Heterostructure Control. The prospects of
crystallographic phases. The observed room-temperature reducing thermal conductivity at multiple phonon-scattering
Seebeck coefficients for CuS, Cu1.75S, Cu1.80S, and Cu2S were interfaces and inducing low-energy carrier filtering to increase
10.5, 25.1, 30.2, and 91.6 μV K−1, respectively. Meanwhile, the the power factor can be realized by heterostructure formation.
electrical conductivity decreased from CuS to Cu2S. While The heterostructure was formed via heterogeneous nucleation
CuS, Cu1.75S, and Cu1.80S exhibited similar power factor values and growth, or compositing with metals (Cu, Ag, Sn, Pt,
of 30−38 μW m−1 K−2, Cu2S gave a significantly greater power etc.),1212−1215 MCs (Bi2Se3, Bi2Te3, PbTe, Ag2Te, Sb2Te3
factor of 84 μW m−1 K−2 at 100 °C. The maximum power etc.),1216−1219 carbonaceous materials (graphene, rGO,
output by the Cu2S device was 3.4 μW. CNT), 1220−1224 and polymers (PEDOT:PSS, P3HT,
Piao et al. synthesized 1T phase and 2H phase WS2, and etc.).1225−1227 Guo et al. fabricated wearable thermoelectric
compared their thermoelectric performances.1196 1T-WS2 was devices based on MoS2 NSs of the lateral dimension of 1−2
synthesized by the hydrothermal process using ammonium μm that were decorated with Au nanoparticles (5−10 nm).1213
tungsten oxide hydrate, thiourea, and oxalic acid dihydrate as Au-decorated MoS2 was synthesized by in situ reduction of
the catalyst. 2H-WS2 was obtained by the surfactant-assisted HAuCl4 by ascorbic acid in the presence of exfoliated MoS2
liquid exfoliation with sodium cholate as the surfactant. At NSs through Li intercalation. After synthesis, thin films were
room temperature, the Seebeck coefficient of 1T-WS2 was 30 obtained via vacuum filtration. Due to the metallic nature of
μV K−1, and the electrical conductivity was 45 S cm−1 which the Au nanoparticles, the electrical conductivity increased after
was superior to that of 2H-WS2 (10−6 − 10−5 S cm−1). They Au decoration from 88.7 S cm−1 to 177.1 S cm−1 at 290 K.
found that heat treatment at mild temperature (125 °C) Meanwhile, the Seebeck coefficient increased slightly from 84.6
improved the electrical conductivity to 120 S cm−1 while to 96.9 μV K−1, which resulted in an optimal power factor of
maintaining the Seebeck coefficient (28 μV K−1). This 166.3 μW m−1 K−2. To illustrate the potential of the flexible
films for harvesting human body heat, the authors fabricated a
improvement was attributed to adsorbed H2O and O 2
fabric-based wrist band with five rectangular ribbons. The
molecules as the scattering centers were removed. MoS2
voltage output of the wrist band was about 2.4 mV for a
showed similar phase-dependent thermoelectric properties.
temperature gradient of about 5 K, and the power factor was
The Seebeck coefficient and electrical conductivity of 1T-MoS2
retained by 97% after bending for 500 cycles with a bending
were reported to be +85.6 μV K−1 and 9978.3 S m−1, whereas radius of 5 mm.
those of 2H-MoS2 were −706.4 μV K−1 and 1.1 S m−1.1197 As Min et al. compared the thermoelectric properties of Bi2Se3/
a consequence, 1T-MoS2 showed a significantly higher power Bi2Te3 nanoflake mixtures and Bi2Se3@Bi2Te3 core−shell NPs.
factor of 73.1 μW m−1 K−2 than 2H-MoS2 (0.5 μW m−1 K−2). They synthesized surfactant-free gram-scale Bi2Se3 (BS) or
The authors revealed that H2O in atmosphere (40% relative Bi2Te3 (BT) NPs with thicknesses of 4−20 nm by the hot
humidity) degraded the power factor of 1T-MoS2 by 63% injection methods.1191 The individual plates were pelletized
while N2 and O2 showed negligible effect. with various mixing ratios (BS, BS1BT9, BS1.5BT8.5, BS2BT8,
7.7.3. Doping Control. Doping has been widely used for BS), and the thermoelectric properties were measured. The
tuning the carrier concentration to achieve the desired electrical conductivities monotonically decreased from 440 to
electrical conductivity. As well as control over carrier 200 S cm−1 at room temperature as the BS component
concentration, lattice thermal conductivity is reduced by increased, while the Seebeck coefficient showed a maximum at
dopant through point defect scattering. Various dopants −200 μV K−1 with BS1.5BT8.5. The thermal conductivity
including cations (Cu, Ag, Tl, Sm, Ce, Na, Er, La) and anions (κtot) of the nanocomposite ranged from 0.55 to 0.68 W m−1
(Cl, I, S, Se, Te) have been reported to enhance thermoelectric K−1 at room temperature, which is significantly lower than that
performances.1198−1210 Shi et al. synthesized a p-type heavily of the bulk Bi2Te3 with microsized grains (∼1.5 W m−1 K−1).
Cu-doped polycrystalline SnSe with different concentrations of The maximum ZT obtained in the BT85BS15 samples was
Cu. 1211 In the absence of Cu, rectangular plate-like 0.71 at 480 K. They synthesized the multiple core−shell
morphologies with lateral dimensions between 30−200 μm heterostructured NPs such as Bi2Se3 and Bi2Te3, Bi2Se3@
were observed, but the morphology changed to long belts Bi2Te3 core−shell NPs by the epitaxial growth by a one-pot
when a maximum Cu solubility of 11.8% was reached (Figure heat up method.1228 By repeating the epitaxial process,
52d). The elements (Sn, Cu, Se) were homogeneously consecutive multishell NPs (BS@BT@BS@BT) were obtained
distributed in the 1D belt structure (Figure 52e). The doped (Figure 52g). The maximum power factor (0.9 mW m−1 K−2 at
Cu (mainly Cu(I)) produced additional holes, thus σ from 9.9 450 K), significantly low thermal conductivity (0.53−0.55 W
to 53.7 S cm−1. A high power factor of 5.34 μW m−1 K−2 at m−1 K−1), and a high ZT of 0.71 at 450 K were obtained when
873 K was achieved. The doped Cu acted as point defects and the weight fraction of BS@BT was 2:8, which resulted from
induced crystal defects, which scatters phonons and κ phonon scattering at the interfaces and hot carrier filtering
decreases. The ZT continued to increase with the Cu fraction (Figure 52h).
and reached a high ZT (1.41) at 823 K (Figure 52f). Hong et
al. achieved a high ZT of 1.23 at 480 K by using Bi2Te2.7Se0.3 8. OUTLOOK
NPs with a lateral dimension of ∼1 μm and thickness of ∼30 The strong in-plane anisotropy of chalcogenides has opened up
nm.1207 σ was low and continued to decrease over the entire a plethora of opportunities for novel physicochemical proper-
temperature region (5.9 × 104 to 4.7 × 104 S m−1). The peak ties and practical applications in next generation devices,
value of S (−198 μV K−1) was achieved at 460 K in catalysts, and sensing platforms.37,125,146,153,896,1229 Significant
Bi2Te2.7Se0.3 whereas the peak (−173 μV K−1) was at 420 K for advances have been made in the synthesis of 1D and 2D MC
Bi2Te3. The Bi2Te2.7Se0.3 exhibited the highest power factor of nanocrystals with a certain degree of controllability over
Chem. Rev. 2023, 123, 3329−3442
dimensions, compositions, doping, and heterostructures. High dimension control, synthetic routes to independent control of
throughput production by the solution phase synthesis and the dimensional parameters should be found. Successive
exfoliation is readily achieved now; hence, the anisotropic MC morphological control has been achieved in the solution
crystal dispersions can be immediately applied as electrodes or phase synthesis mainly by using the shape-directing surfactants.
catalysts in electrochemical devices such as batteries and Unfortunately, the use of surfactants would degrade electrical,
supercapacitors.1124−1126 Postmodulation of the presynthe- electrochemical, and catalytic properties. Henckel et al.
sized MC crystals or in situ modulation during synthesis to demonstrated that salt could remove the adsorbed dodecyl-
obtain target properties has been actively developed amine, hence reducing overpotential and charge transfer
recently,150,381,718 and it is expected that reliable property resistance for HER.1235 More efforts to clearly remove the
engineering of anisotropic MCs will be achieved in the near surfactants from the MC crystal surfaces should be undertaken.
future. Exfoliation is a possible way to produce clean-surface MCs.
1D MC crystals with intrinsic anisotropic metallic properties However, the sizes are inevitably nonuniform and the
remained conductive under severe mechanical deformation.99 uncontrollable defects caused by the high-power ultra-
Efforts have also been made to theoretically understand the sonication is the technological issue to be solved. Self-assembly
effect of intercalation and heteroatom doping on the physical, is rather easier in the solution phase than in the vapor phase;
electronic, transport, and mechanical properties of the metallic thus, surface energy control of 1D or 2D MC crystals may lead
1D NWs.1230 A variety of semiconducting 1D MCs have been to the tip-to-tip or edge-to-edge heterostructures. There have
synthesized and used as functional active channels, especially been several demonstrations of 1D radial heterostructure
for chemical sensing and photodetection.147 The possibility of between MoS2/CNT1236 and the 2D vertical heterostructure
band gap opening of conductive NWs has been investigated by of Sn0.5W0.5S2/SnS2;1237 however, the uniformity in size and
theoretical modeling, suggesting that an isolated NW possesses composition without defective points is still difficult to achieve.
a small gap (≈ 0.3 eV) semiconducting property, while the Effective ways to passivate the high-energy facets and activate
NW bundles are predicted to be metallic.2 With the discovery low-energy facets during the synthesis are required.
of many emerging functionalities of 1D chalcogenides (such as The lack of availability of high-quality wafer-scale MC
superconductor−insulator transitions,119 lower levels of the specimens is also a significant roadblock. Uniformly controlled
normalized noise spectral density,168 disorder-enhanced quasi- growth and environmental stability of 2D MCs in their
one-dimensional superconductivity,1231 strong magnetocrystal- semiconducting and metallic phases require remarkable
line anisotropy,101 etc.), fabrication techniques for uniform breakthroughs. Although considerable progress has been
functions should be realized for full potential uses. made in the wafer-scale uniform growth of polycrystalline 2D
2D semiconducting MCs and interconversion to the metallic MCs (e.g., MoS2 and WS2) by CVD and MOCVD,457 the
phase have been attracting intensive studies.502 State-of-the-art challenges associated with precise control of the number of
carrier mobility exceeding 103 cm2 V−1 s−1 at room layers and phase targeting of the MCs over the wafer scale
temperature was achieved with hBN-encapsulated InSe-based should be addressed in a practical way. Alkali metal salts
FETs.208 Vertical vdW heterostructures between metallic and assisted CVD and MOCVD synthesis has been an efficient way
semiconducting MCs showed ohmic contact and improved the to modulate the grain size in the 2D MCs thin films.445
carrier mobility with a narrower mobility distribution.130 The Postgrowth phase engineering has also been achieved by
heterostructures and superlattices consisting of two semi- seeded 2D epitaxy to produce wafer-scale single crystal 2H-
conducting 2D MCs or one semiconducting MC and one MoTe2.727 The most recent success of the epitaxial growth of
metallic MC have presented a high degree of flexibility in wafer-scale single crystal MCs (e.g., MoS2, WS2) has been
material species.1232 Especially, the vdW epitaxial integration achieved on atomically flat vicinal step-edged c-plane Al2O3
has defied the limits imposed by the requirements of lattice and Au (111) substrates.484 However, reproducible prepara-
commensurability and processing compatibility.1233 The tion of the step-edged substrate is a big challenge. A recent
potential of 2D MC-based semiconductors and their vdW approach of surface diffusion and epitaxial self-planarization
heterostructures have been intensively explored in various 2D may be a possible way to remove the substrate issue.500 The
devices such as thin tunnelling FETs,5 memtransistors,4 approach allowed for the growth of wafer-scale single-crystal
phototransistors,13,935 light emitting and light harvesting 2D MCs (e.g., Si2Te3, GeTe, GeSe, etc.) by directly reacting
devices.987,988 However, their prospects for scalable integration chalcogen sources with commercial single crystal substrates
with state-of-the-art Si based production line remain a great (e.g., Si wafer and Ge wafer). The reaction is speedy and does
challenge. It is mainly due to the inferior carrier mobilities of not require the transfer process for fabrication of switching
MC-based devices compared to the conventional semi- devices.
conductors (e.g., Si and GaAs).457 Moreover, the transfer Exploring the full potential of MCs requires a robust strategy
process currently required in 2D thin films for device for precise modulation of the grain, grain boundaries, chemical
fabrication is not compatible to the industrial manufacturing compositions, crystal phases, heterostructures, and defects
process.1234 formation. The native defects and extrinsic dopants in 2D MCs
Well-controlled dimensions and compositions has been are found to tune the Fermi level, create mid gap states, and
achieved mainly through the vapor-phase synthesis. Although enable semiconducting p−n junction formation.838 Exciting
solution-based volumetric production of anisotropic MC opportunities are available to control the defect and doping
crystals is possible through the bottom-up synthesis and the process to adjust the optoelectronic and photovoltaic proper-
exfoliation, detailed structural control and heterostructure ties of 2D MCs. Another emerging opportunity for 2D MC-
formation have not been successful so far. Control of the based devices may lie in the unconventional flexible
dimensions (diameter, thickness, length, width) in solution electronics, which is currently dominated by organic semi-
phase is complicated because the dimensional parameters conductors. High carrier mobility, flexibility, and environ-
mutually affect each other during the synthesis. For delicate mental stability of 2D MCs can provide an ideal platform for
Chem. Rev. 2023, 123, 3329−3442
high-speed low power flexible electronic devices. However, Biographies

there are some obstacles to overcome to realize flexible devices.
Anupam Giri is currently an Assistant Professor of Chemistry at the
First, scalable and high-quality MCs production is necessary
University of Allahabad, Prayagraj, India. He received his B.Sc. (2007)
for practical large-area devices. Although vapor phase synthesis
and M.Sc. (2009) degrees in Chemistry from the University of
can produce high-quality diverse MCs, their high growth
Calcutta, India. He completed his Ph.D. in Chemistry (2014) from
temperature limits the growth of MCs directly on the
Jadavpur University, Kolkata under the supervision of Prof. Samir
polymeric substrates. Solution phase synthesis has advantages
Kumar Pal at S. N. Bose National Centre for Basic Sciences, Kolkata,
in control over dimension/composition; however, the
India. As a postdoctoral fellow, he joined Prof. Unyong Jeong’s group
existence of ligands alters or degrades their properties when
in 2014 and worked until 2020 at the Department of Materials
the nanocrystals are made in a thin film. Exfoliation allows
Science and Engineering, POSTECH, Korea, before being promoted
scalable production of high-quality MCs with a low-cost and
to research associate professor in the same department, where he
low-temperature process. Unfortunately, dimension and
worked until 2021. His research interests focus on the synthesis and
homogeneity are not easily achieved. Second, device
electronic applications of two-dimensional materials.
fabrication with low contact resistance under a high degree
of strain should be improved. The contact resistance during Gyeongbae Park is currently a senior researcher in Korea Institute of
mechanical deformation deteriorates the properties of devices, Industrial Technology (KITECH). He received his B.S. degree from
requiring the optimization of electrical and mechanical contact the Department of Materials Science and Engineering, Yonsei
interfaces. In some devices, brittle SiO2 dielectrics, or Al2O3 University, Republic of Korea (2013). He received his Ph.D. degree
encapsulation layers, are needed. Even though reducing the under the supervision of Prof. Unyong Jeong at the Department of
thickness of brittle layers can be helpful for improving Materials Science and Engineering, Pohang University of Science and
flexibility, it is still challenging to achieve high flexibility Technology(POSTECH), Republic of Korea (2020). He worked as a
without degradation of material properties. postdoctoral fellow in Prof. Unyong Jeong’s group until 2022. His
With the recent discovery of 2D magnetism in binary and research interests include synthesis of metal-oxides and -chalcogenides
ternary semiconducting MCs,42 magnetic vdW materials in the nanomaterials, and its applications.
vdW heterostructures may facilitate fabrication of magneto- Unyong Jeong is a professor of Material Science and Engineering at
optical and magnetoelectric devices for ultracompact spin- Pohang University of Science and Technology (POSTECH) in Korea
tronics and on-chip optical communications. The metallic and a member of Korea Academy of Science and Technology. He
counterparts of 2D MCs are recognized as a promising received B.S. degree (1998), M.A. degree (2000), and Ph.D. degree
substitute to noble metal catalysts.1238 Since the active sites of (2003) in chemical engineering in POSTECH. After working as a
MC crystals lie in their defects and edges,153 nanoengineering postdoctoral fellow at University of Washing in Seattle, he started his
to control MC-based composites is of great importance to independent research career as an assistant professor in Yonsei
expose more defects and edge sites with smaller and thinner University in Korea (2006). He moved to POSTECH (2015) as a Se-
nanostructures. Ah distinguished professor. He is a member of Korean Academy of
Science and Technology and an associate editor of J. Mater. Chem. C.
AUTHOR INFORMATION His research includes fabrication of flexible stretchable electronic
Corresponding Author devices and synthesis of nanostructured materials.
Unyong Jeong − Department of Materials Science and
Engineering, Pohang University of Science and Technology, ACKNOWLEDGMENTS
Pohang, Gyeongbuk 790-784, Korea; orcid.org/0000- This work was supported by Samsung Research Funding &
0002-7519-7595; Email: ujeong@postech.ac.kr Incubation Center of Samsung Electronics under Project
Authors Number SRFC-MA2001-02. A.G. acknowledges support of the
Ramanujan Fellowship (SERB) under Award Number RJF/
Anupam Giri − Department of Chemistry, Faculty of Science, 2020/000086.
University of Allahabad, Prayagraj, UP 211002, India
Gyeongbae Park − Department of Materials Science and
Engineering, Pohang University of Science and Technology, REFERENCES
Pohang, Gyeongbuk 790-784, Korea; Functional Materials (1) Wang, Q. H.; Kalantar-Zadeh, K.; Kis, A.; Coleman, J. N.;
and Components R&D Group, Korea Institute of Industrial Strano, M. S. Electronics and Optoelectronics of Two-Dimensional
Technology, Gangneung, Gangwon-do 25440, Republic of Transition Metal Dichalcogenides. Nat. Nanotechnol. 2012, 7, 699−
Korea 712.
(2) Shang, C.; Fu, L.; Zhou, S.; Zhao, J. Atomic Wires of Transition
Complete contact information is available at: Metal Chalcogenides: A Family of 1D Materials for Flexible
https://pubs.acs.org/10.1021/acs.chemrev.2c00455 Electronics and Spintronics. JACS Au 2021, 1, 147−155.
(3) Wu, F.; Tian, H.; Shen, Y.; Hou, Z.; Ren, J.; Gou, G.; Sun, Y.;
Author Contributions Yang, Y.; Ren, T.-L. Vertical MoS2 Transistors with Sub-1-nm Gate
∥ Lengths. Nature 2022, 603, 259−264.
A.G. and G.P. contributed equally to this work. CRediT: (4) Sangwan, V. K.; Lee, H.-S.; Bergeron, H.; Balla, I.; Beck, M. E.;
Anupam Giri conceptualization, writing-original draft, writing- Chen, K.-S.; Hersam, M. C. Multi-Terminal Memtransistors from
review & editing; Gyeongbae Park conceptualization, writing- Polycrystalline Monolayer Molybdenum Disulfide. Nature 2018, 554,
original draft, writing-review & editing; Unyong Jeong content 500−504.
organization, conceptualization, writing-review & editing. (5) Sarkar, D.; Xie, X.; Liu, W.; Cao, W.; Kang, J.; Gong, Y.;
Kraemer, S.; Ajayan, P. M.; Banerjee, K. A Subthermionic Tunnel
Notes
Field-Effect Transistor with an Atomically Thin Channel. Nature
The authors declare no competing financial interest. 2015, 526, 91−95.
Chem. Rev. 2023, 123, 3329−3442
(6) Li, S.; Lin, Y.-C.; Zhao, W.; Wu, J.; Wang, Z.; Hu, Z.; Shen, Y.; Their Carbon-Based Hybrids for Advanced Potassium Battery
Tang, D.-M.; Wang, J.; Zhang, Q.; et al. Vapour−Liquid−Solid Anodes. Mater. Chem. Front. 2021, 5, 4401−4423.
Growth of Monolayer MoS2 Nanoribbons. Nat. Mater. 2018, 17, (25) Ma, Q.; Zheng, Y.; Luo, D.; Or, T.; Liu, Y.; Yang, L.; Dou, H.;
535−542. Liang, J.; Nie, Y.; Wang, X.; Yu, A.; Chen, Z. 2D Materials for All-
(7) Xia, F.; Wang, H.; Xiao, D.; Dubey, M.; Ramasubramaniam, A. Solid-State Lithium Batteries. Adv. Mater. 2022, 34, 2108079.
Two-Dimensional Material Nanophotonics. Nat. Photonics 2014, 8, (26) Goodenough, J. B. How We Made the Li-Ion Rechargeable
899−907. Battery. Nat. Electron. 2018, 1, 204−204.
(8) Empante, T. A.; Martinez, A.; Wurch, M.; Zhu, Y.; Geremew, A. (27) Tan, S. M.; Pumera, M. Two-Dimensional Materials on the
K.; Yamaguchi, K.; Isarraraz, M.; Rumyantsev, S.; Reed, E. J.; Rocks: Positive and Negative Role of Dopants and Impurities in
Balandin, A. A.; et al. Low Resistivity and High Breakdown Current Electrochemistry. ACS Nano 2019, 13, 2681−2728.
Density of 10 nm Diameter vdW TaSe3 Nanowires by Chemical (28) Voiry, D.; Yang, J.; Chhowalla, M. Recent Strategies for
Vapor Deposition. Nano Lett. 2019, 19, 4355−4361. Improving the Catalytic Activity of 2D TMD Nanosheets toward the
(9) Zhu, Y.; Rehn, D. A.; Antoniuk, E. R.; Cheon, G.; Freitas, R.; Hydrogen Evolution Reaction. Adv. Mater. 2016, 28, 6197−6206.
Krishnapriyan, A.; Reed, E. J. Spectrum of Exfoliable 1D vdW (29) Yin, J.; Jin, J.; Lin, H.; Yin, Z.; Li, J.; Lu, M.; Guo, L.; Xi, P.;
Molecular Wires and Their Electronic Properties. ACS Nano 2021, Tang, Y.; Yan, C.-H. Optimized Metal Chalcogenides for Boosting
15, 9851−9859. Water Splitting. Adv. Sci. 2020, 7, 1903070.
(10) Shimizu, H.; Pu, J.; Liu, Z.; Lim, H. E.; Maruyama, M.; (30) Lu, Q.; Yu, Y.; Ma, Q.; Chen, B.; Zhang, H. 2D Transition-
Nakanishi, Y.; Ito, S.; Kikuchi, I.; Endo, T.; Yanagi, K.; Oshima, Y.; Metal-Dichalcogenide-Nanosheet-Based Composites for Photocata-
et al. Formation of a Two-Dimensional Electronic System in Laterally lytic and Electrocatalytic Hydrogen Evolution Reactions. Adv. Mater.
Assembled WTe Nanowires. ACS Appl. Nano Mater. 2022, 5, 6277− 2016, 28, 1917−1933.
6284. (31) Sarkar, D.; Liu, W.; Xie, X.; Anselmo, A. C.; Mitragotri, S.;
(11) Ajayan, P.; Kim, P.; Banerjee, K. Two-Dimensional vdW Banerjee, K. MoS2 Field-Effect Transistor for Next-Generation Label-
Materials. Phys. Today 2016, 69, 38−44. Free Biosensors. ACS Nano 2014, 8, 3992−4003.
(12) Li, X.; Kahn, E.; Chen, G.; Sang, X.; Lei, J.; Passarello, D.; (32) Bolotsky, A.; Butler, D.; Dong, C.; Gerace, K.; Glavin, N. R.;
Oyedele, A. D.; Zakhidov, D.; Chen, K.-W.; Chen, Y.-X.; et al. Muratore, C.; Robinson, J. A.; Ebrahimi, A. Two-Dimensional
Surfactant-Mediated Growth and Patterning of Atomically Thin Materials in Biosensing and Healthcare: From in vitro Diagnostics
Transition Metal Dichalcogenides. ACS Nano 2020, 14, 6570−6581. to Optogenetics and Beyond. ACS Nano 2019, 13, 9781−9810.
(13) Zhang, Z.; Niu, J.; Yang, P.; Gong, Y.; Ji, Q.; Shi, J.; Fang, Q.; (33) Barua, S.; Dutta, H. S.; Gogoi, S.; Devi, R.; Khan, R.
Jiang, S.; Li, H.; Zhou, X.; et al. vdW Epitaxial Growth of 2D Metallic Nanostructured MoS2-Based Advanced Biosensors: A Review. ACS
Vanadium Diselenide Single Crystals and Their Extra-High Electrical Appl. Nano Mater. 2018, 1, 2−25.
Conductivity. Adv. Mater. 2017, 29, 1702359. (34) Kalantar-zadeh, K.; Ou, J. Z. Biosensors Based on Two-
(14) Lin, Z.; Liu, Y.; Halim, U.; Ding, M.; Liu, Y.; Wang, Y.; Jia, C.;
Dimensional MoS2. ACS Sens. 2016, 1, 5−16.
Chen, P.; Duan, X.; Wang, C.; Song, F.; Li, M.; Wan, C.; Huang, Y.; (35) Wang, X.; Ding, W.; Li, H.; Li, H.; Zhu, S.; Zhu, X.; Dai, J.;
Duan, X. Solution-Processable 2D Semiconductors for High-Perform-
Sheng, Z.; Wang, H.; Zhu, X.; Sun, Y.; Dou, S. X. Unveiling Highly
ance Large-Area Electronics. Nature 2018, 562, 254−258.
Ambient-Stable Multilayered 1T-MoS2 Towards All-Solid-State
(15) Giri, A.; Yang, H.; Thiyagarajan, K.; Jang, W.; Myoung, J. M.;
Flexible Supercapacitors. J. Mater. Chem. A 2019, 7, 19152−19160.
Singh, R.; Soon, A.; Cho, K.; Jeong, U. One-Step Solution Phase
(36) Joseph, N.; Shafi, P. M.; Bose, A. C. Recent Advances in 2D-
Growth of Transition Metal Dichalcogenide Thin Films Directly on
MoS2 and its Composite Nanostructures for Supercapacitor Electrode
Solid Substrates. Adv. Mater. 2017, 29, 1700291.
(16) Wang, X.; Wang, P.; Wang, J.; Hu, W.; Zhou, X.; Guo, N.; Application. Energy Fuels 2020, 34, 6558−6597.
(37) Acerce, M.; Voiry, D.; Chhowalla, M. Metallic 1T Phase MoS2
Huang, H.; Sun, S.; Shen, H.; Lin, T.; et al. Ultrasensitive and
Broadband MoS2 Photodetector Driven by Ferroelectrics. Adv. Mater. Nanosheets as Supercapacitor Electrode Materials. Nat. Nanotechnol.
2015, 27, 6575−6581. 2015, 10, 313−318.
(17) Massicotte, M.; Schmidt, P.; Vialla, F.; Schädler, K. G.; (38) Kayyalha, M.; Maassen, J.; Lundstrom, M.; Shi, L.; Chen, Y. P.
Reserbat-Plantey, A.; Watanabe, K.; Taniguchi, T.; Tielrooij, K. J.; Gate-Tunable and Thickness-Dependent Electronic and Thermo-
Koppens, F. H. L. Picosecond Photoresponse in vdW Hetero- electric Transport in Few-Layer MoS2. J. Appl. Phys. 2016, 120,
structures. Nat. Nanotechnol. 2016, 11, 42−46. 134305.
(18) Shin, G. H.; Park, C.; Lee, K. J.; Jin, H. J.; Choi, S.-Y. (39) Pang, H.; Qiu, Y.; Wang, D.; Qin, Y.; Huang, R.; Yang, Z.;
Ultrasensitive Phototransistor Based on WSe2−MoS2 vdW Hetero- Zhang, X.; Zhao, L.-D. Realizing n-Type Snte Thermoelectrics with
junction. Nano Lett. 2020, 20, 5741−5748. Competitive Performance through Suppressing Sn Vacancies. J. Am.
(19) Singh, R.; Giri, A.; Pal, M.; Thiyagarajan, K.; Kwak, J.; Lee, J.-J.; Chem. Soc. 2021, 143, 8538−8542.
Jeong, U.; Cho, K. Perovskite Solar Cells with an MoS2 Electron (40) Qian, X.; Liu, J.; Fu, L.; Li, J. Quantum Spin Hall Effect in
Transport Layer. J. Mater. Chem. A 2019, 7, 7151−7158. Two-Dimensional Transition Metal Dichalcogenides. Science 2014,
(20) Yu, W. J.; Liu, Y.; Zhou, H.; Yin, A.; Li, Z.; Huang, Y.; Duan, X. 346, 1344.
Highly Efficient Gate-Tunable Photocurrent Generation in Vertical (41) Xiao, D.; Liu, G.-B.; Feng, W.; Xu, X.; Yao, W. Coupled Spin
Heterostructures of Layered Materials. Nat. Nanotechnol. 2013, 8, and Valley Physics in Monolayers of MoS2 and Other Group-Vi
952−958. Dichalcogenides. Phys. Rev. Lett. 2012, 108, 196802.
(21) Li, W.; Yang, L.; Wang, J.; Xiang, B.; Yu, Y. Three- (42) Gong, C.; Li, L.; Li, Z.; Ji, H.; Stern, A.; Xia, Y.; Cao, T.; Bao,
Dimensionally Interconnected TaS3 Nanowire Network as Anode W.; Wang, C.; Wang, Y.; et al. Discovery of Intrinsic Ferromagnetism
for High-Performance Flexible Li-Ion Battery. ACS Appl. Mater. in Two-Dimensional vdW Crystals. Nature 2017, 546, 265−269.
Interfaces 2015, 7, 5629−5633. (43) Deng, Y.; Yu, Y.; Song, Y.; Zhang, J.; Wang, N. Z.; Sun, Z.; Yi,
(22) Tanibata, N.; Matsuyama, T.; Hayashi, A.; Tatsumisago, M. All- Y.; Wu, Y. Z.; Wu, S.; Zhu, J.; et al. Gate-Tunable Room-Temperature
Solid-State Sodium Batteries Using Amorphous TiS3 Electrode with Ferromagnetism in Two-Dimensional Fe3GeTe2. Nature 2018, 563,
High Capacity. J. Power Sources 2015, 275, 284−287. 94−99.
(23) Lei, Z.; Zhan, J.; Tang, L.; Zhang, Y.; Wang, Y. Recent (44) Saito, Y.; Nojima, T.; Iwasa, Y. Highly Crystalline 2D
Development of Metallic (1T) Phase of Molybdenum Disulfide for Superconductors. Nat. Rev. Mater. 2017, 2, 16094.
Energy Conversion and Storage. Adv. Energy Mater. 2018, 8, 1703482. (45) Nasilowski, M.; Mahler, B.; Lhuillier, E.; Ithurria, S.; Dubertret,
(24) Li, Z.; Sun, R.; Qin, Z.; Liu, X.; Wang, C.; Fan, H.; Zhang, Y.; B. Two-Dimensional Colloidal Nanocrystals. Chem. Rev. 2016, 116,
Lu, S. Recent Progress of Nanostructured metal chalcogenides and 10934−10982.
Chem. Rev. 2023, 123, 3329−3442
(46) Min, Y.; Moon, G. D.; Kim, C.-E.; Lee, J.-H.; Yang, H.; Soon, Reactions from WS2 Nanoribbons. Adv. Energy Mater. 2014, 4,
A.; Jeong, U. Solution-Based Synthesis of Anisotropic Metal 1301875.
Chalcogenide Nanocrystals and Their Applications. J. Mater. Chem. (66) Qi, R.; Wang, S.; Wang, M.; Liu, W.; Yan, Z.; Bi, X.; Huang, Q.
C 2014, 2, 6222−6248. Towards Well-Defined MoS2 Nanoribbons on a Large Scale. Chem.
(47) Wang, F.; Buhro, W. E. An Easy Shortcut Synthesis of Size- Commun. 2017, 53, 9757−9760.
Controlled Bismuth Nanoparticles and Their Use in the SLS Growth (67) Khalil, A.; Liu, Q.; He, Q.; Xiang, T.; Liu, D.; Wang, C.; Fang,
of High-Quality Colloidal Cadmium Selenide Quantum Wires. Small Q.; Song, L. Metallic 1T-WS2 Nanoribbons as Highly Conductive
2010, 6, 573−581. Electrodes for Supercapacitors. RSC Adv. 2016, 6, 48788−48791.
(48) Sun, J.; Wang, L.-W.; Buhro, W. E. Synthesis of Cadmium (68) Zhang, H.; Li, X.-B.; Liu, L.-M. Tunable Electronic and
Telluride Quantum Wires and the Similarity of Their Effective Band Magnetic Properties of WS2 Nanoribbons. J. Appl. Phys. 2013, 114,
Gaps to Those of Equidiameter Cadmium Telluride Quantum Dots. J. No. 093710.
Am. Chem. Soc. 2008, 130, 7997−8005. (69) Sutter, P.; French, J. S.; Khosravi Khorashad, L.; Argyropoulos,
(49) Ratnaweera, R. J.; Rodríguez Ortiz, F. A.; Gripp, N. J.; Sheldon, C.; Sutter, E. Optoelectronics and Nanophotonics of Vapor−Liquid−
M. T. Quantifying Order During Field-Driven Alignment of Colloidal Solid Grown GaSe vdW Nanoribbons. Nano Lett. 2021, 21, 4335−
Semiconductor Nanorods. ACS Nano 2022, 16, 3834−3842. 4342.
(50) Talapin, D. V.; Shevchenko, E. V.; Murray, C. B.; Kornowski, (70) Zhou, J. Structures and Electronic Properties of GaSe and GaS
A.; Förster, S.; Weller, H. CdSe and CdSSe/CdS Nanorod Solids. J. Nanoribbons. RSC Adv. 2015, 5, 94679−94684.
Am. Chem. Soc. 2004, 126, 12984−12988. (71) Xiong, X.; Zhang, Q.; Zhou, X.; Jin, B.; Li, H.; Zhai, T. One-
(51) Kim, D.; Bae, W. K.; Kim, S.-H.; Lee, D. C. Depletion- Step Synthesis of P-Type GaSe Nanoribbons and Their Excellent
Mediated Interfacial Assembly of Semiconductor Nanorods. Nano Performance in Photodetectors and Phototransistors. J. Mater. Chem.
Lett. 2019, 19, 963−970. C 2016, 4, 7817−7823.
(52) Ning, J.; Kershaw, S. V.; Rogach, A. L. Temperature-Controlled (72) Jung, C. S.; Park, K.; Shojaei, F.; Oh, J. Y.; Im, H. S.; Lee, J. A.;
Fragmentation and Ripening: Synthesis of ZnSe Nanorods with Jang, D. M.; Park, J.; Myoung, N.; Lee, C.-L.; et al. Photo-
Variable Dimensions and Crystal Structure Starting from Ultrathin luminescence and Photocurrents of GaS1−XSex Nanobelts. Chem.
ZnSe Nanowires. Chem. Mater. 2020, 32, 3960−3969. Mater. 2016, 28, 5811−5820.
(53) Xu, X.; Li, S.; Chen, J.; Cai, S.; Long, Z.; Fang, X. Design (73) Fan, Z.-Q.; Jiang, X.-W.; Wei, Z.; Luo, J.-W.; Li, S.-S. Tunable
Principles and Material Engineering of ZnS for Optoelectronic Electronic Structures of GeSe Nanosheets and Nanoribbons. J. Phys.
Devices and Catalysis. Adv. Funct. Mater. 2018, 28, 1802029. Chem. C 2017, 121, 14373−14379.
(54) Yong, K.-T.; Sahoo, Y.; Zeng, H.; Swihart, M. T.; Minter, J. R.; (74) He, W.; Chen, H.; Ouyang, H.; Zhou, J.; Sui, Y.; Zhang, C.;
Zheng, X.; Zhang, R.; Yuan, X.; Xu, Z.; Cheng, X. a. Tunable
Prasad, P. N. Formation of ZnTe Nanowires by Oriented Attachment.
Anisotropic Plasmon Response of Monolayer GeSe Nanoribbon
Chem. Mater. 2007, 19, 4108−4110.
Arrays. Nanoscale 2020, 12, 16762−16769.
(55) Dong, K.; Chen, Q.-C.; Xing, Z.; Chen, Y.; Qi, Y.; Pavlpoulos,
(75) Sutter, E.; Sutter, P. 1D Wires of 2D Layered Materials:
N. G.; Amirav, L. Silver Tipping of CdSe@CdS Nanorods: How to
Germanium Sulfide Nanowires as Efficient Light Emitters. ACS Appl.
Avoid Cation Exchange. Chem. Mater. 2021, 33, 6394−6402.
Nano Mater. 2018, 1, 1042−1049.
(56) Yang, Y.; Wang, K.; Liang, H.-W.; Liu, G.-Q.; Feng, M.; Xu, L.;
(76) Chen, Z.; Hoang, A. T.; Seo, D.; Cho, M.; Kim, Y. D.; Yang, L.;
Liu, J.-W.; Wang, J.-L.; Yu, S.-H. A New Generation of Alloyed/
Ahn, J.-H.; Choi, H.-J. Topography Dependence of Conductivity in
Multimetal chalcogenide Nanowires by Chemical Transformation. Sci.
Electrostrictive Germanium Sulfide Nanoribbons. 2D Mater. 2022, 9,
Adv. 2015, 1, e1500714. No. 045008.
(57) Hu, J.; Li, L.-s.; Yang, W.; Manna, L.; Wang, L.-w.; Alivisatos, A. (77) Vaughn, D.; Sun, D.; Levin, S. M.; Biacchi, A. J.; Mayer, T. S.;
P. Linearly Polarized Emission from Colloidal Semiconductor Schaak, R. E. Colloidal Synthesis and Electrical Properties of GeSe
Quantum Rods. Science 2001, 292, 2060−2063. NBs. Chem. Mater. 2012, 24, 3643−3649.
(58) Shabaev, A.; Efros, A. L. 1D Exciton Spectroscopy of (78) Yim, J. W. L.; Xiang, B.; Wu, J. Sublimation of GeTe Nanowires
Semiconductor NRs. Nano Lett. 2004, 4, 1821−1825. and Evidence of Its Size Effect Studied by in Situ Tem. J. Am. Chem.
(59) Nam, S.; Oh, N.; Zhai, Y.; Shim, M. High Efficiency and Soc. 2009, 131, 14526−14530.
Optical Anisotropy in Double-Heterojunction Nanorod Light- (79) Zhang, J.; Tse, P.-L.; Jalil, A.-R.; Kölzer, J.; Rosenbach, D.;
Emitting Diodes. ACS Nano 2015, 9, 878−885. Luysberg, M.; Panaitov, G.; Lüth, H.; Hu, Z.; Grützmacher, D.; et al.
(60) Liu, Q.; Hong, X.; Zhang, X.; You, X.; Zhao, X.; Liu, X.; Ye, M. Flux Periodic Oscillations and Phase-Coherent Transport in GeTe
Hierarchical Cu2S Nanorods with Different Crystal Phases for Nanowire-Based Devices. Nat. Commun. 2021, 12, 754.
Asymmetrical Supercapacitors and Visible-Light Photocatalysis. (80) Lim, H. E.; Nakanishi, Y.; Liu, Z.; Pu, J.; Maruyama, M.; Endo,
Dalton Trans. 2018, 47, 15189−15196. T.; Ando, C.; Shimizu, H.; Yanagi, K.; Okada, S.; et al. Wafer-Scale
(61) Sigman, M. B.; Ghezelbash, A.; Hanrath, T.; Saunders, A. E.; Growth of One-Dimensional Transition-Metal Telluride Nanowires.
Lee, F.; Korgel, B. A. Solventless Synthesis of Monodisperse Cu2S Nano Lett. 2021, 21, 243−249.
Nanorods, Nanodisks, and Nanoplatelets. J. Am. Chem. Soc. 2003, (81) Basuvalingam, S. B.; Zhang, Y.; Bloodgood, M. A.; Godiksen, R.
125, 16050−16057. H.; Curto, A. G.; Hofmann, J. P.; Verheijen, M. A.; Kessels, W. M. M.;
(62) Luther, J. M.; Zheng, H.; Sadtler, B.; Alivisatos, A. P. Synthesis Bol, A. A. Low-Temperature Phase-Controlled Synthesis of Titanium
of PbS Nanorods and Other Ionic Nanocrystals of Complex Di- and Tri-Sulfide by Atomic Layer Deposition. Chem. Mater. 2019,
Morphology by Sequential Cation Exchange Reactions. J. Am. 31, 9354−9362.
Chem. Soc. 2009, 131, 16851−16857. (82) Island, J. O.; Biele, R.; Barawi, M.; Clamagirand, J. M.; Ares, J.
(63) Saraidarov, T.; Reisfeld, R.; Sashchiuk, A.; Lifshitz, E. Synthesis R.; Sánchez, C.; van der Zant, H. S. J.; Ferrer, I. J.; D’Agosta, R.;
and Characterization of PbS Nanorods and Nanowires. Phys. E: Low- Castellanos-Gomez, A. Titanium Trisulfide (TiS3): A 2D Semi-
dimens. Syst. Nanostructures 2007, 37, 173−177. conductor with Quasi-1D Optical and Electronic Properties. Sci. Rep.
(64) Wang, Z.; Li, H.; Liu, Z.; Shi, Z.; Lu, J.; Suenaga, K.; Joung, S.- 2016, 6, 22214.
K.; Okazaki, T.; Gu, Z.; Zhou, J.; et al. Mixed Low-Dimensional (83) Zhang, W.; Lv, T.; Deng, C.; Gao, H.; Hu, S.; Chen, F.; Liu, J.;
Nanomaterial: 2D Ultranarrow MoS2 Inorganic Nanoribbons Fan, X.; Liu, Y.; Jiao, B.; et al. Rapid Solid-Phase Sulfurization Growth
Encapsulated in Quasi-1D Carbon Nanotubes. J. Am. Chem. Soc. and Nonlinear Optical Characterization of Transfer-Free TiS3
2010, 132, 13840−13847. Nanoribbons. Chem. Mater. 2022, 34, 2790−2797.
(65) Lin, J.; Peng, Z.; Wang, G.; Zakhidov, D.; Larios, E.; Yacaman, (84) Nicholson, C. W.; Schwier, E. F.; Shimada, K.; Berger, H.;
M. J.; Tour, J. M. Enhanced Electrocatalysis for Hydrogen Evolution Hoesch, M.; Berthod, C.; Monney, C. Role of a Higher-Dimensional
Chem. Rev. 2023, 123, 3329−3442
Interaction in Stabilizing Charge Density Waves in Quasi-One- Ultrathin Single-Crystal Nanowires from Quasi-One-Dimensional
Dimensional NbSe3 Revealed by Angle-Resolved Photoemission vdW Crystals. Nano Lett. 2016, 16, 6188−6195.
Spectroscopy. Phys. Rev. B 2020, 101, No. 045412. (103) Lin, J.; Cretu, O.; Zhou, W.; Suenaga, K.; Prasai, D.; Bolotin,
(85) Chen, H.; Ma, Z.; Shao, Y.; Rehman, Z. U.; Zhang, K.; He, Q.; K. I.; Cuong, N. T.; Otani, M.; Okada, S.; Lupini, A. R.; Idrobo, J.-C.;
Song, L. Angle-/Temperature-Dependence of Raman Scattering in et al. Flexible Metallic Nanowires with Self-Adaptive Contacts to
Layered NbSe3 Crystal. AIP Adv. 2017, 7, No. 095316. Semiconducting Transition-Metal Dichalcogenide Monolayers. Nat.
(86) Pan, Z.; Yang, L.; Tao, Y.; Zhu, Y.; Xu, Y.-Q.; Mao, Z.; Li, D. Nanotechnol. 2014, 9, 436−442.
Net Negative Contributions of Free Electrons to the Thermal (104) Huang, X.; Zeng, Z.; Zhang, H. Metal Dichalcogenide
Conductivity of NbSe3 Nanowires. Phys. Chem. Chem. Phys. 2020, 22, Nanosheets: Preparation, Properties and Applications. Chem. Soc. Rev.
21131−21138. 2013, 42, 1934−1946.
(87) Stonemeyer, S.; Dogan, M.; Cain, J. D.; Azizi, A.; Popple, D. C.; (105) Sun, Y.; Terrones, M.; Schaak, R. E. Colloidal Nanostructures
Culp, A.; Song, C.; Ercius, P.; Cohen, M. L.; Zettl, A. Targeting One- of Transition-Metal Dichalcogenides. Acc. Chem. Res. 2021, 54, 1517−
and Two-Dimensional Ta−Te Structures via Nanotube Encapsula- 1527.
tion. Nano Lett. 2022, 22, 2285−2292. (106) Sangwan, V. K.; Hersam, M. C. Electronic Transport in Two-
(88) Liu, Z. Y.; Li, J.; Zhang, J. F.; Li, J.; Yang, P. T.; Zhang, S.; Dimensional Materials. Ann. Rev. Phys. Chem. 2018, 69, 299−325.
Chen, G. F.; Uwatoko, Y.; Yang, H. X.; Sui, Y.; et al. Quasi-One- (107) Yao, W.; Wu, B.; Liu, Y. Growth and Grain Boundaries in 2D
Dimensional Superconductivity in the Pressurized Charge-Density- Materials. ACS Nano 2020, 14, 9320−9346.
Wave Conductor HfTe3. npj Quantum Mater. 2021, 6, 90. (108) Huang, Y.; Pan, Y.-H.; Yang, R.; Bao, L.-H.; Meng, L.; Luo,
(89) Meyer, S.; Pham, T.; Oh, S.; Ercius, P.; Kisielowski, C.; Cohen, H.-L.; Cai, Y.-Q.; Liu, G.-D.; Zhao, W.-J.; Zhou, Z.; et al. Universal
M. L.; Zettl, A. Metal-Insulator Transition in Quasi-One-Dimensional Mechanical Exfoliation of Large-Area 2D Crystals. Nat. Commun.
HfTe3 in the Few-Chain Limit. Phys. Rev. B 2019, 100, No. 041403. 2020, 11, 2453.
(90) Hoesch, M.; Gannon, L.; Shimada, K.; Parrett, B. J.; Watson, (109) Ji, L.-J.; Qin, Y.; Gui, D.; Li, W.; Li, Y.; Li, X.; Lu, P.
M. D.; Kim, T. K.; Zhu, X.; Petrovic, C. Disorder Quenching of the Quantifying the Exfoliation Ease Level of 2D Materials via Mechanical
Charge Density Wave in ZrTe3. Phys. Rev. Lett. 2019, 122, Anisotropy. Chem. Mater. 2018, 30, 8732−8738.
No. 017601. (110) Alzakia, F. I.; Tan, S. C. Liquid-Exfoliated 2D Materials for
(91) Jin, J.; Wurch, M.; Baraghani, S.; Coyle, D. J.; Empante, T. A.; Optoelectronic Applications. Adv. Sci. 2021, 8, 2003864.
Kargar, F.; Balandin, A. A.; Bartels, L. Metallic Transport in Chemical (111) Shen, J.; He, Y.; Wu, J.; Gao, C.; Keyshar, K.; Zhang, X.; Yang,
Vapor Deposition ZrTe3 Nanoribbons on a SiO2 Wafer Substrate. Y.; Ye, M.; Vajtai, R.; Lou, J.; et al. Liquid Phase Exfoliation of Two-
Cryst. Growth Des. 2021, 21, 6537−6542. Dimensional Materials by Directly Probing and Matching Surface
(92) Yan, H.; Hohman, J. N.; Li, F. H.; Jia, C.; Solis-Ibarra, D.; Wu, Tension Components. Nano Lett. 2015, 15, 5449−5454.
B.; Dahl, J. E. P.; Carlson, R. M. K.; Tkachenko, B. A.; Fokin, A. A.; (112) Yoo, D.; Kim, M.; Jeong, S.; Han, J.; Cheon, J. Chemical
et al. Hybrid Metal−Organic Chalcogenide Nanowires with Electri- Synthetic Strategy for Single-Layer Transition-Metal Chalcogenides. J.
cally Conductive Inorganic Core through Diamondoid-Directed Am. Chem. Soc. 2014, 136, 14670−14673.
Assembly. Nat. Mater. 2017, 16, 349−355. (113) Tan, C.; Cao, X.; Wu, X.-J.; He, Q.; Yang, J.; Zhang, X.; Chen,
(93) Kibsgaard, J.; Tuxen, A.; Levisen, M.; Lægsgaard, E.; Gemming, J.; Zhao, W.; Han, S.; Nam, G.-H.; et al. Recent Advances in Ultrathin
S.; Seifert, G.; Lauritsen, J. V.; Besenbacher, F. Atomic-Scale Structure Two-Dimensional Nanomaterials. Chem. Rev. 2017, 117, 6225−6331.
of Mo6S6 Nanowires. Nano Lett. 2008, 8, 3928−3931. (114) Cai, Z.; Liu, B.; Zou, X.; Cheng, H.-M. Chemical Vapor
(94) Xu, K.; Deng, S.; Liang, T.; Cao, X.; Han, M.; Zeng, X.; Zhang, Deposition Growth and Applications of Two-Dimensional Materials
Z.; Yang, N.; Wu, J. Efficient Mechanical Modulation of the Phonon and Their Heterostructures. Chem. Rev. 2018, 118, 6091−6133.
Thermal Conductivity of Mo6S6 Nanowires. Nanoscale 2022, 14, (115) Kim, S.-Y.; Kwak, J.; Ciobanu, C. V.; Kwon, S.-Y. Recent
3078−3086. Developments in Controlled Vapor-Phase Growth of 2D Group 6
(95) Huang, W.; Wang, X.; Ji, X.; Zhang, Z.; Jin, C. In-Situ Transition Metal Dichalcogenides. Adv. Mater. 2019, 31, 1804939.
Fabrication of Mo6S6-Nanowire-Terminated Edges in Monolayer (116) Yang, H.; Giri, A.; Moon, S.; Shin, S.; Myoung, J.-M.; Jeong,
Molybdenum Disulfide. Nano Res. 2018, 11, 5849−5857. U. Highly Scalable Synthesis of MoS2 Thin Films with Precise
(96) Xia, Y.; Wang, B.; Zhang, J.; Jin, Y.; Tian, H.; Ho, W.; Xu, H.; Thickness Control via Polymer-Assisted Deposition. Chem. Mater.
Jin, C.; Xie, M. Quantum Confined Tomonaga−Luttinger Liquid in 2017, 29, 5772−5776.
Mo6Se6 Nanowires Converted from an Epitaxial MoSe2 Monolayer. (117) Giri, A.; Park, G.; Yang, H.; Pal, M.; Kwak, J.; Jeong, U.
Nano Lett. 2020, 20, 2094−2099. Synthesis of 2D Metal Chalcogenide Thin Films through the Process
(97) Zhu, H.; Wang, Q.; Zhang, C.; Addou, R.; Cho, K.; Wallace, R. Involving Solution-Phase Deposition. Adv. Mater. 2018, 30, 1707577.
M.; Kim, M. J. New Mo6Te6 Sub-Nanometer-Diameter Nanowire (118) Liu, Y.-H.; Porter, S. H.; Goldberger, J. E. Dimensional
Phase from 2H-MoTe2. Adv. Mater. 2017, 29, 1606264. Reduction of a Layered Metal Chalcogenide into a 1D near-IR Direct
(98) Deng, J.; Huo, D.; Bai, Y.; Guo, Y.; Pan, Z.; Lu, S.; Cui, P.; Band Gap Semiconductor. J. Am. Chem. Soc. 2012, 134, 5044−5047.
Zhang, Z.; Zhang, C. Precise Tuning of Band Structures and Electron (119) Ning, W.; Yu, H.; Liu, Y.; Han, Y.; Wang, N.; Yang, J.; Du, H.;
Correlations by vdW Stacking of One-Dimensional W6Te6 Wires. Zhang, C.; Mao, Z.; Liu, Y.; Tian, M.; Zhang, Y. Superconductor−
Nano Lett. 2020, 20, 8866−8873. Insulator Transition in Quasi-One-Dimensional Single-Crystal
(99) Lin, J.; Zhang, Y.; Zhou, W.; Pantelides, S. T. Structural Nb2PdS5 Nanowires. Nano Lett. 2015, 15, 869−875.
Flexibility and Alloying in Ultrathin Transition-Metal Chalcogenide (120) Stolyarov, M. A.; Liu, G.; Bloodgood, M. A.; Aytan, E.; Jiang,
Nanowires. ACS Nano 2016, 10, 2782−2790. C.; Samnakay, R.; Salguero, T. T.; Nika, D. L.; Rumyantsev, S. L.;
(100) Tang, J.; Wang, X.; Zhang, J.; Wang, J.; Yin, W.; Li, D.-S.; Wu, Shur, M. S.; et al. Breakdown Current Density in h-BN-Capped
T. A Chalcogenide-Cluster-Based Semiconducting Nanotube Array Quasi-1D TaSe3 Metallic Nanowires: Prospects of Interconnect
with Oriented Photoconductive Behavior. Nat. Commun. 2021, 12, Applications. Nanoscale 2016, 8, 15774−15782.
4275. (121) Li, H.; Jiang, J.; Huang, J.; Wang, Y.; Peng, Y.; Zhang, Y.;
(101) Qu, Y.; Arguilla, M. Q.; Zhang, Q.; He, X.; Dincă, M. Hwang, B.-J.; Zhao, J. Investigation of the Na Storage Property of
Ultrathin, High-Aspect Ratio, and Free-Standing Magnetic Nanowires One-Dimensional Cu2−XSe Nanorods. ACS Appl. Mater. Interfaces
by Exfoliation of Ferromagnetic Quasi-One-Dimensional vdW 2018, 10, 13491−13498.
Lattices. J. Am. Chem. Soc. 2021, 143, 19551−19558. (122) Xiong, W.-W.; Chen, J.-Q.; Wu, X.-C.; Zhu, J.-J. Individual
(102) Liu, X.; Liu, J.; Antipina, L. Y.; Hu, J.; Yue, C.; Sanchez, A. M.; HfS3 NB for Field-Effect Transistor and High Performance Visible-
Sorokin, P. B.; Mao, Z.; Wei, J. Direct Fabrication of Functional Light Detector. J. Mater. Chem. C 2014, 2, 7392−7395.
Chem. Rev. 2023, 123, 3329−3442
(123) Tao, Y.-R.; Wu, X.-C.; Xiong, W.-W. Flexible Visible-Light Advanced Interface Engineering of a CH3NH3PbI3 Perovskite Solar
Photodetectors with Broad Photoresponse Based on ZrS3 NB Films. Cell with an Efficiency of over 20%. ACS Nano 2018, 12, 10736−
Small 2014, 10, 4905−4911. 10754.
(124) Cheng, L.; Liu, Y. What Limits the Intrinsic Mobility of (142) Li, S.; Liu, Y.; Zhao, X.; Shen, Q.; Zhao, W.; Tan, Q.; Zhang,
Electrons and Holes in Two Dimensional Metal Dichalcogenides? J. N.; Li, P.; Jiao, L.; Qu, X. Sandwich-Like Heterostructures of MoS2/
Am. Chem. Soc. 2018, 140, 17895−17900. Graphene with Enlarged Interlayer Spacing and Enhanced Hydro-
(125) Zeng, M.; Xiao, Y.; Liu, J.; Yang, K.; Fu, L. Exploring Two- philicity as High-Performance Cathodes for Aqueous Zinc-Ion
Dimensional Materials toward the Next-Generation Circuits: From Batteries. Adv. Mater. 2021, 33, 2007480.
Monomer Design to Assembly Control. Chem. Rev. 2018, 118, 6236− (143) Li, S.; Liu, Y.; Zhao, X.; Cui, K.; Shen, Q.; Li, P.; Qu, X.; Jiao,
6296. L. Molecular Engineering on MoS2 Enables Large Interlayers and
(126) Yu, Z.; Ong, Z.-Y.; Pan, Y.; Cui, Y.; Xin, R.; Shi, Y.; Wang, B.; Unlocked Basal Planes for High-Performance Aqueous Zn-Ion
Wu, Y.; Chen, T.; Zhang, Y.-W.; et al. Realization of Room- Storage. Angew. Chem., Int. Ed. 2021, 60, 20286−20293.
Temperature Phonon-Limited Carrier Transport in Monolayer MoS2 (144) Tan, C.; Luo, Z.; Chaturvedi, A.; Cai, Y.; Du, Y.; Gong, Y.;
by Dielectric and Carrier Screening. Adv. Mater. 2016, 28, 547−552. Huang, Y.; Lai, Z.; Zhang, X.; Zheng, L.; Qi, X.; Goh, M. H.; et al.
(127) Desai, S. B.; Madhvapathy, S. R.; Sachid, A. B.; Llinas, J. P.; Preparation of High-Percentage 1T-Phase Transition Metal Dichal-
Wang, Q.; Ahn, G. H.; Pitner, G.; Kim, M. J.; Bokor, J.; Hu, C.; et al. cogenide Nanodots for Electrochemical Hydrogen Evolution. Adv.
MoS2 Transistors with 1-Nanometer Gate Lengths. Science 2016, 354, Mater. 2018, 30, 1705509.
99−102. (145) Zhang, Y.; Zheng, B.; Zhu, C.; Zhang, X.; Tan, C.; Li, H.;
(128) Xu, W.; Liu, W.; Schmidt, J. F.; Zhao, W.; Lu, X.; Raab, T.; Chen, B.; Yang, J.; Chen, J.; Huang, Y.; Wang, L.; Zhang, H. Single-
Diederichs, C.; Gao, W.; Seletskiy, D. V.; Xiong, Q. Correlated Layer Transition Metal Dichalcogenide Nanosheet-Based Nano-
Fluorescence Blinking in Two-Dimensional Semiconductor Hetero- sensors for Rapid, Sensitive, and Multiplexed Detection of DNA.
structures. Nature 2017, 541, 62−67. Adv. Mater. 2015, 27, 935−939.
(129) Rivera, P.; Seyler, K. L.; Yu, H.; Schaibley, J. R.; Yan, J.; (146) Chowdhury, T.; Sadler, E. C.; Kempa, T. J. Progress and
Mandrus, D. G.; Yao, W.; Xu, X. Valley-Polarized Exciton Dynamics Prospects in Transition-Metal Dichalcogenide Research Beyond 2D.
in a 2D Semiconductor Heterostructure. Science 2016, 351, 688−691. Chem. Rev. 2020, 120, 12563−12591.
(130) Li, J.; Yang, X.; Liu, Y.; Huang, B.; Wu, R.; Zhang, Z.; Zhao, (147) Patra, A.; Rout, C. S. Anisotropic Quasi-One-Dimensional
B.; Ma, H.; Dang, W.; Wei, Z.; et al. General Synthesis of Two- Layered Transition-Metal Trichalcogenides: Synthesis, Properties and
Dimensional vdW Heterostructure Arrays. Nature 2020, 579, 368− Applications. RSC Adv. 2020, 10, 36413−36438.
374. (148) Island, J. O.; Molina-Mendoza, A. J.; Barawi, M.; Biele, R.;
(131) Cheng, J.; Wang, C.; Zou, X.; Liao, L. Recent Advances in
Flores, E.; Clamagirand, J. M.; Ares, J. R.; Sánchez, C.; van der Zant,
Optoelectronic Devices Based on 2D Materials and Their
H. S. J.; D’Agosta, R.; et al. Electronics and Optoelectronics of Quasi-
Heterostructures. Adv. Opt. Mater. 2019, 7, 1800441.
1D Layered Transition Metal Trichalcogenides. 2D Mater. 2017, 4,
(132) Timpel, M.; Ligorio, G.; Ghiami, A.; Gavioli, L.; Cavaliere, E.;
No. 022003.
Chiappini, A.; Rossi, F.; Pasquali, L.; Gärisch, F.; List-Kratochvil, E. J.
(149) Xu, M.; Liang, T.; Shi, M.; Chen, H. Graphene-Like Two-
W.; et al. 2D-MoS2 Goes 3D: Transferring Optoelectronic Properties
Dimensional Materials. Chem. Rev. 2013, 113, 3766−3798.
of 2D MoS2 to a Large-Area Thin Film. npj 2D Mater. Appl. 2021, 5,
(150) Han, J. H.; Kwak, M.; Kim, Y.; Cheon, J. Recent Advances in
64.
(133) Zhang, W.; Huang, J.-K.; Chen, C.-H.; Chang, Y.-H.; Cheng, the Solution-Based Preparation of Two-Dimensional Layered
Y.-J.; Li, L.-J. High-Gain Phototransistors Based on a CVD MoS2 Transition Metal Chalcogenide Nanostructures. Chem. Rev. 2018,
Monolayer. Adv. Mater. 2013, 25, 3456−3461. 118, 6151−6188.
(134) Yin, Z.; Li, H.; Li, H.; Jiang, L.; Shi, Y.; Sun, Y.; Lu, G.; Zhang, (151) Han, G. H.; Duong, D. L.; Keum, D. H.; Yun, S. J.; Lee, Y. H.
Q.; Chen, X.; Zhang, H. Single-Layer MoS2 Phototransistors. ACS vdW Metallic Transition Metal Dichalcogenides. Chem. Rev. 2018,
Nano 2012, 6, 74−80. 118, 6297−6336.
(135) Mennucci, C.; Mazzanti, A.; Martella, C.; Lamperti, A.; (152) Wang, H.; Yuan, H.; Sae Hong, S.; Li, Y.; Cui, Y. Physical and
Bhatnagar, M.; Lo Savio, R.; Repetto, L.; Camellini, A.; Zavelani- Chemical Tuning of Two-Dimensional Transition Metal Dichalcoge-
Rossi, M.; Molle, A.; et al. Geometrical Engineering of Giant Optical nides. Chem. Soc. Rev. 2015, 44, 2664−2680.
Dichroism in Rippled MoS2 Nanosheets. Adv. Opt. Mater. 2021, 9, (153) Jin, H.; Guo, C.; Liu, X.; Liu, J.; Vasileff, A.; Jiao, Y.; Zheng,
2001408. Y.; Qiao, S.-Z. Emerging Two-Dimensional Nanomaterials for
(136) Li, X.; Hu, K.; Lyu, B.; Zhang, J.; Wang, Y.; Wang, P.; Xiao, S.; Electrocatalysis. Chem. Rev. 2018, 118, 6337−6408.
Gao, Y.; He, J. Enhanced Nonlinear Optical Response of Rectangular (154) Yun, Q.; Li, L.; Hu, Z.; Lu, Q.; Chen, B.; Zhang, H. Layered
MoS2 and MoS2/TiO2 in Dispersion and Film. J. Phys. Chem. C 2016, Transition Metal Dichalcogenide-Based Nanomaterials for Electro-
120, 18243−18248. chemical Energy Storage. Adv. Mater. 2020, 32, 1903826.
(137) Fang, Y.; Hu, X.; Zhao, W.; Pan, J.; Wang, D.; Bu, K.; Mao, Y.; (155) Sajanlal, P. R.; Sreeprasad, T. S.; Samal, A. K.; Pradeep, T.
Chu, S.; Liu, P.; Zhai, T.; Huang, F. Structural Determination and Anisotropic Nanomaterials: Structure, Growth, Assembly, and
Nonlinear Optical Properties of New 1T‴-Type MoS2 Compound. J. Functions. Nano Rev. 2011, 2, 5883.
Am. Chem. Soc. 2019, 141, 790−793. (156) Zhao, S.; Dong, B.; Wang, H.; Wang, H.; Zhang, Y.; Han, Z.
(138) Ermolaev, G. A.; Stebunov, Y. V.; Vyshnevyy, A. A.; Tatarkin, V.; Zhang, H. In-Plane Anisotropic Electronics Based on Low-
D. E.; Yakubovsky, D. I.; Novikov, S. M.; Baranov, D. G.; Shegai, T.; Symmetry 2D Materials: Progress and Prospects. Nanoscale Adv.
Nikitin, A. Y.; Arsenin, A. V.; et al. Broadband Optical Properties of 2020, 2, 109−139.
Monolayer and Bulk MoS2. npj 2D Mater. Appl. 2020, 4, 21. (157) Cui, Y.; Zhou, Z.; Li, T.; Wang, K.; Li, J.; Wei, Z. Versatile
(139) Singh, E.; Kim, K. S.; Yeom, G. Y.; Nalwa, H. S. Atomically Crystal Structures and (Opto)Electronic Applications of the 2D Metal
Thin-Layered Molybdenum Disulfide (MoS2) for Bulk-Heterojunc- Mono-, Di-, and Tri-Chalcogenide Nanosheets. Adv. Funct. Mater.
tion Solar Cells. ACS Appl. Mater. Interfaces 2017, 9, 3223−3245. 2019, 29, 1900040.
(140) Tsai, M.-L.; Su, S.-H.; Chang, J.-K.; Tsai, D.-S.; Chen, C.-H.; (158) Wang, F.; Dong, A.; Buhro, W. E. Solution−Liquid−Solid
Wu, C.-I.; Li, L.-J.; Chen, L.-J.; He, J.-H. Monolayer MoS2 Synthesis, Properties, and Applications of One-Dimensional Colloidal
Heterojunction Solar Cells. ACS Nano 2014, 8, 8317−8322. Semiconductor Nanorods and Nanowires. Chem. Rev. 2016, 116,
(141) Najafi, L.; Taheri, B.; Martín-García, B.; Bellani, S.; Di 10888−10933.
Girolamo, D.; Agresti, A.; Oropesa-Nuñez, R.; Pescetelli, S.; Vesce, L.; (159) Singh, A.; Li, X.; Protasenko, V.; Galantai, G.; Kuno, M.; Xing,
Calabrò, E.; et al. MoS2 Quantum Dot/Graphene Hybrids for H.; Jena, D. Polarization-Sensitive Nanowire Photodetectors Based on
Chem. Rev. 2023, 123, 3329−3442
Solution-Synthesized CdSe Quantum-Wire Solids. Nano Lett. 2007, 7, Ta2NiS5 Single Crystals Revealed by High-Resolution Angle-Resolved
2999−3006. Photoemission Spectroscopy. J. Mater. Chem. C 2018, 6, 3976−3981.
(160) Quan, L. N.; Kang, J.; Ning, C.-Z.; Yang, P. Nanowires for (180) Yang, B.; Wang, L.; Han, J.; Zhou, Y.; Song, H.; Chen, S.;
Photonics. Chem. Rev. 2019, 119, 9153−9169. Zhong, J.; Lv, L.; Niu, D.; Tang, J. CuSbS2 as a Promising Earth-
(161) Moore, D.; Wang, Z. L. Growth of Anisotropic One- Abundant Photovoltaic Absorber Material: A Combined Theoretical
Dimensional ZnS Nanostructures. J. Mater. Chem. 2006, 16, 3898− and Experimental Study. Chem. Mater. 2014, 26, 3135−3143.
3905. (181) Kale, B. B.; Bhirud, A. P.; Baeg, J.-O.; Kulkarni, M. V.
(162) Liu, H.; Hu, L.; Watanabe, K.; Hu, X.; Dierre, B.; Kim, B.; Template Free Architecture of Hierarchical Nanostructured ZnIn2S4
Sekiguchi, T.; Fang, X. Cathodoluminescence Modulation of ZnS Rose-Like Flowers for Solar Hydrogen Production. J. Nanosci.
Nanostructures by Morphology, Doping, and Temperature. Adv. Nanotechnol. 2017, 17, 1447−1454.
Funct. Mater. 2013, 23, 3701−3709. (182) Deng, Y.; Yu, Y.; Shi, M. Z.; Guo, Z.; Xu, Z.; Wang, J.; Chen,
(163) Wang, Z.; Daemen, L. L.; Zhao, Y.; Zha, C. S.; Downs, R. T.; X. H.; Zhang, Y. Quantum Anomalous Hall Effect in Intrinsic
Wang, X.; Wang, Z. L.; Hemley, R. J. Morphology-Tuned Wurtzite- Magnetic Topological Insulator MnBi2Te4. Science 2020, 367, 895−
Type ZnS Nanobelts. Nat. Mater. 2005, 4, 922−927. 900.
(164) Fan, D. D.; Liu, H. J.; Cheng, L.; Jiang, P. H.; Shi, J.; Tang, X. (183) Zhang, Z.; Chen, P.; Duan, X.; Zang, K.; Luo, J.; Duan, X.
F. MoS2 Nanoribbons as Promising Thermoelectric Materials. Appl. Robust Epitaxial Growth of Two-Dimensional Heterostructures,
Phys. Lett. 2014, 105, 133113. Multiheterostructures, and Superlattices. Science 2017, 357, 788−792.
(165) Murugan, P.; Kumar, V.; Kawazoe, Y.; Ota, N. Assembling (184) Novoselov, K. S.; Mishchenko, A.; Carvalho, A.; Castro Neto,
Nanowires from Mo−S Clusters and Effects of Iodine Doping on A. H. 2D Materials and vdW Heterostructures. Science 2016, 353,
Electronic Structure. Nano Lett. 2007, 7, 2214−2219. aac9439.
(166) Liu, X.; Xu, T.; Wu, X.; Zhang, Z.; Yu, J.; Qiu, H.; Hong, J.-H.; (185) Sahoo, P. K.; Memaran, S.; Xin, Y.; Balicas, L.; Gutiérrez, H.
Jin, C.-H.; Li, J.-X.; Wang, X.-R.; et al. Top−Down Fabrication of R. One-Pot Growth of Two-Dimensional Lateral Heterostructures via
Sub-Nanometre Semiconducting Nanoribbons Derived from Molyb- Sequential Edge-Epitaxy. Nature 2018, 553, 63−67.
denum Disulfide Sheets. Nat. Commun. 2013, 4, 1776. (186) Mahjouri-Samani, M.; Lin, M.-W.; Wang, K.; Lupini, A. R.;
(167) Yu, Y.; Wang, G.; Tan, Y.; Wu, N.; Zhang, X.-A.; Qin, S. Lee, J.; Basile, L.; Boulesbaa, A.; Rouleau, C. M.; Puretzky, A. A.;
Phase-Controlled Growth of One-Dimensional Mo6Te6 Nanowires Ivanov, I. N.; Xiao, K.; et al. Patterned Arrays of Lateral
and Two-Dimensional MoTe2 Ultrathin Films Heterostructures. Heterojunctions within Monolayer Two-Dimensional Semiconduc-
Nano Lett. 2018, 18, 675−681. tors. Nat. Commun. 2015, 6, 7749.
(168) Liu, G.; Rumyantsev, S.; Bloodgood, M. A.; Salguero, T. T.; (187) Gong, Y.; Lin, J.; Wang, X.; Shi, G.; Lei, S.; Lin, Z.; Zou, X.;
Shur, M.; Balandin, A. A. Low-Frequency Electronic Noise in Quasi- Ye, G.; Vajtai, R.; Yakobson, B. I.; et al. Vertical and in-Plane
1D TaSe3 vdW Nanowires. Nano Lett. 2017, 17, 377−383. Heterostructures from WS2/MoS2 Monolayers. Nat. Mater. 2014, 13,
(169) Zhang, Q.; Liu, C.; Liu, X.; Liu, J.; Cui, Z.; Zhang, Y.; Yang, 1135−1142.
L.; Zhao, Y.; Xu, T. T.; Chen, Y.; et al. Thermal Transport in Quasi- (188) Duan, X.; Wang, C.; Pan, A.; Yu, R.; Duan, X. Two-
1D vdW Crystal Ta2Pd3Se8 Nanowires: Size and Length Dependence. Dimensional Transition Metal Dichalcogenides as Atomically Thin
ACS Nano 2018, 12, 2634−2642. Semiconductors: Opportunities and Challenges. Chem. Soc. Rev. 2015,
(170) Kong, T.; Stolze, K.; Ni, D.; Kushwaha, S. K.; Cava, R. J. 44, 8859−8876.
Anisotropic Magnetic Properties of the Ferromagnetic Semiconductor (189) Kang, K.; Lee, K.-H.; Han, Y.; Gao, H.; Xie, S.; Muller, D. A.;
CrSbSe3. Phys. Rev. Mater. 2018, 2, No. 014410. Park, J. Layer-by-Layer Assembly of Two-Dimensional Materials into
(171) Wilson, J. A.; Yoffe, A. D. The Transition Metal Wafer-Scale Heterostructures. Nature 2017, 550, 229−233.
Dichalcogenides Discussion and Interpretation of the Observed (190) Guo, H.; Zhang, X.; Lu, G. Moiré Excitons in Defective vdW
Optical, Electrical and Structural Properties. Adv. Phys. 1969, 18, Heterostructures. Proc. Natl. Acad. Sci. U. S. A. 2021, 118,
193−335. e2105468118.
(172) Zhao, L.-D.; Lo, S.-H.; Zhang, Y.; Sun, H.; Tan, G.; Uher, C.; (191) Kong, W.; Bacaksiz, C.; Chen, B.; Wu, K.; Blei, M.; Fan, X.;
Wolverton, C.; Dravid, V. P.; Kanatzidis, M. G. Ultralow Thermal Shen, Y.; Sahin, H.; Wright, D.; Narang, D. S.; et al. Angle Resolved
Conductivity and High Thermoelectric Figure of Merit in SnSe Vibrational Properties of Anisotropic Transition Metal Trichalcoge-
Crystals. Nature 2014, 508, 373−377. nide Nanosheets. Nanoscale 2017, 9, 4175−4182.
(173) Yuan, H.; Wang, H.; Cui, Y. Two-Dimensional Layered (192) Pant, A.; Torun, E.; Chen, B.; Bhat, S.; Fan, X.; Wu, K.;
Chalcogenides: From Rational Synthesis to Property Control via Wright, D. P.; Peeters, F. M.; Soignard, E.; Sahin, H.; et al. Strong
Orbital Occupation and Electron Filling. Acc. Chem. Res. 2015, 48, Dichroic Emission in the Pseudo One Dimensional Material ZrS3.
81−90. Nanoscale 2016, 8, 16259−16265.
(174) Bergeron, H.; Lebedev, D.; Hersam, M. C. Polymorphism in (193) Autès, G.; Isaeva, A.; Moreschini, L.; Johannsen, J. C.; Pisoni,
Post-Dichalcogenide Two-Dimensional Materials. Chem. Rev. 2021, A.; Mori, R.; Zhang, W.; Filatova, T. G.; Kuznetsov, A. N.; Forró, L.;
121, 2713−2775. et al. A Novel Quasi-One-Dimensional Topological Insulator in
(175) Gong, C.; Zhang, X. Two-Dimensional Magnetic Crystals and Bismuth Iodide Β-Bi4I4. Nat. Mater. 2016, 15, 154−158.
Emergent Heterostructure Devices. Science 2019, 363, eaav4450. (194) Hor, Y. S.; Xiao, Z. L.; Welp, U.; Ito, Y.; Mitchell, J. F.; Cook,
(176) Giri, A.; De, C.; Kumar, M.; Pal, M.; Lee, H. H.; Kim, J. S.; R. E.; Kwok, W. K.; Crabtree, G. W. Nanowires and Nanoribbons of
Cheong, S.-W.; Jeong, U. Large-Area Epitaxial Film Growth of vdW Charge-Density-Wave Conductor NbSe3. Nano Lett. 2005, 5, 397−
Ferromagnetic Ternary Chalcogenides. Adv. Mater. 2021, 33, 401.
2103609. (195) Zhu, X.; Lv, B.; Wei, F.; Xue, Y.; Lorenz, B.; Deng, L.; Sun, Y.;
(177) Seo, J.; De, C.; Ha, H.; Lee, J. E.; Park, S.; Park, J.; Skourski, Chu, C.-W. Disorder-Induced Bulk Superconductivity in ZrTe3 Single
Y.; Choi, E. S.; Kim, B.; Cho, G. Y.; et al. Colossal Angular Crystals via Growth Control. Phys. Rev. B 2013, 87, No. 024508.
Magnetoresistance in Ferrimagnetic Nodal-Line Semiconductors. (196) Slot, E.; Holst, M. A.; van der Zant, H. S. J.; Zaitsev-Zotov, S.
Nature 2021, 599, 576−581. V. One-Dimensional Conduction in Charge-Density-Wave Nano-
(178) Tiwari, A. P.; Azam, A.; Novak, T. G.; Prakash, O.; Jeon, S. wires. Phys. Rev. Lett. 2004, 93, 176602.
Chemical Strain Formation through Anion Substitution in Cu2WS4 (197) Ferrer, I. J.; Ares, J. R.; Clamagirand, J. M.; Barawi, M.;
for Efficient Electrocatalysis of Water Dissociation. J. Mater. Chem. A Sánchez, C. Optical Properties of Titanium Trisulphide (TiS3) Thin
2018, 6, 7786−7793. Films. Thin Solid Films 2013, 535, 398−401.
(179) Mu, K.; Chen, H.; Li, Y.; Zhang, Y.; Wang, P.; Zhang, B.; Liu, (198) Kang, J.; Wang, L.-W. Robust Band Gap of TiS3 Nanofilms.
Y.; Zhang, G.; Song, L.; Sun, Z. Electronic Structures of Layered Phys. Chem. Chem. Phys. 2016, 18, 14805−14809.
Chem. Rev. 2023, 123, 3329−3442
(199) Splendiani, A.; Sun, L.; Zhang, Y.; Li, T.; Kim, J.; Chim, C.-Y.; (220) Song, S.; Keum, D. H.; Cho, S.; Perello, D.; Kim, Y.; Lee, Y.
Galli, G.; Wang, F. Emerging Photoluminescence in Monolayer MoS2. H. Room Temperature Semiconductor−Metal Transition of MoTe2
Nano Lett. 2010, 10, 1271−1275. Thin Films Engineered by Strain. Nano Lett. 2016, 16, 188−193.
(200) Lipatov, A.; Loes, M. J.; Lu, H.; Dai, J.; Patoka, P.; Vorobeva, (221) Byrley, P.; Liu, M.; Yan, R. Photochemically Induced Phase
N. S.; Muratov, D. S.; Ulrich, G.; Kästner, B.; Hoehl, A.; et al. Quasi- Change in Monolayer Molybdenum Disulfide. Front. Chem. 2019, 7,
1D TiS3 Nanoribbons: Mechanical Exfoliation and Thickness- 442.
Dependent Raman Spectroscopy. ACS Nano 2018, 12, 12713−12720. (222) Zhao, B.; Shen, D.; Zhang, Z.; Lu, P.; Hossain, M.; Li, J.; Li,
(201) Yakovkin, I. N. Dirac Cones in Graphene, Interlayer B.; Duan, X. 2D Metallic Transition-Metal Dichalcogenides:
Interaction in Layered Materials, and the Band Gap in MoS2. Crystals Structures, Synthesis, Properties, and Applications. Adv. Funct.
2016, 6, 143. Mater. 2021, 31, 2105132.
(202) Jie, J. S.; Zhang, W. J.; Jiang, Y.; Lee, S. T. Transport (223) Méasson, M. A.; Gallais, Y.; Cazayous, M.; Clair, B.; Rodière,
Properties of Single-Crystal CdS Nanoribbons. Appl. Phys. Lett. 2006, P.; Cario, L.; Sacuto, A. Amplitude Higgs Mode in the 2H-NbSe2
89, 223117. Superconductor. Phys. Rev. B 2014, 89, No. 060503.
(203) Liu, Y. K.; Zapien, J. A.; Geng, C. Y.; Shan, Y. Y.; Lee, C. S.; (224) Shi, J.; Hong, M.; Zhang, Z.; Ji, Q.; Zhang, Y. Physical
Lifshitz, Y.; Lee, S. T. High-Quality CdS Nanoribbons with Lasing Properties and Potential Applications of Two-Dimensional Metallic
Transition Metal Dichalcogenides. Coord. Chem. Rev. 2018, 376, 1−
Cavity. Appl. Phys. Lett. 2004, 85, 3241−3243.
19.
(204) Liu, Y.; Zapien, J. A.; Shan, Y. Y.; Geng, C. Y.; Lee, C. S.; Lee,
(225) Lai, S.; Du, Y. Magnetic Behavior in TiS3 Nanoribbon.
S. T. Wavelength-Controlled Lasing in ZnxCd1‑xS Single-Crystal
Materials 2019, 12, 3501.
Nanoribbons. Adv. Mater. 2005, 17, 1372−1377. (226) Wang, F.; Du, J.; Sun, F.; Sabirianov, R. F.; Al-Aqtash, N.;
(205) Pan, H.; Zhang, Y.-W. Edge-Dependent Structural, Electronic Sengupta, D.; Zeng, H.; Xu, X. Ferromagnetic Cr2Te3 Nanorods with
and Magnetic Properties of MoS2 Nanoribbons. J. Mater. Chem. 2012, Ultrahigh Coercivity. Nanoscale 2018, 10, 11028−11033.
22, 7280−7290. (227) Fei, Z.; Huang, B.; Malinowski, P.; Wang, W.; Song, T.;
(206) Gan, Y.; Quhe, R.; Wu, L.; Hou, S.; Bi, J.; Liu, G.; Lu, P. Sanchez, J.; Yao, W.; Xiao, D.; Zhu, X.; May, A. F.; et al. Two-
Structural and Electronic Properties of PdS2 Nanoribbons. J. Magn. Dimensional Itinerant Ferromagnetism in Atomically Thin Fe3GeTe2.
Magn. Mater. 2018, 458, 310−316. Nat. Mater. 2018, 17, 778−782.
(207) Zhao, W.; Ribeiro, R. M.; Eda, G. Electronic Structure and (228) Li, H.; Ruan, S.; Zeng, Y.-J. Intrinsic vdW Magnetic Materials
Optical Signatures of Semiconducting Transition Metal Dichalcoge- from Bulk to the 2D Limit: New Frontiers of Spintronics. Adv. Mater.
nide Nanosheets. Acc. Chem. Res. 2015, 48, 91−99. 2019, 31, 1900065.
(208) Bandurin, D. A.; Tyurnina, A. V.; Yu, G. L.; Mishchenko, A.; (229) Ohno, H.; Chiba, D.; Matsukura, F.; Omiya, T.; Abe, E.; Dietl,
Zólyomi, V.; Morozov, S. V.; Kumar, R. K.; Gorbachev, R. V.; T.; Ohno, Y.; Ohtani, K. Electric-Field Control of Ferromagnetism.
Kudrynskyi, Z. R.; Pezzini, S.; et al. High Electron Mobility, Quantum Nature 2000, 408, 944−946.
Hall Effect and Anomalous Optical Response in Atomically Thin (230) Chang, C.-Z.; Zhang, J.; Feng, X.; Shen, J.; Zhang, Z.; Guo,
InSe. Nat. Nanotechnol. 2017, 12, 223−227. M.; Li, K.; Ou, Y.; Wei, P.; Wang, L.-L.; et al. Experimental
(209) Mak, K. F.; Lee, C.; Hone, J.; Shan, J.; Heinz, T. F. Atomically Observation of the Quantum Anomalous Hall Effect in a Magnetic
Thin MoS2: A New Direct-Gap Semiconductor. Phys. Rev. Lett. 2010, Topological Insulator. Science 2013, 340, 167−170.
105, 136805. (231) Jagla, E. A. Hysteresis Loops of Magnetic Thin Films with
(210) Pei, J.; Yang, J.; Yildirim, T.; Zhang, H.; Lu, Y. Many-Body Perpendicular Anisotropy. Phys. Rev. B 2005, 72, No. 094406.
Complexes in 2D Semiconductors. Adv. Mater. 2019, 31, 1706945. (232) Li, L.-s.; Hu, J.; Yang, W.; Alivisatos, A. P. Band Gap Variation
(211) Jiang, Z.; Liu, Z.; Li, Y.; Duan, W. Scaling Universality of Size- and Shape-Controlled Colloidal CdSe Quantum Rods. Nano
between Band Gap and Exciton Binding Energy of Two-Dimensional Lett. 2001, 1, 349−351.
Semiconductors. Phys. Rev. Lett. 2017, 118, 266401. (233) Li, Y.; Zhou, Z.; Zhang, S.; Chen, Z. MoS2 Nanoribbons: High
(212) Neri, I.; López-Suárez, M.; Caponi, S.; Mattarelli, M. Fast Stability and Unusual Electronic and Magnetic Properties. J. Am.
MoS2 Thickness Identification by Transmission Imaging. Appl. Chem. Soc. 2008, 130, 16739−16744.
Nanoscience 2021, 11, 605−610. (234) Zheng, J.; Yan, X.; Lu, Z.; Qiu, H.; Xu, G.; Zhou, X.; Wang, P.;
(213) Gomes, L. C.; Carvalho, A. Electronic and Optical Properties Pan, X.; Liu, K.; Jiao, L. High-Mobility Multilayered MoS2 Flakes with
of Low-Dimensional Group-Iv Monochalcogenides. J. Appl. Phys. Low Contact Resistance Grown by Chemical Vapor Deposition. Adv.
2020, 128, 121101. Mater. 2017, 29, 1604540.
(214) Jing, Y.; Liu, B.; Zhu, X.; Ouyang, F.; Sun, J.; Zhou, Y. (235) Hsu, C.; Frisenda, R.; Schmidt, R.; Arora, A.; de Vasconcellos,
Tunable Electronic Structure of Two-Dimensional Transition Metal S. M.; Bratschitsch, R.; van der Zant, H. S. J.; Castellanos-Gomez, A.
Thickness-Dependent Refractive Index of 1l, 2l, and 3l MoS2, MoSe2,
Chalcogenides for Optoelectronic Applications. Nanophotonics 2020,
WS2, and WSe2. Adv. Opt. Mater. 2019, 7, 1900239.
9, 1675−1694.
(236) Kaushik, V.; Varandani, D.; Mehta, B. R. Nanoscale Mapping
(215) Khan, M. A.; Leuenberger, M. N. Optoelectronics with Single
of Layer-Dependent Surface Potential and Junction Properties of
Layer Group-VIB Transition Metal Dichalcogenides. Nanophotonics CVD-Grown MoS2 Domains. J. Phys. Chem. C 2015, 119, 20136−
2018, 7, 1589−1600. 20142.
(216) Xiao, J.; Zhao, M.; Wang, Y.; Zhang, X. Excitons in Atomically (237) Du, H.-Y.; Huang, Y.-F.; Wong, D.; Tseng, M.-F.; Lee, Y.-H.;
Thin 2D Semiconductors and Their Applications. Nanophotonics Wang, C.-H.; Lin, C.-L.; Hoffmann, G.; Chen, K.-H.; Chen, L.-C.
2017, 6, 1309−1328. Nanoscale Redox Mapping at the MoS2-Liquid Interface. Nat.
(217) Chaves, A.; Azadani, J. G.; Alsalman, H.; da Costa, D. R.; Commun. 2021, 12, 1321.
Frisenda, R.; Chaves, A. J.; Song, S. H.; Kim, Y. D.; He, D.; Zhou, J.; (238) Min, S.-W.; Lee, H. S.; Choi, H. J.; Park, M. K.; Nam, T.; Kim,
et al. Bandgap Engineering of Two-Dimensional Semiconductor H.; Ryu, S.; Im, S. Nanosheet Thickness-Modulated MoS2 Dielectric
Materials. npj 2D Mater. Appl. 2020, 4, 29. Property Evidenced by Field-Effect Transistor Performance. Nano-
(218) Duerloo, K.-A. N.; Li, Y.; Reed, E. J. Structural Phase scale 2013, 5, 548−551.
Transitions in Two-Dimensional Mo- and W-Dichalcogenide (239) Nagashio, K.; Nishimura, T.; Kita, K.; Toriumi, A. Mobility
Monolayers. Nat. Commun. 2014, 5, 4214. Variations in Mono- and Multi-Layer Graphene Films. Appl. Phys.
(219) Chhowalla, M.; Voiry, D.; Yang, J.; Shin, H. S.; Loh, K. P. Express 2009, 2, No. 025003.
Phase-Engineered Transition-Metal Dichalcogenides for Energy and (240) Lee, G.-H.; Yu, Y.-J.; Cui, X.; Petrone, N.; Lee, C.-H.; Choi,
Electronics. MRS Bull. 2015, 40, 585−591. M. S.; Lee, D.-Y.; Lee, C.; Yoo, W. J.; Watanabe, K.; et al. Flexible and
Chem. Rev. 2023, 123, 3329−3442
Transparent MoS2 Field-Effect Transistors on Hexagonal Boron (259) Komsa, H.-P.; Krasheninnikov, A. V. Native Defects in Bulk
Nitride-Graphene Heterostructures. ACS Nano 2013, 7, 7931−7936. and Monolayer MoS2 from First Principles. Phys. Rev. B 2015, 91,
(241) Bao, W.; Cai, X.; Kim, D.; Sridhara, K.; Fuhrer, M. S. High 125304.
Mobility Ambipolar MoS2 Field-Effect Transistors: Substrate and (260) Muratov, D. S.; Vanyushin, V. O.; Vorobeva, N. S.; Jukova, P.;
Dielectric Effects. Appl. Phys. Lett. 2013, 102, No. 042104. Lipatov, A.; Kolesnikov, E. A.; Karpenkov, D.; Kuznetsov, D. V.;
(242) Das, S.; Chen, H.-Y.; Penumatcha, A. V.; Appenzeller, J. High Sinitskii, A. Synthesis and Exfoliation of Quasi-1D (Zr,Ti)S3 Solid
Performance Multilayer MoS2 Transistors with Scandium Contacts. Solutions for Device Measurements. J. Alloys Compd. 2020, 815,
Nano Lett. 2013, 13, 100−105. 152316.
(243) Tan, C.; Lee, J.; Jung, S.-G.; Park, T.; Albarakati, S.; Partridge, (261) Wu, K.; Blei, M.; Chen, B.; Liu, L.; Cai, H.; Brayfield, C.;
J.; Field, M. R.; McCulloch, D. G.; Wang, L.; Lee, C. Hard Magnetic Wright, D.; Zhuang, H.; Tongay, S. Phase Transition across
Properties in Nanoflake vdW Fe3GeTe2. Nat. Commun. 2018, 9, 1554. Anisotropic NbS3 and Direct Gap Semiconductor TiS3 at Nominal
(244) Gibertini, M.; Koperski, M.; Morpurgo, A. F.; Novoselov, K. S. Titanium Alloying Limit. Adv. Mater. 2020, 32, 2000018.
Magnetic 2D Materials and Heterostructures. Nat. Nanotechnol. 2019, (262) Island, J. O.; Barawi, M.; Biele, R.; Almazán, A.; Clamagirand,
14, 408−419. J. M.; Ares, J. R.; Sánchez, C.; van der Zant, H. S. J.; Á lvarez, J. V.;
(245) Meng, L.; Zhou, Z.; Xu, M.; Yang, S.; Si, K.; Liu, L.; Wang, X.; D’Agosta, R.; et al. TiS3 Transistors with Tailored Morphology and
Jiang, H.; Li, B.; Qin, P.; et al. Anomalous Thickness Dependence of Electrical Properties. Adv. Mater. 2015, 27, 2595−2601.
Curie Temperature in Air-Stable Two-Dimensional Ferromagnetic (263) Jin, K.-H.; Liu, F. 1D Topological Phases in Transition-Metal
1T-CrTe2 Grown by Chemical Vapor Deposition. Nat. Commun. Monochalcogenide Nanowires. Nanoscale 2020, 12, 14661−14667.
2021, 12, 809. (264) Popov, I.; Yang, T.; Berber, S.; Seifert, G.; Tománek, D.
(246) Rhodes, D.; Chae, S. H.; Ribeiro-Palau, R.; Hone, J. Disorder Unique Structural and Transport Properties of Molybdenum
in vdW Heterostructures of 2D Materials. Nat. Mater. 2019, 18, 541− Chalcohalide Nanowires. Phys. Rev. Lett. 2007, 99, No. 085503.
549. (265) Gemming, S.; Seifert, G.; Vilfan, I. Li Doped Mo6S6
(247) Iyikanat, F.; Sahin, H.; Senger, R. T.; Peeters, F. M. Vacancy Nanowires: Elastic and Electronic Properties. Phys. Status Solidi B
Formation and Oxidation Characteristics of Single Layer TiS3. J. Phys. 2006, 243, 3320−3324.
Chem. C 2015, 119, 10709−10715. (266) Li, D.; Xing, G.; Tang, S.; Li, X.; Fan, L.; Li, Y. Ultrathin ZnSe
(248) Arsentev, M. Y.; Petrov, A. V.; Missyul, A. B.; Hammouri, M. Nanowires: One-Pot Synthesis via a Heat-Triggered Precursor Slow
Exfoliation, Point Defects and Hydrogen Storage Properties of Releasing Route, Controllable Mn Doping and Application in Uv and
Monolayer TiS3: An Ab Initio Study. RSC Adv. 2018, 8, 26169− near-Visible Light Detection. Nanoscale 2017, 9, 15044−15055.
26179. (267) Singh, R.; Basu, S.; Pal, B. Ag+ and Cu2+ Doped CdS
(249) Wei, Y.; Zhou, Z.; Long, R. Defects Slow Down Nonradiative Nanorods with Tunable Band Structure and Superior Photocatalytic
Electron−Hole Recombination in TiS3 Nanoribbons: A Time- Activity under Sunlight. Mater. Res. Bull. 2017, 94, 279−286.
Domain Ab Initio Study. J. Phys. Chem. Lett. 2017, 8, 4522−4529. (268) Lee, C.-H.; Lin, J.; Yang, C.-K. Armchair MoS2 Nanoribbons
(250) Molina-Mendoza, A. J.; Island, J. O.; Paz, W. S.; Clamagirand, Turned into Half Metals through Deposition of Transition-Metal and
J. M.; Ares, J. R.; Flores, E.; Leardini, F.; Sánchez, C.; Agraït, N.; Si Atomic Chains. Sci. Rep. 2018, 8, 13307.
Rubio-Bollinger, G.; et al. High Current Density Electrical Breakdown (269) Pan, J.; Wang, R.; Zhou, X.; Zhong, J.; Xu, X.; Hu, J.
of TiS3 Nanoribbon-Based Field-Effect Transistors. Adv. Funct. Mater. Transition-Metal Doping Induces the Transition of Electronic and
2017, 27, 1605647. Magnetic Properties in Armchair MoS2 Nanoribbons. Phys. Chem.
(251) Trunkin, I. N.; Gorlova, I. G.; Bolotina, N. B.; Bondarenko, V. Chem. Phys. 2017, 19, 24594−24604.
I.; Chesnokov, Y. M.; Vasiliev, A. L. Defect Structure of TiS3 Single (270) Wang, M.; He, X.; Shen, M.; Yang, L.; Shi, Y. Effect of
Crystals with Different Resistivity. J. Mater. Sci. 2021, 56, 2150−2162. Nitrogen Doping on the Electronic Transport of Zigzag MoS2
(252) Zhao, X.; Kotakoski, J.; Meyer, J. C.; Sutter, E.; Sutter, P.; Nanoribbons. Phys. E: Low-Dimens. Syst. Nanostructures 2020, 120,
Krasheninnikov, A. V.; Kaiser, U.; Zhou, W. Engineering and 114039.
Modifying Two-Dimensional Materials by Electron Beams. MRS (271) Kiriya, D.; Tosun, M.; Zhao, P.; Kang, J. S.; Javey, A. Air-
Bull. 2017, 42, 667−676. Stable Surface Charge Transfer Doping of MoS2 by Benzyl Viologen.
(253) Zhou, W.; Zou, X.; Najmaei, S.; Liu, Z.; Shi, Y.; Kong, J.; Lou, J. Am. Chem. Soc. 2014, 136, 7853−7856.
J.; Ajayan, P. M.; Yakobson, B. I.; Idrobo, J.-C. Intrinsic Structural (272) Jo, S.-H.; Kang, D.-H.; Shim, J.; Jeon, J.; Jeon, M. H.; Yoo, G.;
Defects in Monolayer Molybdenum Disulfide. Nano Lett. 2013, 13, Kim, J.; Lee, J.; Yeom, G. Y.; Lee, S.; et al. A High-Performance
2615−2622. WSe2/h-BN Photodetector Using a Triphenylphosphine (PPh3)-
(254) van der Zande, A. M.; Huang, P. Y.; Chenet, D. A.; Based N-Doping Technique. Adv. Mater. 2016, 28, 4824−4831.
Berkelbach, T. C.; You, Y.; Lee, G.-H.; Heinz, T. F.; Reichman, D. R.; (273) Li, H.-M.; Lee, D.; Qu, D.; Liu, X.; Ryu, J.; Seabaugh, A.; Yoo,
Muller, D. A.; Hone, J. C. Grains and Grain Boundaries in Highly W. J. Ultimate Thin Vertical P−N Junction Composed of Two-
Crystalline Monolayer Molybdenum Disulphide. Nat. Mater. 2013, Dimensional Layered Molybdenum Disulfide. Nat. Commun. 2015, 6,
12, 554−561. 6564.
(255) Elibol, K.; Susi, T.; Argentero, G.; Reza Ahmadpour (274) Pető , J.; Ollár, T.; Vancsó, P.; Popov, Z. I.; Magda, G. Z.;
Monazam, M.; Pennycook, T. J.; Meyer, J. C.; Kotakoski, J. Atomic Dobrik, G.; Hwang, C.; Sorokin, P. B.; Tapasztó, L. Spontaneous
Structure of Intrinsic and Electron-Irradiation-Induced Defects in Doping of the Basal Plane of MoS2 Single Layers through Oxygen
MoTe2. Chem. Mater. 2018, 30, 1230−1238. Substitution under Ambient Conditions. Nat. Chem. 2018, 10, 1246−
(256) Azizi, A.; Zou, X.; Ercius, P.; Zhang, Z.; Elías, A. L.; Perea- 1251.
López, N.; Stone, G.; Terrones, M.; Yakobson, B. I.; Alem, N. (275) Yang, S.-Z.; Gong, Y.; Manchanda, P.; Zhang, Y.-Y.; Ye, G.;
Dislocation Motion and Grain Boundary Migration in Two- Chen, S.; Song, L.; Pantelides, S. T.; Ajayan, P. M.; Chisholm, M. F.;
Dimensional Tungsten Disulphide. Nat. Commun. 2014, 5, 4867. et al. Rhenium-Doped and Stabilized MoS2 Atomic Layers with Basal-
(257) Bertoldo, F.; Unocic, R. R.; Lin, Y.-C.; Sang, X.; Puretzky, A. Plane Catalytic Activity. Adv. Mater. 2018, 30, 1803477.
A.; Yu, Y.; Miakota, D.; Rouleau, C. M.; Schou, J.; Thygesen, K. S.; (276) Zhou, J.; Lin, J.; Sims, H.; Jiang, C.; Cong, C.; Brehm, J. A.;
et al. Intrinsic Defects in MoS2 Grown by Pulsed Laser Deposition: Zhang, Z.; Niu, L.; Chen, Y.; Zhou, Y.; et al. Synthesis of Co-Doped
From Monolayers to Bilayers. ACS Nano 2021, 15, 2858−2868. MoS2 Monolayers with Enhanced Valley Splitting. Adv. Mater. 2020,
(258) Li, L.; Long, R.; Prezhdo, O. V. Why Chemical Vapor 32, 1906536.
Deposition Grown MoS2 Samples Outperform Physical Vapor (277) Zhang, S.; Hill, H. M.; Moudgil, K.; Richter, C. A.; Hight
Deposition Samples: Time-Domain Ab Initio Analysis. Nano Lett. Walker, A. R.; Barlow, S.; Marder, S. R.; Hacker, C. A.;
2018, 18, 4008−4014. Pookpanratana, S. J. Controllable, Wide-Ranging N-Doping and P-
Chem. Rev. 2023, 123, 3329−3442
Doping of Monolayer Group 6 Transition-Metal Disulfides and Transformation in Solution Phase. Chem. Mater. 2018, 30, 2463−
Diselenides. Adv. Mater. 2018, 30, 1802991. 2473.
(278) Chen, M.; Nam, H.; Wi, S.; Ji, L.; Ren, X.; Bian, L.; Lu, S.; (295) Min, Y.; Kwak, J.; Soon, A.; Jeong, U. Nonstoichiometric
Liang, X. Stable Few-Layer MoS2 Rectifying Diodes Formed by Nucleation and Growth of Multicomponent Nanocrystals in Solution.
Plasma-Assisted Doping. Appl. Phys. Lett. 2013, 103, 142110. Acc. Chem. Res. 2014, 47, 2887−2893.
(279) Kang, D.-H.; Kim, M.-S.; Shim, J.; Jeon, J.; Park, H.-Y.; Jung, (296) Im, H. J.; Koo, B.; Kim, M.-S.; Lee, J. E. Solvothermal
W.-S.; Yu, H.-Y.; Pang, C.-H.; Lee, S.; Park, J.-H. High-Performance Synthesis of Sb2Te3 Nanoplates under Various Synthetic Conditions
Transition Metal Dichalcogenide Photodetectors Enhanced by Self- and Their Thermoelectric Properties. Appl. Surf. Sci. 2019, 475, 510−
Assembled Monolayer Doping. Adv. Funct. Mater. 2015, 25, 4219− 514.
4227. (297) Wang, H.; Zhang, S.; Zhang, T.; Liu, J.; Zhang, Z.; Yuan, G.;
(280) Liu, X.; Qu, D.; Ryu, J.; Ahmed, F.; Yang, Z.; Lee, D.; Yoo, W. Liang, Y.; Tan, J.; Ren, Y.; Lei, W. SnSe Nanoplates for
J. P-Type Polar Transition of Chemically Doped Multilayer MoS2 Photodetectors with a High Signal/Noise Ratio. ACS Appl. Nano
Transistor. Adv. Mater. 2016, 28, 2345−2351. Mater. 2021, 4, 13071−13078.
(281) Tsai, M.-Y.; Zhang, S.; Campbell, P. M.; Dasari, R. R.; Ba, X.; (298) Liu, F.; Jiang, Y.; Yang, J.; Hao, M.; Tong, Z.; Jiang, L.; Wu, Z.
Tarasov, A.; Graham, S.; Barlow, S.; Marder, S. R.; Vogel, E. M. MoS2 Nanodot Decorated In2S3 Nanoplates: A Novel Heterojunction
Solution-Processed Doping of Trilayer WSe2 with Redox-Active with Enhanced Photoelectrochemical Performance. Chem. Commun.
Molecules. Chem. Mater. 2017, 29, 7296−7304. 2016, 52, 1867−1870.
(282) Tarasov, A.; Zhang, S.; Tsai, M.-Y.; Campbell, P. M.; Graham, (299) Yu, X.; Zhou, J.; Li, Q.; Zhao, W.-N.; Zhao, S.; Chen, H.; Tao,
S.; Barlow, S.; Marder, S. R.; Vogel, E. M. Controlled Doping of K.; Han, L. Bi2S3 Nanorod-Stacked Hollow Microtubes Self-
Large-Area Trilayer MoS2 with Molecular Reductants and Oxidants. Assembled from Bismuth-Based Metal−Organic Frameworks as
Adv. Mater. 2015, 27, 1175−1181. Advanced Negative Electrodes for Hybrid Supercapacitors. Dalton
(283) Luo, Z.; Ouyang, Y.; Zhang, H.; Xiao, M.; Ge, J.; Jiang, Z.; Trans. 2019, 48, 9057−9061.
Wang, J.; Tang, D.; Cao, X.; Liu, C.; Xing, W. Chemically Activating (300) Wu, Y.; Zheng, J.; Tong, Y.; Liu, X.; Sun, Y.; Niu, L.; Li, H.
MoS2 via Spontaneous Atomic Palladium Interfacial Doping Towards Carbon Hollow Tube-Confined Sb/Sb2S3 Nanorod Fragments as
Efficient Hydrogen Evolution. Nat. Commun. 2018, 9, 2120. Highly Stable Anodes for Potassium-Ion Batteries. ACS Appl. Mater.
(284) Chu, X. S.; Yousaf, A.; Li, D. O.; Tang, A. A.; Debnath, A.; Interfaces 2021, 13, 51066−51077.
Ma, D.; Green, A. A.; Santos, E. J. G.; Wang, Q. H. Direct Covalent (301) Park, S.-N.; Kim, S.-Y.; Lee, S.-J.; Sung, S.-J.; Yang, K.-J.;
Chemical Functionalization of Unmodified Two-Dimensional Mo- Kang, J.-K.; Kim, D.-H. Facile Growth of a Sb2Se3 Nanorod Array
lybdenum Disulfide. Chem. Mater. 2018, 30, 2112−2128. Induced by a MoSe2 Interlayer and Its Application in 3D P−N
(285) Voiry, D.; Goswami, A.; Kappera, R.; Silva, C. d. C. C. e.; Junction Solar Cells. Mater. Adv. 2022, 3, 978−985.
Kaplan, D.; Fujita, T.; Chen, M.; Asefa, T.; Chhowalla, M. Covalent (302) Wang, Y.; Chen, J.; Wang, P.; Chen, L.; Chen, Y.-B.; Wu, L.-
Functionalization of Monolayered Transition Metal Dichalcogenides M. Syntheses, Growth Mechanism, and Optical Properties of [001]
by Phase Engineering. Nat. Chem. 2015, 7, 45−49. Growing Bi2S3 Nanorods. J. Phys. Chem. C 2009, 113, 16009−16014.
(286) Presolski, S.; Pumera, M. Covalent Functionalization of MoS2. (303) Luo, W.; Calas, A.; Tang, C.; Li, F.; Zhou, L.; Mai, L.
Mater. Today 2016, 19, 140−145. Ultralong Sb2Se3 Nanowire-Based Free-Standing Membrane Anode
(287) Ries, L.; Petit, E.; Michel, T.; Diogo, C. C.; Gervais, C.; for Lithium/Sodium Ion Batteries. ACS Appl. Mater. Interfaces 2016,
Salameh, C.; Bechelany, M.; Balme, S.; Miele, P.; Onofrio, N.; et al. 8, 35219−35226.
Enhanced Sieving from Exfoliated MoS2 Membranes via Covalent (304) Jang, J. T.; Jeong, S.; Seo, J. W.; Kim, M. C.; Sim, E.; Oh, Y.;
Functionalization. Nat. Mater. 2019, 18, 1112−1117. Nam, S.; Park, B.; Cheon, J. Ultrathin Zirconium Disulfide Nanodiscs.
(288) Ji, H. G.; Solís-Fernández, P.; Yoshimura, D.; Maruyama, M.; J. Am. Chem. Soc. 2011, 133, 7636−7639.
Endo, T.; Miyata, Y.; Okada, S.; Ago, H. Chemically Tuned P- and N- (305) Leng, F.; Liu, Y.; Li, G.; Lai, W.; Zhang, Q.; Liu, W.; Hu, C.;
Type WSe2 Monolayers with High Carrier Mobility for Advanced Li, P.; Sheng, F.; Huang, J.; et al. Cu2−xSe Nanoparticles (Cu2−xSe
Electronics. Adv. Mater. 2019, 31, 1903613. NPs) Mediated Neurotoxicity via Oxidative Stress Damage in Pc-12
(289) Tuci, G.; Mosconi, D.; Rossin, A.; Luconi, L.; Agnoli, S.; Cells and Balb/C Mice. RSC Adv. 2019, 9, 36558−36569.
Righetto, M.; Pham-Huu, C.; Ba, H.; Cicchi, S.; Granozzi, G.; et al. (306) Yu, H.; Wang, J.; Wang, T.; Yu, H.; Yang, J.; Liu, G.; Qiao, G.;
Surface Engineering of Chemically Exfoliated MoS2 in a “Click”: How Yang, Q.; Cheng, X. Scalable Colloidal Synthesis of Uniform Bi2S3
to Generate Versatile Multifunctional Transition Metal Dichalcoge- Nanorods as Sensitive Materials for Visible-Light Photodetectors.
nides-Based Platforms. Chem. Mater. 2018, 30, 8257−8269. CrystEngComm 2017, 19, 727−733.
(290) Cao, J.; Zhou, J.; Zhang, Y.; Wang, Y.; Liu, X. Dominating (307) Southouse, J. P.; Lazzarini, L.; Ibhadon, A. O.; Francesconi,
Role of Aligned MoS2/Ni3S2 Nanoarrays Supported on Three- M. G. Ultra-Small FeS2 Nanoparticles for Highly Efficient Chemo-
Dimensional Ni Foam with Hydrophilic Interface for Highly selective Transfer Hydrogenation of Nitroarenes. New J. Chem. 2021,
Enhanced Hydrogen Evolution Reaction. ACS Appl. Mater. Interfaces 45, 17808−17815.
2018, 10, 1752−1760. (308) McCarthy, S. A.; Ratkic, R.; Purcell-Milton, F.; Perova, T. S.;
(291) Xia, Y.; Xiong, Y.; Lim, B.; Skrabalak, S. E. Shape-Controlled Gun’ko, Y. K. Adaptable Surfactant-Mediated Method for the
Synthesis of Metal Nanocrystals: Simple Chemistry Meets Complex Preparation of Anisotropic Metal Chalcogenide Nanomaterials. Sci.
Physics? Angew. Chem., Int. Ed. 2009, 48, 60−103. Rep. 2018, 8, 2860.
(292) Park, G.; Lee, J.; Moon, S.; Yang, H.; Giri, A.; Kwak, J.; Jung, (309) Georgiadou, V.; Kokotidou, C.; Le Droumaguet, B.;
Y.-K.; Soon, A.; Jeong, U. Eventual Chemical Transformation of Carbonnier, B.; Choli-Papadopoulou, T.; Dendrinou-Samara, C.
Metals and Chalcogens into Metal Chalcogenide Nanoplates through Oleylamine as a Beneficial Agent for the Synthesis of CoFe2O4
a Surface Nucleation-Detachment-Reorganization Mechanism. Chem. Nanoparticles with Potential Biomedical Uses. Dalton. Trans. 2014,
Mater. 2017, 29, 3219−3227. 43, 6377−6388.
(293) Mi, J.-L.; Christensen, M.; Tyrsted, C.; Jensen, K. Ø.; Becker, (310) Ma, Y.; Zeng, J.; Li, W.; McKiernan, M.; Xie, Z.; Xia, Y. Seed-
J.; Hald, P.; Iversen, B. B. Formation and Growth of Bi2Te3 in Mediated Synthesis of Truncated Gold Decahedrons with a AuCl/
Biomolecule-Assisted near-Critical Water: In Situ Synchrotron Oleylamine Complex as Precursor. Adv. Mater. 2010, 22, 1930−1934.
Radiation Study. J. Phys. Chem. C 2010, 114, 12133−12138. (311) Mourdikoudis, S.; Liz-Marzán, L. M. Oleylamine in Nano-
(294) Giri, A.; Yang, H.; Jang, W.; Kwak, J.; Thiyagarajan, K.; Pal, particle Synthesis. Chem. Mater. 2013, 25, 1465−1476.
M.; Lee, D.; Singh, R.; Kim, C.; Cho, K.; et al. Synthesis of Atomically (312) Zhang, S.; Chowdari, B. V. R.; Wen, Z.; Jin, J.; Yang, J.
Thin Transition Metal Ditelluride Films by Rapid Chemical Constructing Highly Oriented Configuration by Few-Layer MoS2:
Chem. Rev. 2023, 123, 3329−3442
Toward High-Performance Lithium-Ion Batteries and Hydrogen (330) Min Lim, H.; Batabyal, S. K.; Pramana, S. S.; Wong, L. H.;
Evolution Reactions. ACS Nano 2015, 9, 12464−12472. Magdassi, S.; Mhaisalkar, S. G. Chemical Welding of Binary
(313) Whitehead, C. B.; Ö zkar, S.; Finke, R. G. Lamer’s 1950 Model Nanoparticles: Room Temperature Sintering of CuSe and In2S3
of Particle Formation: A Review and Critical Analysis of Its Classical Nanoparticles for Solution-Processed CuInSxSe1‑x Solar Cells. Chem.
Nucleation and Fluctuation Theory Basis, of Competing Models and Commun. 2013, 49, 5351−5353.
Mechanisms for Phase-Changes and Particle Formation, and Then of (331) Lim, H. M.; Tan, J. Y.; Batabyal, S. K.; Magdassi, S.;
Its Application to Silver Halide, Semiconductor, Metal, and Metal- Mhaisalkar, S. G.; Wong, L. H. Photoactive Nanocrystals by Low-
Oxide Nanoparticles. Mater. Adv. 2021, 2, 186−235. Temperature Welding of Copper Sulfide Nanoparticles and Indium
(314) Penn, R. L.; Banfield, J. F. Imperfect Oriented Attachment: Sulfide Nanosheets. ChemSusChem 2014, 7, 3290−3294.
Dislocation Generation in Defect-Free Nanocrystals. Science 1998, (332) Gates, B.; Wu, Y.; Yin, Y.; Yang, P.; Xia, Y. Single-Crystalline
281, 969−971. Nanowires of Ag2Se Can Be Synthesized by Templating against
(315) Song, J.; Xia, F.; Zhao, M.; Zhong, Y. L.; Li, W.; Loh, K. P.; Nanowires of Trigonal Se. J. Am. Chem. Soc. 2001, 123, 11500−
Caruso, R. A.; Bao, Q. Solvothermal Growth of Bismuth 11501.
Chalcogenide Nanoplatelets by the Oriented Attachment Mechanism: (333) Xiao, F.; Yoo, B.; Lee, K. H.; Myung, N. V. Synthesis of Bi2Te3
An in Situ Pxrd Study. Chem. Mater. 2015, 27, 3471−3482. Nanotubes by Galvanic Displacement. J. Am. Chem. Soc. 2007, 129,
(316) Vaughn, D. D.; In, S.-I.; Schaak, R. E. A Precursor-Limited 10068−10069.
Nanoparticle Coalescence Pathway for Tuning the Thickness of (334) Fan, H.; Zhang, Y.; Zhang, M.; Wang, X.; Qian, Y. Glucose-
Laterally-Uniform Colloidal Nanosheets: The Case of SnSe. ACS Assisted Synthesis of CoTe Nanotubes in Situ Templated by Te
Nano 2011, 5, 8852−8860. Nanorods. Cryst. Growth Des. 2008, 8, 2838−2841.
(317) Zhang, G.; Wang, W.; Lu, X.; Li, X. Solvothermal Synthesis of (335) Li, J.; Tang, X.; Song, L.; Zhu, Y.; Qian, Y. From Te
V−VI Binary and Ternary Hexagonal Platelets: The Oriented Nanotubes to CoTe2 Nanotubes: A General Strategy for the
Attachment Mechanism. Cryst. Growth Des. 2009, 9, 145−150. Formation of 1D Metal Telluride Nanostructures. J. Cryst. Growth
(318) Son, J. S.; Park, K.; Kwon, S. G.; Yang, J.; Choi, M. K.; Kim, J.; 2009, 311, 4467−4472.
Yu, J. H.; Joo, J.; Hyeon, T. Dimension-Controlled Synthesis of CdS (336) Finefrock, S. W.; Fang, H.; Yang, H.; Darsono, H.; Wu, Y.
Nanocrystals: From 0D Quantum Dots to 2D Nanoplates. Small Large-Scale Solution-Phase Production of Bi2Te3 and PbTe Nano-
2012, 8, 2394−2402. wires Using Te Nanowire Templates. Nanoscale 2014, 6, 7872−7876.
(319) Li, L.; Chen, Z.; Hu, Y.; Wang, X.; Zhang, T.; Chen, W.; (337) Jeong, U.; Xia, Y.; Yin, Y. Large-Scale Synthesis of Single-
Wang, Q. Single-Layer Single-Crystalline SnSe Nanosheets. J. Am. Crystal CdSe Nanowires through a Cation-Exchange Route. Chem.
Chem. Soc. 2013, 135, 1213−1216. Phys. Lett. 2005, 416, 246−250.
(320) Hemati, T.; Zhang, X.; Weng, B. A Direct Oriented- (338) Park, W. I.; Kim, H. S.; Jang, S. Y.; Park, J.; Bae, S. Y.; Jung,
Attachment Growth of Lead-Chalcogenide Mid-Infrared Nanocrystals M.; Lee, H.; Kim, J. Transformation of ZnTe Nanowires to CdTe
Nanowires through the Formation of ZnCdTe−CdTe Core−Shell
Film on Amorphous Substrates. J. Mater. Chem. C 2020, 8, 13205−
Structure by Vapor Transport. J. Mater. Chem. 2008, 18, 875−880.
13212.
(339) Samal, A. K.; Pradeep, T. Room-Temperature Chemical
(321) Qian, H.-m.; Zhao, Q.; Dai, B.-s.; Guo, L.-j.; Zhang, J.-x.; Liu,
Synthesis of Silver Telluride Nanowires. J. Phys. Chem. C 2009, 113,
J.-j.; Zhang, J.-t.; Zhu, H.-s. Oriented Attachment of Nanoparticles to
13539−13544.
Form Micrometer-Sized Nanosheets/Nanobelts by Topotactic
(340) Samal, A. K.; Pradeep, T. Lanthanum Telluride Nanowires:
Reaction on Rigid/Flexible Substrates with Improved Electronic
Formation, Doping, and Raman Studies. J. Phys. Chem. C 2010, 114,
Properties. NPG Asia Mater. 2015, 7, e152−e152. 5871−5878.
(322) Min, Y.; Moon, G. D.; Kim, B. S.; Lim, B.; Kim, J. S.; Kang, C. (341) Ning, J.; Kershaw, S. V.; Rogach, A. L. Synthesis of
Y.; Jeong, U. Quick, Controlled Synthesis of Ultrathin Bi2Se3 Anisotropic ZnSe Nanorods with Zinc Blende Crystal Structure.
Nanodiscs and Nanosheets. J. Am. Chem. Soc. 2012, 134, 2872−2875. Angew. Chem., Int. Ed. 2020, 59, 5385−5391.
(323) Schliehe, C.; Juarez, B. H.; Pelletier, M.; Jander, S.; (342) Coogan, Á .; Gun’ko, Y. K. Solution-Based “Bottom-up”
Greshnykh, D.; Nagel, M.; Meyer, A.; Foerster, S.; Kornowski, A.; Synthesis of Group VI Transition Metal Dichalcogenides and Their
Klinke, C.; Weller, H.; et al. Ultrathin PbS Sheets by Two- Applications. Mater. Adv. 2021, 2, 146−164.
Dimensional Oriented Attachment. Science 2010, 329, 550−553. (343) Moon, G. D.; Ko, S.; Xia, Y.; Jeong, U. Chemical
(324) Cho, K.-S.; Talapin, D. V.; Gaschler, W.; Murray, C. B. Transformations in Ultrathin Chalcogenide Nanowires. ACS Nano
Designing Pbse Nanowires and Nanorings through Oriented 2010, 4, 2307−2319.
Attachment of Nanoparticles. J. Am. Chem. Soc. 2005, 127, 7140− (344) Shinde, V. R.; Gujar, T. P.; Noda, T.; Fujita, D.; Lokhande, C.
7147. D.; Joo, O.-S. Ultralong Cadmium Chalcogenide Nanotubes from
(325) Xue, X.; Huang, Y.; Zhuang, Z.; Huang, F.; Lin, Z. One-Dimensional Cadmium Hydroxide Nanowire Bundles by Soft
Temperature-Sensitive Growth Kinetics and Photoluminescence Solution Chemistry. J. Phys. Chem. C 2009, 113, 14179−14183.
Properties of CdS Quantum Dots. CrystEngComm 2013, 15, 4963− (345) Sines, I. T.; Vaughn, D. D.; Biacchi, A. J.; Kingsley, C. E.;
4969. Popczun, E. J.; Schaak, R. E. Engineering Porosity into Single-Crystal
(326) Tang, Z.; Zhang, Z.; Wang, Y.; Glotzer, S. C.; Kotov, N. A. Colloidal Nanosheets Using Epitaxial Nucleation and Chalcogenide
Self-Assembly of CdTe Nanocrystals into Free-Floating Sheets. Anion Exchange Reactions: The Conversion of SnSe to SnTe. Chem.
Science 2006, 314, 274−278. Mater. 2012, 24, 3088−3093.
(327) Xue, X.; Penn, R. L.; Leite, E. R.; Huang, F.; Lin, Z. Crystal (346) Seo, J.-W.; Jun, Y.-W.; Park, S.-W.; Nah, H.; Moon, T.; Park,
Growth by Oriented Attachment: Kinetic Models and Control B.; Kim, J.-G.; Kim, Y. J.; Cheon, J. Two-Dimensional Nanosheet
Factors. CrystEngComm 2014, 16, 1419−1429. Crystals. Angew. Chem., Int. Ed. 2007, 46, 8828−8831.
(328) Wang, Z.; Schliehe, C.; Wang, T.; Nagaoka, Y.; Cao, Y. C.; (347) Zhuo, S.; Xu, Y.; Zhao, W.; Zhang, J.; Zhang, B. Hierarchical
Bassett, W. A.; Wu, H.; Fan, H.; Weller, H. Deviatoric Stress Driven Nanosheet-Based MoS2 Nanotubes Fabricated by an Anion-Exchange
Formation of Large Single-Crystal PbS Nanosheet from Nanoparticles Reaction of MoO3−Amine Hybrid Nanowires. Angew. Chem., Int. Ed.
and in Situ Monitoring of Oriented Attachment. J. Am. Chem. Soc. 2013, 52, 8602−8606.
2011, 133, 14484−14487. (348) He, Z.; Yang, Y.; Liang, H. W.; Liu, J. W.; Yu, S. H. Nanowire
(329) van Overbeek, C.; Peters, J. L.; van Rossum, S. A. P.; Smits, Genome: A Magic Toolbox for 1D Nanostructures. Adv. Mater. 2019,
M.; van Huis, M. A.; Vanmaekelbergh, D. Interfacial Self-Assembly 31, 1902807.
and Oriented Attachment in the Family of PbX (X = S, Se, Te) (349) Yang, Y.; Wang, K.; Liang, H.-W.; Liu, G.-Q; Feng, M.; Xu, L.;
Nanocrystals. J. Phys. Chem. C 2018, 122, 12464−12473. Liu, J.-W; Wang, J.-L.; Yu, S.-H. A New Generation of Alloyed/
Chem. Rev. 2023, 123, 3329−3442
MultiMetal Chalcogenide Nanowires by Chemical Transformation. (367) Son, J. S.; Park, K.; Kwon, S. G.; Yang, J.; Choi, M. K.; Kim, J.;
Sci. Adv. 2015, 1, e1500714. Yu, J. H.; Joo, J.; Hyeon, T. Dimension-Controlled Synthesis of CdS
(350) Sciacca, B.; Yalcin, A. O.; Garnett, E. C. Transformation of Ag Nanocrystals: From 0D Quantum Dots to 2D Nanoplates. Small
Nanowires into Semiconducting AgFeS2 Nanowires. J. Am. Chem. Soc. 2012, 8, 2394−2402.
2015, 137, 4340−4343. (368) van der Stam, W.; Akkerman, Q. A.; Ke, X.; van Huis, M. A.;
(351) Zhou, C.; Dun, C.; Wang, K.; Zhang, X.; Shi, Z.; Liu, G.; Bals, S.; de Mello Donega, C. Solution-Processable Ultrathin Size- and
Hewitt, C. A.; Qiao, G.; Carroll, D. L. General Method of Synthesis Shape-Controlled Colloidal Cu2−xS Nanosheets. Chem. Mater. 2015,
Ultrathin Ternary Metal Chalcogenide Nanowires for Potential 27, 283−291.
Thermoelectric Applications. Nano Energy 2016, 30, 709−716. (369) Malakooti, R.; Cademartiri, L.; Migliori, A.; Ozin, G. A.
(352) Xu, B.; Agne, M. T.; Feng, T.; Chasapis, T. C.; Ruan, X.; Ultrathin Sb2S3 Nanowires and Nanoplatelets. J. Mater. Chem. 2008,
Zhou, Y.; Zheng, H.; Bahk, J. H.; Kanatzidis, M. G.; Snyder, G. J.; 18, 66−69.
et al. Nanocomposites from Solution-Synthesized PbTe-Bisbte (370) Busatto, S.; Spallacci, C.; Meeldijk, J. D.; Howes, S.; de Mello
Nanoheterostructure with Unity Figure of Merit at Low-Medium Donega, C. Room-Temperature Interconversion between Ultrathin
Temperatures (500−600 K). Adv. Mater. 2017, 29, 1605140. CdTe Magic-Size Nanowires Induced by Ligand Shell Dynamics. J.
(353) Hong, W.; Wang, J.; Wang, E. Facile Synthesis of PdAgTe Phys. Chem. C 2022, 126, 15280−15297.
Nanowires with Superior Electrocatalytic Activity. J. Power Sources (371) Pun, A. B.; Mazzotti, S.; Mule, A. S.; Norris, D. J.
2014, 272, 940−945. Understanding Discrete Growth in Semiconductor Nanocrystals:
(354) Li, H. H.; Zhao, S.; Gong, M.; Cui, C. H.; He, D.; Liang, H. Nanoplatelets and Magic-Sized Clusters. Acc. Chem. Res. 2021, 54,
W.; Wu, L.; Yu, S. H. Ultrathin Ptpdte Nanowires as Superior 1545−1554.
Catalysts for Methanol Electrooxidation. Angew. Chem., Int. Ed. Engl. (372) Salzmann, B. B. V.; van der Sluijs, M. M.; Soligno, G.;
2013, 52, 7472−7476. Vanmaekelbergh, D. Oriented Attachment: From Natural Crystal
(355) Ma, S. Y.; Li, H. H.; Hu, B. C.; Cheng, X.; Fu, Q. Q.; Yu, S. H. Growth to a Materials Engineering Tool. Acc. Chem. Res. 2021, 54,
Synthesis of Low Pt-Based Quaternary Ptpdrute Nanotubes with 787−797.
Optimized Incorporation of Pd for Enhanced Electrocatalytic Activity. (373) Wang, F.; Wang, Y.; Liu, Y. H.; Morrison, P. J.; Loomis, R. A.;
J. Am. Chem. Soc. 2017, 139, 5890−5895. Buhro, W. E. Two-Dimensional Semiconductor Nanocrystals:
(356) Ramasamy, P.; Kim, M.; Ra, H. S.; Kim, J.; Lee, J. S. Bandgap Properties, Templated Formation, and Magic-Size Nanocluster
Tunable Colloidal Cu-Based Ternary and Quaternary Chalcogenide Intermediates. Acc. Chem. Res. 2015, 48, 13−21.
Nanosheets via Partial Cation Exchange. Nanoscale 2016, 8, 7906− (374) Busatto, S.; de Mello Donega, C. Magic-Size Semiconductor
7913. Nanostructures: Where Does the Magic Come From? ACS Mater. Au
(357) Deng, J.; Li, H.; Wang, S.; Ding, D.; Chen, M.; Liu, C.; Tian, 2022, 2, 237−249.
Z.; Novoselov, K. S.; Ma, C.; Deng, D.; Bao, X. Multiscale Structural (375) Park, H.; Chung, H.; Kim, W. Synthesis of Ultrathin Wurtzite
and Electronic Control of Molybdenum Disulfide Foam for Highly ZnSe Nanosheets. Mater. Lett. 2013, 99, 172−175.
Efficient Hydrogen Production. Nat. Commun. 2017, 8, 14430. (376) Zhang, J.; Rowland, C.; Liu, Y.; Xiong, H.; Kwon, S.;
(358) Zhang, L.; Wu, H. B.; Yan, Y.; Wang, X.; Lou, X. W. Shevchenko, E.; Schaller, R. D.; Prakapenka, V. B.; Tkachev, S.; Rajh,
Hierarchical MoS2 Microboxes Constructed by Nanosheets with T. Evolution of Self-Assembled ZnTe Magic-Sized Nanoclusters. J.
Enhanced Electrochemical Properties for Lithium Storage and Water Am. Chem. Soc. 2015, 137, 742−749.
Splitting. Energy Environ. Sci. 2014, 7, 3302−3306. (377) Pradhan, N.; Xu, H.; Peng, X. Colloidal Cdse Quantum Wires
(359) Tan, L.; Li, X.; Wang, Z.; Guo, H.; Wang, J. Lightweight by Oriented Attachment. Nano Lett. 2006, 6, 720−724.
Reduced Graphene Oxide@MoS2 Interlayer as Polysulfide Barrier for (378) Riedinger, A.; Ott, F. D.; Mule, A.; Mazzotti, S.; Knusel, P. N.;
High-Performance Lithium−Sulfur Batteries. ACS Appl. Mater. Kress, S. J. P.; Prins, F.; Erwin, S. C.; Norris, D. J. An Intrinsic Growth
Interfaces 2018, 10, 3707−3713. Instability in Isotropic Materials Leads to Quasi-Two-Dimensional
(360) Liu, Y.; Wang, W.; Zhang, S.; Li, W.; Wang, G.; Zhang, Y.; Nanoplatelets. Nat. Mater. 2017, 16, 743−748.
Han, M.; Zhang, H. MoS2 Nanodots Anchored on Reduced Graphene (379) Berends, A. C.; de Mello Donega, C. Ultrathin One- and Two-
Oxide for Efficient N2 Fixation to NH3. ACS Sustainable Chem. Eng. Dimensional Colloidal Semiconductor Nanocrystals: Pushing Quan-
2020, 8, 2320−2326. tum Confinement to the Limit. J. Phys. Chem. Lett. 2017, 8, 4077−
(361) Chong, S.; Sun, L.; Shu, C.; Guo, S.; Liu, Y.; Wang, W.; Liu, 4090.
H. K. Chemical Bonding Boosts Nano-Rose-Like MoS2 Anchored on (380) Cunningham, P. D.; Coropceanu, I.; Mulloy, K.; Cho, W.;
Reduced Graphene Oxide for Superior Potassium-Ion Storage. Nano Talapin, D. V. Quantized Reaction Pathways for Solution Synthesis of
Energy 2019, 63, 103868. Colloidal ZnSe Nanostructures: A Connection between Clusters,
(362) Yang, X.; Zhang, Z.; Fu, Y.; Li, Q. Porous Hollow Carbon Nanowires, and Two-Dimensional Nanoplatelets. ACS Nano 2020,
Spheres Decorated with Molybdenum Diselenide Nanosheets as 14, 3847−3857.
Anodes for Highly Reversible Lithium and Sodium Storage. Nanoscale (381) Porotnikov, D.; Zamkov, M. Progress and Prospects of
2015, 7, 10198−10203. Solution-Processed Two-Dimensional Semiconductor Nanocrystals. J.
(363) Guo, B.; Yu, K.; Song, H.; Li, H.; Tan, Y.; Fu, H.; Li, C.; Lei, Phys. Chem. C 2020, 124, 21895−21908.
X.; Zhu, Z. Preparation of Hollow Microsphere@Onion-Like Solid (382) Son, D.; Chae, S. I.; Kim, M.; Choi, M. K.; Yang, J.; Park, K.;
Nanosphere MoS2 Coated by a Carbon Shell as a Stable Anode for Kale, V. S.; Koo, J. H.; Choi, C.; Lee, M.; et al. Colloidal Synthesis of
Optimized Lithium Storage. Nanoscale 2016, 8, 420−430. Uniform-Sized Molybdenum Disulfide Nanosheets for Wafer-Scale
(364) Jin, J.; Kim, B.; Kim, M.; Park, N.; Kang, S.; Lee, S. M.; Kim, Flexible Nonvolatile Memory. Adv. Mater. 2016, 28, 9326−9332.
H. J.; Son, S. U. Template Synthesis of Hollow MoS2-Carbon (383) Jung, W.; Lee, S.; Yoo, D.; Jeong, S.; Miro, P.; Kuc, A.; Heine,
Nanocomposites Using Microporous Organic Polymers and Their T.; Cheon, J. Colloidal Synthesis of Single-Layer MSe2 (M = Mo, W)
Lithium Storage Properties. Nanoscale 2015, 7, 11280−11285. Nanosheets via Anisotropic Solution-Phase Growth Approach. J. Am.
(365) Wang, J.; Liu, J.; Chao, D.; Yan, J.; Lin, J.; Shen, Z. X. Self- Chem. Soc. 2015, 137, 7266−7269.
Assembly of Honeycomb-Like MoS2 Nanoarchitectures Anchored (384) Sun, Y.; Fujisawa, K.; Terrones, M.; Schaak, R. E. Solution
into Graphene Foam for Enhanced Lithium-Ion Storage. Adv. Mater. Synthesis of Few-Layer WTe2 and MoxW1−xTe2 Nanostructures. J.
2014, 26, 7162−7169. Mater. Chem. C 2017, 5, 11317−11323.
(366) Choi, S. H.; Ko, Y. N.; Lee, J.-K.; Kang, Y. C. 3D MoS2− (385) Chen, J.; Wu, X. J.; Gong, Y.; Zhu, Y.; Yang, Z.; Li, B.; Lu, Q.;
Graphene Microspheres Consisting of Multiple Nanospheres with Yu, Y.; Han, S.; Zhang, Z.; et al. Edge Epitaxy of Two-Dimensional
Superior Sodium Ion Storage Properties. Adv. Funct. Mater. 2015, 25, MoSe2 and MoS2 Nanosheets on One-Dimensional Nanowires. J. Am.
1780−1788. Chem. Soc. 2017, 139, 8653−8660.
Chem. Rev. 2023, 123, 3329−3442
(386) Sun, D.; Feng, S.; Terrones, M.; Schaak, R. E. Formation and (403) Bansal, N.; O’Mahony, F. T. F.; Lutz, T.; Haque, S. A.
Interlayer Decoupling of Colloidal MoSe2 Nanoflowers. Chem. Mater. Solution Processed Polymer−Inorganic Semiconductor Solar Cells
2015, 27, 3167−3175. Employing Sb2S3 as a Light Harvesting and Electron Transporting
(387) Sokolikova, M. S.; Sherrell, P. C.; Palczynski, P.; Bemmer, V. Material. Adv. Energy Mater. 2013, 3, 986−990.
L.; Mattevi, C. Direct Solution-Phase Synthesis of 1T’ WSe2 (404) Rath, T.; Edler, M.; Haas, W.; Fischereder, A.; Moscher, S.;
Nanosheets. Nat. Commun. 2019, 10, 712. Schenk, A.; Trattnig, R.; Sezen, M.; Mauthner, G.; Pein, A.; et al. A
(388) Jin, H.; Ahn, M.; Jeong, S.; Han, J. H.; Yoo, D.; Son, D. H.; Direct Route Towards Polymer/Copper Indium Sulfide Nano-
Cheon, J. Colloidal Single-Layer Quantum Dots with Lateral composite Solar Cells. Adv. Energy Mater. 2011, 1, 1046−1050.
Confinement Effects on 2D Exciton. J. Am. Chem. Soc. 2016, 138, (405) Leventis, H. C.; King, S. P.; Sudlow, A.; Hill, M. S.; Molloy, K.
13253−13259. C.; Haque, S. A. Nanostructured Hybrid Polymer-Inorganic Solar Cell
(389) Sun, Y.; Wang, Y.; Sun, D.; Carvalho, B. R.; Read, C. G.; Lee, Active Layers Formed by Controllable in Situ Growth of Semi-
C.-h.; Lin, Z.; Fujisawa, K.; Robinson, J. A.; Crespi, V. H.; et al. Low- conducting Sulfide Networks. Nano Lett. 2010, 10, 1253−1258.
Temperature Solution Synthesis of Few-Layer 1T ′-MoTe2 Nano- (406) Dowland, S.; Lutz, T.; Ward, A.; King, S. P.; Sudlow, A.; Hill,
structures Exhibiting Lattice Compression. Angew. Chem., Int. Ed. M. S.; Molloy, K. C.; Haque, S. A. Direct Growth of Metal Sulfide
2016, 55, 2830−2834. Nanoparticle Networks in Solid-State Polymer Films for Hybrid
(390) Jeong, S.; Yoo, D.; Jang, J. T.; Kim, M.; Cheon, J. Well- Inorganic−Organic Solar Cells. Adv. Mater. 2011, 23, 2739−2744.
Defined Colloidal 2-D Layered Transition-Metal Chalcogenide (407) MacLachlan, A. J.; Rath, T.; Cappel, U. B.; Dowland, S. A.;
Nanocrystals via Generalized Synthetic Protocols. J. Am. Chem. Soc. Amenitsch, H.; Knall, A.-C.; Buchmaier, C.; Trimmel, G.; Nelson, J.;
2012, 134, 18233−18236. Haque, S. A. Polymer/Nanocrystal Hybrid Solar Cells: Influence of
(391) Zhao, Y.; Cong, H.; Li, P.; Wu, D.; Chen, S.; Luo, W. Molecular Precursor Design on Film Nanomorphology, Charge
Hexagonal RuSe2 Nanosheets for Highly Efficient Hydrogen Generation and Device Performance. Adv. Funct. Mater. 2015, 25,
Evolution Electrocatalysis. Angew. Chem., Int. Ed. Engl. 2021, 60, 409−420.
7013−7017. (408) Savjani, N.; Lewis, E. A.; Bissett, M. A.; Brent, J. R.; Dryfe, R.
(392) Zhao, W.; Dong, B.; Guo, Z.; Su, G.; Gao, R.; Wang, W.; Cao, A. W.; Haigh, S. J.; O’Brien, P. Synthesis of Lateral Size-Controlled
L. Colloidal Synthesis of VSe2 Single-Layer Nanosheets as Novel Monolayer 1H-MoS2@Oleylamine as Supercapacitor Electrodes.
Electrocatalysts for the Hydrogen Evolution Reaction. Chem. Chem. Mater. 2016, 28, 657−664.
Commun. 2016, 52, 9228−9231. (409) Dubois, T.; Demazeau, G. Preparation of Fe3o4 Fine Particles
(393) Choi, S.-H.; An, K.; Kim, E.-G.; Yu, J. H.; Kim, J. H.; Hyeon, through a Solvothermal Process. Mater. Lett. 1994, 19, 38−47.
T. Simple and Generalized Synthesis of Semiconducting Metal Sulfide (410) Morey, G. W.; Niggli, P. The Hydrothermal Formation of
Nanocrystals. Adv. Funct. Mater. 2009, 19, 1645−1649. Silicates, a Review. J. Am. Chem. Soc. 1913, 35, 1086−1130.
(394) Vaughn, D. D.; Patel, R. J.; Hickner, M. A.; Schaak, R. E. (411) Feng, S.; Xu, R. New Materials in Hydrothermal Synthesis.
Single-Crystal Colloidal Nanosheets of GeS and GeSe. J. Am. Chem. Acc. Chem. Res. 2001, 34, 239−247.
Soc. 2010, 132, 15170−15172. (412) Shi, W.; Song, S.; Zhang, H. Hydrothermal Synthetic
(395) Kaltenhauser, V.; Rath, T.; Haas, W.; Torvisco, A.; Müller, S. Strategies of Inorganic Semiconducting Nanostructures. Chem. Soc.
K.; Friedel, B.; Kunert, B.; Saf, R.; Hofer, F.; Trimmel, G. Bismuth Rev. 2013, 42, 5714−5743.
Sulphide−Polymer Nanocomposites from a Highly Soluble Bismuth (413) Yang, K.; Wang, X.; Li, H.; Chen, B.; Zhang, X.; Li, S.; Wang,
Xanthate Precursor. J. Mater. Chem. C 2013, 1, 7825. N.; Zhang, H.; Huang, X.; Huang, W. Composition- and Phase-
(396) Antolini, F.; Di Luccio, T.; Laera, A. M.; Mirenghi, L.; Controlled Synthesis and Applications of Alloyed Phase Hetero-
Piscopiello, E.; Re, M.; Tapfer, L. Direct Synthesis of II−VI structures of Transition Metal Disulphides. Nanoscale 2017, 9, 5102−
Compound Nanocrystals in Polymer Matrix. Phys. Status Solidi B 5109.
2007, 244, 2768−2781. (414) Liu, Z.; Gao, Z.; Liu, Y.; Xia, M.; Wang, R.; Li, N.
(397) Brent, J. R.; McNaughter, P. D.; O’Brien, P. Precursor Heterogeneous Nanostructure Based on 1T-Phase MoS2 for
Determined Lateral Size Control of Monolayer MoS2 Nanosheets Enhanced Electrocatalytic Hydrogen Evolution. ACS Appl. Mater.
from a Series of Alkylammonium Thiomolybdates: A Reversal of Interfaces 2017, 9, 25291−25297.
Trend between Growth Media. Chem. Commun. 2017, 53, 6428− (415) Shao, J.; Qu, Q.; Wan, Z.; Gao, T.; Zuo, Z.; Zheng, H. From
6431. Dispersed Microspheres to Interconnected Nanospheres: Carbon-
(398) Shupp, J. P.; Kinne, A. S.; Arman, H. D.; Tonzetich, Z. J. Sandwiched Monolayered MoS2 as High-Performance Anode of Li-
Synthesis and Characterization of Molybdenum(0) and Tungsten(0) Ion Batteries. ACS Appl. Mater. Interfaces 2015, 7, 22927−22934.
Complexes of Tetramethylthiourea: Single-Source Precursors for (416) Xie, J.; Zhang, H.; Li, S.; Wang, R.; Sun, X.; Zhou, M.; Zhou,
MoS2 and WS2. Organometallics 2014, 33, 5238−5245. J.; Lou, X. W.; Xie, Y. Defect-Rich MoS2 Ultrathin Nanosheets with
(399) Athanassiou, A.; Blasi, L.; De Giorgi, M.; Caputo, G.; Fragouli, Additional Active Edge Sites for Enhanced Electrocatalytic Hydrogen
D.; Tsiranidou, E.; Laera, A. M.; Tapfer, L.; Cingolani, R. Comparison Evolution. Adv. Mater. 2013, 25, 5807−5813.
between Laser-Induced Nucleation of ZnS and CdS Nanocrystals (417) Xie, J.; Zhang, J.; Li, S.; Grote, F.; Zhang, X.; Zhang, H.;
Directly into Polymer Matrices. Polym. Compos. 2010, 31, 1075− Wang, R.; Lei, Y.; Pan, B.; Xie, Y. Controllable Disorder Engineering
1083. in Oxygen-Incorporated MoS2 Ultrathin Nanosheets for Efficient
(400) Boudjouk, P.; Seidler, D. J.; Grier, D.; McCarthy, G. J. Benzyl- Hydrogen Evolution. J. Am. Chem. Soc. 2013, 135, 17881−17888.
Substituted Tin Chalcogenides. Efficient Single-Source Precursors for (418) Martínez-Merino, P.; Sani, E.; Mercatelli, L.; Alcántara, R.;
Tin Sulfide, Tin Selenide, and Sn(SxSe1‑x) Solid Solutions. Chem. Navas, J. WSe2 Nanosheets Synthesized by a Solvothermal Process as
Mater. 1996, 8, 1189−1196. Advanced Nanofluids for Thermal Solar Energy. ACS Sustainable
(401) Lewis, E. A.; McNaughter, P. D.; Yin, Z.; Chen, Y.; Brent, J. Chem. Eng. 2020, 8, 1627−1636.
R.; Saah, S. A.; Raftery, J.; Awudza, J. A. M.; Malik, M. A.; O’Brien, P.; (419) Liu, Y.; Zhang, N.; Kang, H.; Shang, M.; Jiao, L.; Chen, J. WS2
et al. In Situ Synthesis of PbS Nanocrystals in Polymer Thin Films Nanowires as a High-Performance Anode for Sodium-Ion Batteries.
from Lead(II) Xanthate and Dithiocarbamate Complexes: Evidence Chemistry 2015, 21, 11878−11884.
for Size and Morphology Control. Chem. Mater. 2015, 27, 2127− (420) Liu, Q.; Li, X.; He, Q.; Khalil, A.; Liu, D.; Xiang, T.; Wu, X.;
2136. Song, L. Gram-Scale Aqueous Synthesis of Stable Few-Layered 1T-
(402) Reynolds, L. X.; Lutz, T.; Dowland, S.; MacLachlan, A.; King, MoS2: Applications for Visible-Light-Driven Photocatalytic Hydrogen
S.; Haque, S. A. Charge Photogeneration in Hybrid Solar Cells: A Evolution. Small 2015, 11, 5556−5564.
Comparison between Quantum Dots and in Situ Grown CdS. (421) Liu, Q.; Li, X.; Xiao, Z.; Zhou, Y.; Chen, H.; Khalil, A.; Xiang,
Nanoscale 2012, 4, 1561−1564. T.; Xu, J.; Chu, W.; Wu, X.; et al. Stable Metallic 1T-WS2
Chem. Rev. 2023, 123, 3329−3442
Nanoribbons Intercalated with Ammonia Ions: The Correlation (439) Sang, X.; Li, X.; Zhao, W.; Dong, J.; Rouleau, C. M.;
between Structure and Electrical/Optical Properties. Adv. Mater. Geohegan, D. B.; Ding, F.; Xiao, K.; Unocic, R. R. In Situ Edge
2015, 27, 4837−4844. Engineering in Two-Dimensional Transition Metal Dichalcogenides.
(422) Hu, Z.; Wang, L.; Zhang, K.; Wang, J.; Cheng, F.; Tao, Z.; Nat. Commun. 2018, 9, 2051.
Chen, J. MoS2 Nanoflowers with Expanded Interlayers as High- (440) Zhu, D.; Shu, H.; Jiang, F.; Lv, D.; Asokan, V.; Omar, O.;
Performance Anodes for Sodium-Ion Batteries. Angew. Chem., Int. Ed. Yuan, J.; Zhang, Z.; Jin, C. Capture the Growth Kinetics of CVD
Engl. 2014, 53, 12794−12798. Growth of Two-Dimensional MoS2. npj 2D Mater. Appl. 2017, 1, 8.
(423) Zhang, J.; Kang, W.; Jiang, M.; You, Y.; Cao, Y.; Ng, T. W.; (441) Jo, S.; Jung, J.-W.; Baik, J.; Kang, J.-W.; Park, I.-K.; Bae, T.-S.;
Yu, D. Y.; Lee, C. S.; Xu, J. Conversion of 1T-MoSe2 to 2H- Chung, H.-S.; Cho, C.-H. Surface-Diffusion-Limited Growth of
MoS2xSe2−2x Mesoporous Nanospheres for Superior Sodium Storage Atomically Thin WS2 Crystals from Core−Shell Nuclei. Nanoscale
Performance. Nanoscale 2017, 9, 1484−1490. 2019, 11, 8706−8714.
(424) Anto Jeffery, A.; Nethravathi, C.; Rajamathi, M. Two- (442) Xu, Z.-Q.; Zhang, Y.; Lin, S.; Zheng, C.; Zhong, Y. L.; Xia, X.;
Dimensional Nanosheets and Layered Hybrids of MoS2 and WS2 Li, Z.; Sophia, P. J.; Fuhrer, M. S.; Cheng, Y.-B.; Bao, Q. Synthesis and
through Exfoliation of Ammoniated MS2 (M = Mo,W). J. Phys. Chem. Transfer of Large-Area Monolayer WS2 Crystals: Moving toward the
C 2014, 118, 1386−1396. Recyclable Use of Sapphire Substrates. ACS Nano 2015, 9, 6178−
(425) Kitchen, H. J.; Vallance, S. R.; Kennedy, J. L.; Tapia-Ruiz, N.; 6187.
Carassiti, L.; Harrison, A.; Whittaker, A. G.; Drysdale, T. D.; (443) Zhang, X.; Nan, H.; Xiao, S.; Wan, X.; Gu, X.; Du, A.; Ni, Z.;
Kingman, S. W.; Gregory, D. H. Modern Microwave Methods in Ostrikov, K. Transition Metal Dichalcogenides Bilayer Single Crystals
Solid-State Inorganic Materials Chemistry: From Fundamentals to by Reverse-Flow Chemical Vapor Epitaxy. Nat. Commun. 2019, 10,
Manufacturing. Chem. Rev. 2014, 114, 1170−1206. 598.
(426) Sun, J.; Wang, W.; Yue, Q. Review on Microwave-Matter (444) Qiang, X.; Iwamoto, Y.; Watanabe, A.; Kameyama, T.; He, X.;
Interaction Fundamentals and Efficient Microwave-Associated Heat- Kaneko, T.; Shibuta, Y.; Kato, T. Non-Classical Nucleation in Vapor−
ing Strategies. Materials 2016, 9, 231. Liquid−Solid Growth of Monolayer WS2 Revealed by in-Situ
(427) Levin, E. E.; Grebenkemper, J. H.; Pollock, T. M.; Seshadri, R. Monitoring Chemical Vapor Deposition. Sci. Rep. 2021, 11, 22285.
Protocols for High Temperature Assisted-Microwave Preparation of (445) Zhou, J.; Lin, J.; Huang, X.; Zhou, Y.; Chen, Y.; Xia, J.; Wang,
Inorganic Compounds. Chem. Mater. 2019, 31, 7151−7159. H.; Xie, Y.; Yu, H.; Lei, J.; et al. A Library of Atomically Thin Metal
(428) Kitchen, H. J.; Vallance, S. R.; Kennedy, J. L.; Tapia-Ruiz, N.; Chalcogenides. Nature 2018, 556, 355−359.
Carassiti, L.; Harrison, A.; Whittaker, A. G.; Drysdale, T. D.; (446) Chen, W.; Zhao, J.; Zhang, J.; Gu, L.; Yang, Z.; Li, X.; Yu, H.;
Kingman, S. W.; Gregory, D. H. Modern Microwave Methods in Zhu, X.; Yang, R.; Shi, D.; et al. Oxygen-Assisted Chemical Vapor
Solid-State Inorganic Materials Chemistry: From Fundamentals to Deposition Growth of Large Single-Crystal and High-Quality
Manufacturing. Chem. Rev. 2014, 114, 1170−1206. Monolayer MoS2. J. Am. Chem. Soc. 2015, 137, 15632−15635.
(429) Bilecka, I.; Niederberger, M. Microwave Chemistry for (447) Gao, Y.; Hong, Y.-L.; Yin, L.-C.; Wu, Z.; Yang, Z.; Chen, M.-
Inorganic Nanomaterials Synthesis. Nanoscale 2010, 2, 1358−1374. L.; Liu, Z.; Ma, T.; Sun, D.-M.; Ni, Z.; et al. Ultrafast Growth of High-
(430) Lee, Y. B.; Kim, S. K.; Ji, S.; Song, W.; Chung, H.-S.; Choi, M. Quality Monolayer WSe2 on Au. Adv. Mater. 2017, 29, 1700990.
K.; Lee, M.; Myung, S.; Lim, J.; An, K.-S.; et al. Facile Microwave (448) Chen, J.; Zhao, X.; Tan, S. J. R.; Xu, H.; Wu, B.; Liu, B.; Fu,
Assisted Synthesis of Vastly Edge Exposed 1T/2H-MoS2 with D.; Fu, W.; Geng, D.; Liu, Y.; et al. Chemical Vapor Deposition of
Enhanced Activity for Hydrogen Evolution Catalysis. J. Mater. Large-Size Monolayer MoSe2 Crystals on Molten Glass. J. Am. Chem.
Chem. A 2019, 7, 3563−3569. Soc. 2017, 139, 1073−1076.
(431) Kwak, J.; Jung, S.; Lee, N.; Thiyagarajan, K.; Kim, J. K.; Giri, (449) Yang, P.; Zhang, S.; Pan, S.; Tang, B.; Liang, Y.; Zhao, X.;
A.; Jeong, U. Microwave-Assisted Synthesis of Group 5 Transition Zhang, Z.; Shi, J.; Huan, Y.; Shi, Y.; et al. Epitaxial Growth of
Metal Dichalcogenide Thin Films. J. Mater. Chem. C 2018, 6, 11303− Centimeter-Scale Single-Crystal MoS2 Monolayer on Au(111). ACS
11311. Nano 2020, 14, 5036−5045.
(432) Lee, Y.-H.; Zhang, X.-Q.; Zhang, W.; Chang, M.-T.; Lin, C.- (450) Tang, L.; Tan, J.; Nong, H.; Liu, B.; Cheng, H.-M. Chemical
T.; Chang, K.-D.; Yu, Y.-C.; Wang, J. T.-W.; Chang, C.-S.; Li, L.-J.; Vapor Deposition Growth of Two-Dimensional Compound Materi-
et al. Synthesis of Large-Area MoS2 Atomic Layers with Chemical als: Controllability, Material Quality, and Growth Mechanism. Acc.
Vapor Deposition. Adv. Mater. 2012, 24, 2320−2325. Mater. Res. 2021, 2, 36−47.
(433) Feldman, Y.; Wasserman, E.; Srolovitz, D. J.; Tenne, R. High- (451) Ji, Q.; Zhang, Y.; Zhang, Y.; Liu, Z. Chemical Vapour
Rate, Gas-Phase Growth of MoS2 Nested Inorganic Fullerenes and Deposition of Group-VIB Metal Dichalcogenide Monolayers:
Nanotubes. Science 1995, 267, 222−225. Engineered Substrates from Amorphous to Single Crystalline. Chem.
(434) Zhan, Y.; Liu, Z.; Najmaei, S.; Ajayan, P. M.; Lou, J. Large- Soc. Rev. 2015, 44, 2587−2602.
Area Vapor-Phase Growth and Characterization of MoS2 Atomic (452) Wang, X.; Gong, Y.; Shi, G.; Chow, W. L.; Keyshar, K.; Ye, G.;
Layers on a SiO2 Substrate. Small 2012, 8, 966−971. Vajtai, R.; Lou, J.; Liu, Z.; Ringe, E.; et al. Chemical Vapor Deposition
(435) Kim, H.; Mattevi, C.; Calvo, M. R.; Oberg, J. C.; Artiglia, L.; Growth of Crystalline Monolayer MoSe2. ACS Nano 2014, 8, 5125−
Agnoli, S.; Hirjibehedin, C. F.; Chhowalla, M.; Saiz, E. Activation 5131.
Energy Paths for Graphene Nucleation and Growth on Cu. ACS Nano (453) Chen, K.; Wan, X.; Xie, W.; Wen, J.; Kang, Z.; Zeng, X.; Chen,
2012, 6, 3614−3623. H.; Xu, J. Lateral Built-in Potential of Monolayer MoS2−WS2 in-Plane
(436) Zhao, B.; Dang, W.; Liu, Y.; Li, B.; Li, J.; Luo, J.; Zhang, Z.; Heterostructures by a Shortcut Growth Strategy. Adv. Mater. 2015,
Wu, R.; Ma, H.; Sun, G.; et al. Synthetic Control of Two-Dimensional 27, 6431−6437.
NiTe2 Single Crystals with Highly Uniform Thickness Distributions. J. (454) Chen, K.; Chen, Z.; Wan, X.; Zheng, Z.; Xie, F.; Chen, W.;
Am. Chem. Soc. 2018, 140, 14217−14223. Gui, X.; Chen, H.; Xie, W.; Xu, J. A Simple Method for Synthesis of
(437) Chang, Y.-H.; Zhang, W.; Zhu, Y.; Han, Y.; Pu, J.; Chang, J.- High-Quality Millimeter-Scale 1T′ Transition-Metal Telluride and
K.; Hsu, W.-T.; Huang, J.-K.; Hsu, C.-L.; Chiu, M.-H.; et al. near-Field Nanooptical Properties. Adv. Mater. 2017, 29, 1700704.
Monolayer MoSe2 Grown by Chemical Vapor Deposition for Fast (455) Yang, P.; Zou, X.; Zhang, Z.; Hong, M.; Shi, J.; Chen, S.; Shu,
Photodetection. ACS Nano 2014, 8, 8582−8590. J.; Zhao, L.; Jiang, S.; Zhou, X.; et al. Batch Production of 6-Inch
(438) Huang, J.-K.; Pu, J.; Hsu, C.-L.; Chiu, M.-H.; Juang, Z.-Y.; Uniform Monolayer Molybdenum Disulfide Catalyzed by Sodium in
Chang, Y.-H.; Chang, W.-H.; Iwasa, Y.; Takenobu, T.; Li, L.-J. Large- Glass. Nat. Commun. 2018, 9, 979.
Area Synthesis of Highly Crystalline WSe2 Monolayers and Device (456) Kim, H.; Ovchinnikov, D.; Deiana, D.; Unuchek, D.; Kis, A.
Applications. ACS Nano 2014, 8, 923−930. Suppressing Nucleation in Metal−Organic Chemical Vapor Deposi-
Chem. Rev. 2023, 123, 3329−3442
tion of MoS2 Monolayers by Alkali Metal Halides. Nano Lett. 2017, of Highly-Oriented Monolayer MoS2 Continuous Films. ACS Nano
17, 5056−5063. 2017, 11, 12001−12007.
(457) Kang, K.; Xie, S.; Huang, L.; Han, Y.; Huang, P. Y.; Mak, K. (475) Zhang, X.; Choudhury, T. H.; Chubarov, M.; Xiang, Y.;
F.; Kim, C.-J.; Muller, D.; Park, J. High-Mobility Three-Atom-Thick Jariwala, B.; Zhang, F.; Alem, N.; Wang, G.-C.; Robinson, J. A.;
Semiconducting Films with Wafer-Scale Homogeneity. Nature 2015, Redwing, J. M. Diffusion-Controlled Epitaxy of Large Area Coalesced
520, 656−660. WSe2 Monolayers on Sapphire. Nano Lett. 2018, 18, 1049−1056.
(458) Eichfeld, S. M.; Hossain, L.; Lin, Y.-C.; Piasecki, A. F.; Kupp, (476) Nakano, M.; Wang, Y.; Kashiwabara, Y.; Matsuoka, H.; Iwasa,
B.; Birdwell, A. G.; Burke, R. A.; Lu, N.; Peng, X.; Li, J.; et al. Highly Y. Layer-by-Layer Epitaxial Growth of Scalable WSe2 on Sapphire by
Scalable, Atomically Thin WSe2 Grown via Metal−Organic Chemical Molecular Beam Epitaxy. Nano Lett. 2017, 17, 5595−5599.
Vapor Deposition. ACS Nano 2015, 9, 2080−2087. (477) Chen, M.-W.; Ovchinnikov, D.; Lazar, S.; Pizzochero, M.;
(459) Kobayashi, Y.; Yoshida, S.; Maruyama, M.; Mogi, H.; Murase, Whitwick, M. B.; Surrente, A.; Baranowski, M.; Sanchez, O. L.; Gillet,
K.; Maniwa, Y.; Takeuchi, O.; Okada, S.; Shigekawa, H.; Miyata, Y. P.; Plochocka, P.; et al. Highly Oriented Atomically Thin Ambipolar
Continuous Heteroepitaxy of Two-Dimensional Heterostructures MoSe2 Grown by Molecular Beam Epitaxy. ACS Nano 2017, 11,
Based on Layered Chalcogenides. ACS Nano 2019, 13, 7527−7535. 6355−6361.
(460) Dumcenco, D.; Ovchinnikov, D.; Lopez Sanchez, O.; Gillet, (478) Chen, P.; Xu, W.; Gao, Y.; Warner, J. H.; Castell, M. R.
P.; Alexander, D. T. L.; Lazar, S.; Radenovic, A.; Kis, A. Large-Area Epitaxial Growth of Monolayer MoS2 on SrTiO3 Single Crystal
MoS2 Grown Using H2S as the Sulphur Source. 2D Mater. 2015, 2, Substrates for Applications in Nanoelectronics. ACS Appl. Nano
No. 044005. Mater. 2018, 1, 6976−6988.
(461) Yun, S. J.; Chae, S. H.; Kim, H.; Park, J. C.; Park, J.-H.; Han, (479) Wan, Y.; Xiao, J.; Li, J.; Fang, X.; Zhang, K.; Fu, L.; Li, P.;
G. H.; Lee, J. S.; Kim, S. M.; Oh, H. M.; Seok, J.; et al. Synthesis of Song, Z.; Zhang, H.; Wang, Y.; et al. Epitaxial Single-Layer MoS2 on
Centimeter-Scale Monolayer Tungsten Disulfide Film on Gold Foils. Gan with Enhanced Valley Helicity. Adv. Mater. 2018, 30, 1703888.
ACS Nano 2015, 9, 5510−5519. (480) Zhang, X.; Zhang, F.; Wang, Y.; Schulman, D. S.; Zhang, T.;
(462) Choudhury, T. H.; Zhang, X.; Al Balushi, Z. Y.; Chubarov, M.; Bansal, A.; Alem, N.; Das, S.; Crespi, V. H.; Terrones, M.; et al.
Redwing, J. M. Epitaxial Growth of Two-Dimensional Layered Defect-Controlled Nucleation and Orientation of WSe2 on hBN: A
Transition Metal Dichalcogenides. Annu. Rev. Mater. Res. 2020, 50, Route to Single-Crystal Epitaxial Monolayers. ACS Nano 2019, 13,
155−177. 3341−3352.
(463) Wang, J.; Li, T.; Wang, Q.; Wang, W.; Shi, R.; Wang, N.; (481) Suenaga, K.; Ji, H. G.; Lin, Y.-C.; Vincent, T.; Maruyama, M.;
Amini, A.; Cheng, C. Controlled Growth of Atomically Thin Aji, A. S.; Shiratsuchi, Y.; Ding, D.; Kawahara, K.; Okada, S.; et al.
Transition Metal Dichalcogenides via Chemical Vapor Deposition Surface-Mediated Aligned Growth of Monolayer MoS2 and in-Plane
Method. Mater. Today Adv. 2020, 8, 100098. Heterostructures with Graphene on Sapphire. ACS Nano 2018, 12,
(464) Wang, L.; Chen, L.; Wong, S. L.; Huang, X.; Liao, W.; Zhu, 10032−10044.
C.; Lim, Y.-F.; Li, D.; Liu, X.; Chi, D.; Ang, K.-W. Electronic Devices (482) Cui, F.; Wang, C.; Li, X.; Wang, G.; Liu, K.; Yang, Z.; Feng,
and Circuits Based on Wafer-Scale Polycrystalline Monolayer MoS2 Q.; Liang, X.; Zhang, Z.; Liu, S.; et al. Tellurium-Assisted Epitaxial
by Chemical Vapor Deposition. Adv. Electron. Mater. 2019, 5, Growth of Large-Area, Highly Crystalline ReS2 Atomic Layers on
1900393. Mica Substrate. Adv. Mater. 2016, 28, 5019−5024.
(465) Dumcenco, D.; Ovchinnikov, D.; Marinov, K.; Lazić, P.; (483) Aljarb, A.; Cao, Z.; Tang, H.-L.; Huang, J.-K.; Li, M.; Hu, W.;
Gibertini, M.; Marzari, N.; Sanchez, O. L.; Kung, Y.-C.; Krasnozhon, Cavallo, L.; Li, L.-J. Substrate Lattice-Guided Seed Formation
D.; Chen, M.-W.; et al. Large-Area Epitaxial Monolayer MoS2. ACS Controls the Orientation of 2D Transition-Metal Dichalcogenides.
Nano 2015, 9, 4611−4620. ACS Nano 2017, 11, 9215−9222.
(466) Li, B.; Gong, Y.; Hu, Z.; Brunetto, G.; Yang, Y.; Ye, G.; Zhang, (484) Wang, J.; Xu, X.; Cheng, T.; Gu, L.; Qiao, R.; Liang, Z.; Ding,
Z.; Lei, S.; Jin, Z.; Bianco, E.; et al. Solid−Vapor Reaction Growth of D.; Hong, H.; Zheng, P.; Zhang, Z.; et al. Dual-Coupling-Guided
Transition-Metal Dichalcogenide Monolayers. Angew. Chem., Int. Ed. Epitaxial Growth of Wafer-Scale Single-Crystal WS2 Monolayer on
2016, 55, 10656−10661. Vicinal a-Plane Sapphire. Nat. Nanotechnol. 2022, 17, 33−38.
(467) Gong, Y.; Ye, G.; Lei, S.; Shi, G.; He, Y.; Lin, J.; Zhang, X.; (485) Li, T.; Guo, W.; Ma, L.; Li, W.; Yu, Z.; Han, Z.; Gao, S.; Liu,
Vajtai, R.; Pantelides, S. T.; Zhou, W.; et al. Synthesis of Millimeter- L.; Fan, D.; Wang, Z.; et al. Epitaxial Growth of Wafer-Scale
Scale Transition Metal Dichalcogenides Single Crystals. Adv. Funct. Molybdenum Disulfide Semiconductor Single Crystals on Sapphire.
Mater. 2016, 26, 2009−2015. Nat. Nanotechnol. 2021, 16, 1201−1207.
(468) Yu, J.; Li, J.; Zhang, W.; Chang, H. Synthesis of High Quality (486) Aljarb, A.; Fu, J.-H.; Hsu, C.-C.; Chuu, C.-P.; Wan, Y.;
Two-Dimensional Materials via Chemical Vapor Deposition. Chem. Hakami, M.; Naphade, D. R.; Yengel, E.; Lee, C.-J.; Brems, S.; et al.
Sci. 2015, 6, 6705−6716. Ledge-Directed Epitaxy of Continuously Self-Aligned Single-Crystal-
(469) He, Y.; Sobhani, A.; Lei, S.; Zhang, Z.; Gong, Y.; Jin, Z.; Zhou, line Nanoribbons of Transition Metal Dichalcogenides. Nat. Mater.
W.; Yang, Y.; Zhang, Y.; Wang, X.; et al. Layer Engineering of 2D 2020, 19, 1300−1306.
Semiconductor Junctions. Adv. Mater. 2016, 28, 5126−5132. (487) Cheng, F.; Ding, Z.; Xu, H.; Tan, S. J. R.; Abdelwahab, I.; Su,
(470) Ohring, M.Chapter 6 - Chemical Vapor Deposition. In J.; Zhou, P.; Martin, J.; Loh, K. P. Epitaxial Growth of Single-Layer
Materials Science of Thin Films (Second Edition); Ohring, M., Ed.; Niobium Selenides with Controlled Stoichiometric Phases. Adv.
Academic Press: San Diego, 2002; pp 277−355. Mater. Interfaces 2018, 5, 1800429.
(471) Ohring, M.Chapter 7 - Substrate Surfaces and Thin-Film (488) Shi, J.; Huan, Y.; Hong, M.; Xu, R.; Yang, P.; Zhang, Z.; Zou,
Nucleation. In Materials Science of Thin Films (Second Edition); X.; Zhang, Y. Chemical Vapor Deposition Grown Large-Scale
Ohring, M., Ed.; Academic Press: San Diego, 2002; pp 357−415. Atomically Thin Platinum Diselenide with Semimetal−Semiconduc-
(472) Liu, B.; Fathi, M.; Chen, L.; Abbas, A.; Ma, Y.; Zhou, C. tor Transition. ACS Nano 2019, 13, 8442−8451.
Chemical Vapor Deposition Growth of Monolayer WSe2 with (489) Gao, Y.; Liu, Z.; Sun, D.-M.; Huang, L.; Ma, L.-P.; Yin, L.-C.;
Tunable Device Characteristics and Growth Mechanism Study. ACS Ma, T.; Zhang, Z.; Ma, X.-L.; Peng, L.-M.; et al. Large-Area Synthesis
Nano 2015, 9, 6119−6127. of High-Quality and Uniform Monolayer WS2 on Reusable Au Foils.
(473) Yu, Y.; Li, C.; Liu, Y.; Su, L.; Zhang, Y.; Cao, L. Controlled Nat. Commun. 2015, 6, 8569.
Scalable Synthesis of Uniform, High-Quality Monolayer and Few- (490) Bana, H.; Travaglia, E.; Bignardi, L.; Lacovig, P.; Sanders, C.
Layer MoS2 Films. Sci. Rep. 2013, 3, 1866. E.; Dendzik, M.; Michiardi, M.; Bianchi, M.; Lizzit, D.; Presel, F.;
(474) Yu, H.; Liao, M.; Zhao, W.; Liu, G.; Zhou, X. J.; Wei, Z.; Xu, et al. Epitaxial Growth of Single-Orientation High-Quality MoS2
X.; Liu, K.; Hu, Z.; Deng, K.; et al. Wafer-Scale Growth and Transfer Monolayers. 2D Mater. 2018, 5, No. 035012.
Chem. Rev. 2023, 123, 3329−3442
(491) Shi, J.; Zhang, X.; Ma, D.; Zhu, J.; Zhang, Y.; Guo, Z.; Yao, Y.; Realizing Large-Scale, Electronic-Grade Two-Dimensional Semi-
Ji, Q.; Song, X.; Zhang, Y.; et al. Substrate Facet Effect on the Growth conductors. ACS Nano 2018, 12, 965−975.
of Monolayer MoS2 on Au Foils. ACS Nano 2015, 9, 4017−4025. (509) Miwa, J. A.; Ulstrup, S.; Sørensen, S. G.; Dendzik, M.; Č abo,
(492) He, T.; Li, Y.; Zhou, Z.; Zeng, C.; Qiao, L.; Lan, C.; Yin, Y.; A. G.; Bianchi, M.; Lauritsen, J. V.; Hofmann, P. Electronic Structure
Li, C.; Liu, Y. Synthesis of Large-Area Uniform MoS2 Films by of Epitaxial Single-Layer MoS2. Phys. Rev. Lett. 2015, 114,
Substrate-Moving Atmospheric Pressure Chemical Vapor Deposition: No. 046802.
From Monolayer to Multilayer. 2D Mater. 2019, 6, No. 025030. (510) Fu, D.; Zhao, X.; Zhang, Y.-Y.; Li, L.; Xu, H.; Jang, A. R.;
(493) Song, S.; Sim, Y.; Kim, S.-Y.; Kim, J. H.; Oh, I.; Na, W.; Lee, Yoon, S. I.; Song, P.; Poh, S. M.; Ren, T.; Ding, Z.; Fu, W.; et al.
D. H.; Wang, J.; Yan, S.; Liu, Y.; et al. Wafer-Scale Production of Molecular Beam Epitaxy of Highly Crystalline Monolayer Molybde-
Patterned Transition Metal Ditelluride Layers for Two-Dimensional num Disulfide on Hexagonal Boron Nitride. J. Am. Chem. Soc. 2017,
Metal−Semiconductor Contacts at the Schottky−Mott Limit. Nat. 139, 9392−9400.
Electron. 2020, 3, 207−215. (511) Miwa, J. A.; Dendzik, M.; Grønborg, S. S.; Bianchi, M.;
(494) Lin, H.; Zhu, Q.; Shu, D.; Lin, D.; Xu, J.; Huang, X.; Shi, W.; Lauritsen, J. V.; Hofmann, P.; Ulstrup, S. vdW Epitaxy of Two-
Xi, X.; Wang, J.; Gao, L. Growth of Environmentally Stable Transition Dimensional MoS2−Graphene Heterostructures in Ultrahigh Vac-
Metal Selenide Films. Nat. Mater. 2019, 18, 602−607. uum. ACS Nano 2015, 9, 6502−6510.
(495) Islam, M. A.; Kim, J. H.; Schropp, A.; Kalita, H.; Choudhary, (512) Muñoz, R.; López-Elvira, E.; Munuera, C.; Frisenda, R.;
N.; Weitzman, D.; Khondaker, S. I.; Oh, K. H.; Roy, T.; Chung, H.-S.; Sánchez-Sánchez, C.; Martín-Gago, J. Á .; García-Hernández, M.
et al. Centimeter-Scale 2D vdW Vertical Heterostructures Integrated Direct Growth of Graphene-MoS2 Heterostructure: Tailored Interface
on Deformable Substrates Enabled by Gold Sacrificial Layer-Assisted for Advanced Devices. Appl. Surf. Sci. 2022, 581, 151858.
Growth. Nano Lett. 2017, 17, 6157−6165. (513) Ji, Q.; Kan, M.; Zhang, Y.; Guo, Y.; Ma, D.; Shi, J.; Sun, Q.;
(496) Zhou, L.; Xu, K.; Zubair, A.; Liao, A. D.; Fang, W.; Ouyang, Chen, Q.; Zhang, Y.; Liu, Z. Unravelling Orientation Distribution and
F.; Lee, Y.-H.; Ueno, K.; Saito, R.; Palacios, T.; et al. Large-Area Merging Behavior of Monolayer MoS2 Domains on Sapphire. Nano
Synthesis of High-Quality Uniform Few-Layer MoTe2. J. Am. Chem. Lett. 2015, 15, 198−205.
Soc. 2015, 137, 11892−11895. (514) Bets, K. V.; Gupta, N.; Yakobson, B. I. How the
(497) Hussain, S.; Shehzad, M. A.; Vikraman, D.; Khan, M. F.; Complementarity at Vicinal Steps Enables Growth of 2D Mono-
Singh, J.; Choi, D.-C.; Seo, Y.; Eom, J.; Lee, W.-G.; Jung, J. Synthesis crystals. Nano Lett. 2019, 19, 2027−2031.
and Characterization of Large-Area and Continuous MoS2 Atomic (515) Wang, L.; Xu, X.; Zhang, L.; Qiao, R.; Wu, M.; Wang, Z.;
Layers by RF Magnetron Sputtering. Nanoscale 2016, 8, 4340−4347. Zhang, S.; Liang, J.; Zhang, Z.; Zhang, Z.; et al. Epitaxial Growth of a
(498) Chow, P. K.; Singh, E.; viana, B. C.; Gao, J.; Luo, J.; Li, J.; Lin, 100-Square-Centimetre Single-Crystal Hexagonal Boron Nitride
Z.; Elías, A. L.; Shi, Y.; Wang, Z.; et al. Wetting of Mono and Few- Monolayer on Copper. Nature 2019, 570, 91−95.
(516) Choi, S. H.; Kim, H.-J.; Song, B.; Kim, Y. I.; Han, G.; Nguyen,
Layered WS2 and MoS2 Films Supported on Si/SiO2 Substrates. ACS
H. T. T.; Ko, H.; Boandoh, S.; Choi, J. H.; Oh, C. S.; et al. Epitaxial
Nano 2015, 9, 3023−3031.
Single-Crystal Growth of Transition Metal Dichalcogenide Mono-
(499) Wang, X.; Feng, H.; Wu, Y.; Jiao, L. Controlled Synthesis of
layers via the Atomic Sawtooth Au Surface. Adv. Mater. 2021, 33,
Highly Crystalline MoS2 Flakes by Chemical Vapor Deposition. J. Am.
2006601.
Chem. Soc. 2013, 135, 5304−5307.
(517) Wu, Y.; Yang, P. Direct Observation of Vapor−Liquid−Solid
(500) Giri, A.; Kumar, M.; Kim, J.; Pal, M.; Banerjee, W.; Nikam, R.
Nanowire Growth. J. Am. Chem. Soc. 2001, 123, 3165−3166.
D.; Kwak, J.; Kong, M.; Kim, S. H.; Thiyagarajan, K.; et al. Surface
(518) Keuleyan, S.; Wang, M.; Chung, F. R.; Commons, J.; Koski, K.
Diffusion and Epitaxial Self-Planarization for Wafer-Scale Single-Grain J. A Silicon-Based Two-Dimensional Chalcogenide: Growth of Si2Te3
Metal Chalcogenide Thin Films. Adv. Mater. 2021, 33, 2102252. Nanoribbons and Nanoplates. Nano Lett. 2015, 15, 2285−2290.
(501) Gao, L.; Sun, J.-T.; Lu, J.-C.; Li, H.; Qian, K.; Zhang, S.; (519) Hao, Y.; Meng, G.; Wang, Z. L.; Ye, C.; Zhang, L. Periodically
Zhang, Y.-Y.; Qian, T.; Ding, H.; Lin, X.; et al. Epitaxial Growth of Twinned Nanowires and Polytypic Nanobelts of ZnS: The Role of
Honeycomb Monolayer CuSe with Dirac Nodal Line Fermions. Adv. Mass Diffusion in Vapor−Liquid−Solid Growth. Nano Lett. 2006, 6,
Mater. 2018, 30, 1707055. 1650−1655.
(502) Lin, X.; Lu, J. C.; Shao, Y.; Zhang, Y. Y.; Wu, X.; Pan, J. B.; (520) Xiao, B.-b.; Xu, Y.-b. VLS Synthesis of Disordered CdSe
Gao, L.; Zhu, S. Y.; Qian, K.; Zhang, Y. F.; et al. Intrinsically Nanowires and Optical Properties of an Individual CdSe Nanowire.
Patterned Two-Dimensional Materials for Selective Adsorption of Phys. E: Low-Dimens. Syst. Nanostructures 2011, 44, 696−699.
Molecules And nanoclusters. Nat. Mater. 2017, 16, 717−721. (521) Wang, Y.; Meng, G.; Zhang, L.; Liang, C.; Zhang, J. Catalytic
(503) Cai, C.; Ma, Y.; Jeon, J.; Huang, F.; Jia, F.; Lai, S.; Xu, Z.; Wu, Growth of Large-Scale Single-Crystal CdS Nanowires by Physical
C.; Zhao, R.; Hao, Y.; Chen, Y.; Lee, S.; Wang, M. Epitaxial Growth of Evaporation and Their Photoluminescence. Chem. Mater. 2002, 14,
Large-Grain Nise Films by Solid-State Reaction for High-Responsivity 1773−1777.
Photodetector Arrays. Adv. Mater. 2017, 29, 1606180. (522) Wang, M.; Fei, G. T. Synthesis of Tapered CdS Nanobelts and
(504) Shao, Y.; Song, S.; Wu, X.; Qi, J.; Lu, H.; Liu, C.; Zhu, S.; Liu, CdSe Nanowires with Good Optical Property by Hydrogen-Assisted
Z.; Wang, J.; Shi, D.; Du, S.; Wang, Y.; Gao, H. J. Epitaxial Fabrication Thermal Evaporation. Nanoscale Res. Lett. 2009, 4, 1166.
of Two-Dimensional NiSe2 on Ni(111) Substrate. Appl. Phys. Lett. (523) Bierman, M. J.; Lau, Y. K. A.; Jin, S. Hyperbranched PbS and
2017, 111, 113107. PbSe Nanowires and the Effect of Hydrogen Gas on Their Synthesis.
(505) Wang, Y.; Li, L.; Yao, W.; Song, S.; Sun, J. T.; Pan, J.; Ren, X.; Nano Lett. 2007, 7, 2907−2912.
Li, C.; Okunishi, E.; Wang, Y.-Q.; et al. Monolayer PtSe2, a New (524) Peng, H.; Meister, S.; Chan, C. K.; Zhang, X. F.; Cui, Y.
Semiconducting Transition-Metal-Dichalcogenide, Epitaxially Grown Morphology Control of Layer-Structured Gallium Selenide Nano-
by Direct Selenization of Pt. Nano Lett. 2015, 15, 4013−4018. wires. Nano Lett. 2007, 7, 199−203.
(506) Tan, C.; Zhang, H. Epitaxial Growth of Hetero-Nanostruc- (525) Sutter, E.; French, J. S.; Sutter, P. Tunable Layer Orientation
tures Based on Ultrathin Two-Dimensional Nanosheets. J. Am. Chem. and Morphology in Vapor−Liquid−Solid Growth of One-Dimen-
Soc. 2015, 137, 12162−12174. sional GeS vdW Nanostructures. Chem. Mater. 2021, 33, 3980−3988.
(507) Ma, Z.; Wang, S.; Deng, Q.; Hou, Z.; Zhou, X.; Li, X.; Cui, F.; (526) Kwak, J.; Jo, Y.; Song, S.; Kim, J. H.; Kim, S.-Y.; Lee, J.-U.;
Si, H.; Zhai, T.; Xu, H. Epitaxial Growth of Rectangle Shape MoS2 Lee, S.; Park, J.; Kim, K.; Lee, G.-D.; et al. Single-Crystalline
with Highly Aligned Orientation on Twofold Symmetry a-Plane Nanobelts Composed of Transition Metal Ditellurides. Adv. Mater.
Sapphire. Small 2020, 16, 2000596. 2018, 30, 1707260.
(508) Lin, Y.-C.; Jariwala, B.; Bersch, B. M.; Xu, K.; Nie, Y.; Wang, (527) Li, S.; Lin, Y.-C.; Liu, X.-Y.; Hu, Z.; Wu, J.; Nakajima, H.; Liu,
B.; Eichfeld, S. M.; Zhang, X.; Choudhury, T. H.; Pan, Y.; et al. S.; Okazaki, T.; Chen, W.; Minari, T.; et al. Wafer-Scale and
Chem. Rev. 2023, 123, 3329−3442
Deterministic Patterned Growth of Monolayer MoS2 via Vapor− of Γ -InSe and Α, Β, and Γ -In2Se3 on Ε -GaSe. 2D Mater. 2018, 5,
Liquid−Solid Method. Nanoscale 2019, 11, 16122−16129. No. 035026.
(528) Das, S.; Robinson, J. A.; Dubey, M.; Terrones, H.; Terrones, (547) An, B.; Ma, Y.; Zhang, G.; You, C.; Zhang, Y. Controlled
M. Beyond Graphene: Progress in Novel Two-Dimensional Materials Synthesis of Few-Layer SnSe2 by Chemical Vapor Deposition. RSC
and vdW Solids. Annu. Rev. Mater. Res. 2015, 45, 1−27. Adv. 2020, 10, 42157−42163.
(529) Lin, L.; Deng, B.; Sun, J.; Peng, H.; Liu, Z. Bridging the Gap (548) Gong, Y.; Lei, S.; Ye, G.; Li, B.; He, Y.; Keyshar, K.; Zhang, X.;
between Reality and Ideal in Chemical Vapor Deposition Growth of Wang, Q.; Lou, J.; Liu, Z.; et al. Two-Step Growth of Two-
Graphene. Chem. Rev. 2018, 118, 9281−9343. Dimensional WSe2/MoSe2 Heterostructures. Nano Lett. 2015, 15,
(530) Li, H.; Li, Y.; Aljarb, A.; Shi, Y.; Li, L.-J. Epitaxial Growth of 6135−6141.
Two-Dimensional Layered Transition-Metal Dichalcogenides: (549) Li, M.-Y.; Shi, Y.; Cheng, C.-C.; Lu, L.-S.; Lin, Y.-C.; Tang,
Growth Mechanism, Controllability, and Scalability. Chem. Rev. H.-L.; Tsai, M.-L.; Chu, C.-W.; Wei, K.-H.; He, J.-H.; et al. Epitaxial
2018, 118, 6134−6150. Growth of a Monolayer WSe2-MoS2 Lateral P-N Junction with an
(531) Li, F.; Feng, Y.; Li, Z.; Ma, C.; Qu, J.; Wu, X.; Li, D.; Zhang, Atomically Sharp Interface. Science 2015, 349, 524−528.
X.; Yang, T.; He, Y.; et al. Rational Kinetics Control toward Universal (550) Zhou, J.; Tang, B.; Lin, J.; Lv, D.; Shi, J.; Sun, L.; Zeng, Q.;
Growth of 2D Vertically Stacked Heterostructures. Adv. Mater. 2019, Niu, L.; Liu, F.; Wang, X.; et al. Morphology Engineering in
31, 1901351. Monolayer MoS2-WS2 Lateral Heterostructures. Adv. Funct. Mater.
(532) Ye, H.; Zhou, J.; Er, D.; Price, C. C.; Yu, Z.; Liu, Y.; 2018, 28, 1801568.
Lowengrub, J.; Lou, J.; Liu, Z.; Shenoy, V. B. Toward a Mechanistic (551) Fu, Q.; Wang, X.; Zhou, J.; Xia, J.; Zeng, Q.; Lv, D.; Zhu, C.;
Understanding of Vertical Growth of vdW Stacked 2D Materials: A Wang, X.; Shen, Y.; Li, X.; et al. One-Step Synthesis of Metal/
Multiscale Model and Experiments. ACS Nano 2017, 11, 12780− Semiconductor Heterostructure NbS2/MoS2. Chem. Mater. 2018, 30,
12788. 4001−4007.
(533) Huang, C.; Fu, J.; Xiang, M.; Zhang, J.; Zeng, H.; Shao, X. (552) Li, D.; Li, Z.; Chen, P.; Pi, L.; Zuo, N.; Peng, Q.; Zhou, X.;
Single-Layer MoS2 Grown on Atomically Flat SrTiO3 Single Crystal Zhai, T. Two-Dimensional Metal Chalcogenide Heterostructures:
for Enhanced Trionic Luminescence. ACS Nano 2021, 15, 8610− Designed Growth and Emerging Novel Applications. Adv. Mater.
8620. Interfaces 2021, 8, 2100515.
(534) Zhang, Z.; Liu, Y.; Dai, C.; Yang, X.; Chen, P.; Ma, H.; Zhao, (553) Xie, S.; Tu, L.; Han, Y.; Huang, L.; Kang, K.; Lao, K. U.;
B.; Wu, R.; Huang, Z.; Wang, D.; et al. Highly Selective Synthesis of Poddar, P.; Park, C.; Muller, D. A.; DiStasio, R. A.; Park, J. Coherent,
Monolayer or Bilayer WSe2 Single Crystals by Pre-Annealing the Solid Atomically Thin Transition-Metal Dichalcogenide Superlattices with
Precursor. Chem. Mater. 2021, 33, 1307−1313. Engineered. Strain. 2018, 359, 1131−1136.
(535) Pace, S.; Martini, L.; Convertino, D.; Keum, D. H.; Forti, S.; (554) Cheng, M.; Zhao, X.; Zeng, Y.; Wang, P.; Wang, Y.; Wang, T.;
Pezzini, S.; Fabbri, F.; Mišeikis, V.; Coletti, C. Synthesis of Large- Pennycook, S. J.; He, J.; Shi, J. Phase-Tunable Synthesis and Etching-
Scale Monolayer 1T′-MoTe2 and Its Stabilization via Scalable Hbn
Free Transfer of Two-Dimensional Magnetic FeTe. ACS Nano 2021,
Encapsulation. ACS Nano 2021, 15, 4213−4225.
15, 19089−19097.
(536) Li, J.; Zhao, B.; Chen, P.; Wu, R.; Li, B.; Xia, Q.; Guo, G.;
(555) Zou, Z.; Liang, J.; Zhang, X.; Ma, C.; Xu, P.; Yang, X.; Zeng,
Luo, J.; Zang, K.; Zhang, Z.; Ma, H.; Sun, G.; Duan, X.; Duan, X.
Z.; Sun, X.; Zhu, C.; Liang, D.; Zhuang, X.; Li, D.; Pan, A. Liquid-
Synthesis of Ultrathin Metallic MTe2 (M = V, Nb, Ta) Single-
Metal-Assisted Growth of Vertical GaSe/MoS2 P−N Heterojunctions
Crystalline Nanoplates. Adv. Mater. 2018, 30, 1801043.
for Sensitive Self-Driven Photodetectors. ACS Nano 2021, 15,
(537) Wang, D.; Meng, J.; Zhang, X.; Guo, G.; Yin, Z.; Liu, H.;
Cheng, L.; Gao, M.; You, J.; Wang, R. Selective Direct Growth of 10039−10047.
(556) Sun, L.; Yuan, G.; Gao, L.; Yang, J.; Chhowalla, M.;
Atomic Layered HfS2 on Hexagonal Boron Nitride for High
Performance Photodetectors. Chem. Mater. 2018, 30, 3819−3826. Gharahcheshmeh, M. H.; Gleason, K. K.; Choi, Y. S.; Hong, B. H.;
(538) Su, J.; Wang, M.; Li, Y.; Wang, F.; Chen, Q.; Luo, P.; Han, J.; Liu, Z. Chemical Vapour Deposition. Nat. Rev. Methods Primers 2021,
Wang, S.; Li, H.; Zhai, T. Sub-Millimeter-Scale Monolayer P-Type H- 1, 5.
Phase VS2. Adv. Funct. Mater. 2020, 30, 2000240. (557) Kang, M.; Chai, H.-J.; Jeong, H. B.; Park, C.; Jung, I.-y.; Park,
(539) Cui, F.; Zhao, X.; Xu, J.; Tang, B.; Shang, Q.; Shi, J.; Huan, Y.; E.; Ç içek, M. M.; Lee, I.; Bae, B.-S.; Durgun, E.; et al. Low-
Liao, J.; Chen, Q.; Hou, Y.; et al. Controlled Growth and Thickness- Temperature and High-Quality Growth of Bi2O2Se Layered Semi-
Dependent Conduction-Type Transition of 2D Ferrimagnetic Cr2S3 conductors via Cracking Metal−Organic Chemical Vapor Deposition.
Semiconductors. Adv. Mater. 2020, 32, 1905896. ACS Nano 2021, 15, 8715−8723.
(540) Zhang, Y.; Chu, J.; Yin, L.; Shifa, T. A.; Cheng, Z.; Cheng, R.; (558) Cohen, A.; Patsha, A.; Mohapatra, P. K.; Kazes, M.;
Wang, F.; Wen, Y.; Zhan, X.; Wang, Z.; et al. Ultrathin Magnetic 2D Ranganathan, K.; Houben, L.; Oron, D.; Ismach, A. Growth-Etch
Single-Crystal CrSe. Adv. Mater. 2019, 31, 1900056. Metal−Organic Chemical Vapor Deposition Approach of WS2
(541) Yin, L.; Cheng, R.; Wen, Y.; Zhai, B.; Jiang, J.; Wang, H.; Liu, Atomic Layers. ACS Nano 2021, 15, 526−538.
C.; He, J. High-Performance Memristors Based on Ultrathin 2D (559) Hong, W.; Park, C.; Shim, G. W.; Yang, S. Y.; Choi, S.-Y.
Copper Chalcogenides. Adv. Mater. 2022, 34, 2108313. Wafer-Scale Uniform Growth of an Atomically Thin MoS2 Film with
(542) Tan, L.; Liu, Q.; Ding, Y.; Lin, X.; Hu, W.; Cai, M.-Q.; Zhou, Controlled Layer Numbers by Metal−Organic Chemical Vapor
H. Effective Shape-Controlled Synthesis of Gallium Selenide Nano- Deposition. ACS Appl. Mater. Interfaces 2021, 13, 50497−50504.
sheets by Vapor Phase Deposition. Nano Res. 2020, 13, 557−563. (560) Seol, M.; Lee, M.-H.; Kim, H.; Shin, K. W.; Cho, Y.; Jeon, I.;
(543) Yumigeta, K.; Brayfield, C.; Cai, H.; Hajra, D.; Blei, M.; Yang, Jeong, M.; Lee, H.-I.; Park, J.; Shin, H.-J. High-Throughput Growth of
S.; Shen, Y.; Tongay, S. The Synthesis of Competing Phase Gese and Wafer-Scale Monolayer Transition Metal Dichalcogenide via Vertical
GeSe2 2D Layered Materials. RSC Adv. 2020, 10, 38227−38232. Ostwald Ripening. Adv. Mater. 2020, 32, 2003542.
(544) Chang, H.-C.; Tu, C.-L.; Lin, K.-I.; Pu, J.; Takenobu, T.; (561) Shinde, S. M.; Das, T.; Hoang, A. T.; Sharma, B. K.; Chen, X.;
Hsiao, C.-N.; Chen, C.-H. Synthesis of Large-Area InSe Monolayers Ahn, J.-H. Surface-Functionalization-Mediated Direct Transfer of
by Chemical Vapor Deposition. Small 2018, 14, 1802351. Molybdenum Disulfide for Large-Area Flexible Devices. Adv. Funct.
(545) Tang, L.; Teng, C.; Luo, Y.; Khan, U.; Pan, H.; Cai, Z.; Zhao, Mater. 2018, 28, 1706231.
Y.; Liu, B.; Cheng, H.-M. Confined vdW Epitaxial Growth of Two- (562) McDonnell, S.; Addou, R.; Buie, C.; Wallace, R. M.; Hinkle,
Dimensional Large Single-Crystal In2Se3 for Flexible Broadband C. L. Defect-Dominated Doping and Contact Resistance in MoS2.
Photodetectors. Research 2019, 2019, 2763704. ACS Nano 2014, 8, 2880−2888.
(546) Balakrishnan, N.; Steer, E. D.; Smith, E. F.; Kudrynskyi, Z. R.; (563) Addou, R.; McDonnell, S.; Barrera, D.; Guo, Z.; Azcatl, A.;
Kovalyuk, Z. D.; Eaves, L.; Patanè, A.; Beton, P. H. Epitaxial Growth Wang, J.; Zhu, H.; Hinkle, C. L.; Quevedo-Lopez, M.; Alshareef, H.
Chem. Rev. 2023, 123, 3329−3442
N.; et al. Impurities and Electronic Property Variations of Natural Covalently Bonded 2D Layered Materials by Self-Intercalation.
MoS2 Crystal Surfaces. ACS Nano 2015, 9, 9124−9133. Nature 2020, 581, 171−177.
(564) Addou, R.; Wallace, R. M. Surface Analysis of WSe2 Crystals: (581) Liang, Y.; Chen, Y.; Sun, Y.; Xu, S.; Wu, J.; Tan, C.; Xu, X.;
Spatial and Electronic Variability. ACS Appl. Mater. Interfaces 2016, 8, Yuan, H.; Yang, L.; Chen, Y.; et al. Molecular Beam Epitaxy and
26400−26406. Electronic Structure of Atomically Thin Oxyselenide Films. Adv.
(565) Schlom, D. G.; Chen, L.-Q.; Pan, X.; Schmehl, A.; Zurbuchen, Mater. 2019, 31, 1901964.
M. A. A Thin Film Approach to Engineering Functionality into (582) Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.;
Oxides. J. Am. Ceram. Soc. 2008, 91, 2429−2454. Zhang, Y.; Dubonos, S. V.; Grigorieva, I. V.; Firsov, A. A. Electric
(566) Liang, Y.; Li, W.; Zhang, S.; Lin, C.; Li, C.; Yao, Y.; Li, Y.; Field Effect in Atomically Thin Carbon Films. Science 2004, 306,
Yang, H.; Guo, J. Homoepitaxial SrTiO3(111) Film with High 666−669.
Dielectric Performance and Atomically Well-Defined Surface. Sci. Rep. (583) Li, H.; Wu, J.; Yin, Z.; Zhang, H. Preparation and Applications
2015, 5, 10634. of Mechanically Exfoliated Single-Layer and Multilayer MoS2 and
(567) He, Q.; Li, P.; Wu, Z.; Yuan, B.; Luo, Z.; Yang, W.; Liu, J.; WSe2 Nanosheets. Acc. Chem. Res. 2014, 47, 1067−1075.
Cao, G.; Zhang, W.; Shen, Y.; et al. Molecular Beam Epitaxy Scalable (584) He, S.; He, J.; Zhang, W.; Zhao, L.; Liu, D.; Liu, X.; Mou, D.;
Growth of Wafer-Scale Continuous Semiconducting Monolayer Ou, Y.-B.; Wang, Q.-Y.; Li, Z.; et al. Phase Diagram and Electronic
MoTe2 on Inert Amorphous Dielectrics. Adv. Mater. 2019, 31, Indication of High-Temperature Superconductivity at 65 K in Single-
1901578. Layer Fese Films. Nat. Mater. 2013, 12, 605−610.
(568) Chua, R.; Zhou, J.; Yu, X.; Yu, W.; Gou, J.; Zhu, R.; Zhang, L.; (585) Zhang, C.; Wang, C.; Yang, F.; Huang, J.-K.; Li, L.-J.; Yao, W.;
Liu, M.; Breese, M. B. H.; Chen, W.; et al. Room Temperature Ji, W.; Shih, C.-K. Engineering Point-Defect States in Monolayer
Ferromagnetism of Monolayer Chromium Telluride with Perpendic- WSe2. ACS Nano 2019, 13, 1595−1602.
ular Magnetic Anisotropy. Adv. Mater. 2021, 33, 2103360. (586) Ezawa, M. Valley-Polarized Metals and Quantum Anomalous
(569) Zhang, L.; Yang, T.; He, X.; Zhang, W.; Vinai, G.; Tang, C. S.; Hall Effect in Silicene. Phys. Rev. Lett. 2012, 109, No. 055502.
Yin, X.; Torelli, P.; Feng, Y. P.; Wong, P. K. J.; et al. Molecular Beam (587) Jiang, S.; Li, L.; Wang, Z.; Mak, K. F.; Shan, J. Controlling
Epitaxy of Two-Dimensional Vanadium-Molybdenum Diselenide Magnetism in 2D CrI3 by Electrostatic Doping. Nat. Nanotechnol.
Alloys. ACS Nano 2020, 14, 11140−11149. 2018, 13, 549−553.
(570) Lasek, K.; Coelho, P. M.; Zberecki, K.; Xin, Y.; Kolekar, S. K.; (588) Huang, Y.; Sutter, E.; Shi, N. N.; Zheng, J.; Yang, T.; Englund,
Li, J.; Batzill, M. Molecular Beam Epitaxy of Transition Metal (Ti-, V-, D.; Gao, H.-J.; Sutter, P. Reliable Exfoliation of Large-Area High-
and Cr-) Tellurides: From Monolayer Ditellurides to Multilayer Self- Quality Flakes of Graphene and Other Two-Dimensional Materials.
Intercalation Compounds. ACS Nano 2020, 14, 8473−8484. ACS Nano 2015, 9, 10612−10620.
(571) Wong, P. K. J.; Zhang, W.; Bussolotti, F.; Yin, X.; Herng, T. S.; (589) Radisavljevic, B.; Radenovic, A.; Brivio, J.; Giacometti, V.; Kis,
Zhang, L.; Huang, Y. L.; Vinai, G.; Krishnamurthi, S.; Bukhvalov, D. A. Single-Layer MoS2 Transistors. Nat. Nanotechnol. 2011, 6, 147−
W.; et al. Evidence of Spin Frustration in a Vanadium Diselenide 150.
Monolayer Magnet. Adv. Mater. 2019, 31, 1901185. (590) McGuire, M. A.; Dixit, H.; Cooper, V. R.; Sales, B. C.
(572) Poh, S. M.; Tan, S. J. R.; Zhao, X.; Chen, Z.; Abdelwahab, I.; Coupling of Crystal Structure and Magnetism in the Layered,
Fu, D.; Xu, H.; Bao, Y.; Zhou, W.; Loh, K. P. Large Area Synthesis of Ferromagnetic Insulator CrI3. Chem. Mater. 2015, 27, 612−620.
1D-MoSe2 Using Molecular Beam Epitaxy. Adv. Mater. 2017, 29, (591) Jiang, D.; Hu, T.; You, L.; Li, Q.; Li, A.; Wang, H.; Mu, G.;
1605641. Chen, Z.; Zhang, H.; Yu, G.; et al. High-Tc Superconductivity in
(573) Barja, S.; Wickenburg, S.; Liu, Z.-F.; Zhang, Y.; Ryu, H.; Ultrathin Bi2Sr2CaCu2O8+x Down to Half-Unit-Cell Thickness by
Ugeda, Miguel M.; Hussain, Z.; Shen, Z.-X.; Mo, S.-K.; Wong, E.; Protection with Graphene. Nat. Commun. 2014, 5, 5708.
et al. Charge Density Wave Order in 1D Mirror Twin Boundaries of (592) Tang, S.; Zhang, C.; Wong, D.; Pedramrazi, Z.; Tsai, H.-Z.;
Single-Layer MoSe2. Nat. Phys. 2016, 12, 751−756. Jia, C.; Moritz, B.; Claassen, M.; Ryu, H.; Kahn, S.; et al. Quantum
(574) Seredyński, B.; Ogorzałek, Z.; Zajkowska, W.; Bożek, R.; Spin Hall State in Monolayer 1T’-WTe2. Nat. Phys. 2017, 13, 683−
Tokarczyk, M.; Suffczyński, J.; Kret, S.; Sadowski, J.; Gryglas- 687.
Borysiewicz, M.; Pacuski, W. Molecular Beam Epitaxy of a 2D (593) Zhang, Y.; Lee, J. J.; Moore, R. G.; Li, W.; Yi, M.; Hashimoto,
Material Nearly Lattice Matched to a 3D Substrate: Nite2 on Gaas. M.; Lu, D. H.; Devereaux, T. P.; Lee, D. H.; Shen, Z. X.
Cryst. Growth Des. 2021, 21, 5773−5779. Superconducting Gap Anisotropy in Monolayer Fese Thin Film.
(575) Wang, Q.; Wang, F.; Li, J.; Wang, Z.; Zhan, X.; He, J. Low- Phys. Rev. Lett. 2016, 117, 117001.
Dimensional Topological Crystalline Insulators. Small 2015, 11, (594) Xu, C.; Mao, J.; Guo, X.; Yan, S.; Chen, Y.; Lo, T. W.; Chen,
4613−4624. C.; Lei, D.; Luo, X.; Hao, J.; et al. Two-Dimensional Ferroelasticity in
(576) Ji, J.; Song, X.; Liu, J.; Yan, Z.; Huo, C.; Zhang, S.; Su, M.; vdW Beta’-In2Se3. Nat. Commun. 2021, 12, 3665.
Liao, L.; Wang, W.; Ni, Z.; et al. Two-Dimensional Antimonene (595) Geremew, A. K.; Rumyantsev, S.; Bloodgood, M. A.; Salguero,
Single Crystals Grown by vdW Epitaxy. Nat. Commun. 2016, 7, T. T.; Balandin, A. A. Unique Features of the Generation-
13352. Recombination Noise in Quasi-One-Dimensional vdW Nanoribbons.
(577) Vishwanath, S.; Liu, X.; Rouvimov, S.; Mende, P. C.; Azcatl, Nanoscale 2018, 10, 19749−19756.
A.; McDonnell, S.; Wallace, R. M.; Feenstra, R. M.; Furdyna, J. K.; (596) Kim, B. J.; Jeong, B. J.; Oh, S.; Chae, S.; Choi, K. H.; Nasir, T.;
Jena, D.; et al. Comprehensive Structural and Optical Character- Lee, S. H.; Kim, K. W.; Lim, H. K.; Choi, I. J.; et al. Exfoliation and
ization of MBE Grown MoSe2 on Graphite, CaF2 and Graphene. 2D Characterization of V2Se9 Atomic Crystals. Nanomaterials (Basel)
Mater. 2015, 2, No. 024007. 2018, 8, 737.
(578) Roy, A.; Movva, H. C. P.; Satpati, B.; Kim, K.; Dey, R.; Rai, A.; (597) Kargar, F.; Krayev, A.; Wurch, M.; Ghafouri, Y.; Debnath, T.;
Pramanik, T.; Guchhait, S.; Tutuc, E.; Banerjee, S. K. Structural and Wickramaratne, D.; Salguero, T. T.; Lake, R. K.; Bartels, L.; Balandin,
Electrical Properties of MoTe2 and MoSe2 Grown by Molecular Beam A. A. Metallic vs. Semiconducting Properties of Quasi-One-Dimen-
Epitaxy. ACS Appl. Mater. Interfaces 2016, 8, 7396−7402. sional Tantalum Selenide vdW Nanoribbons. Nanoscale 2022, 14,
(579) Klein, A.; Tiefenbacher, S.; Eyert, V.; Pettenkofer, C.; 6133−6143.
Jaegermann, W. Electronic Band Structure of Single-Crystal and (598) Zhang, Y.; Chen, X.; Zhang, H.; Hu, S.; Zhao, G.; Zhang, M.;
Single-Layer WS2: Influence of Interlayer vdW Interactions. Phys. Rev. Qin, W.; Wang, Z.; Huang, X.; Wang, J. Facile Exfoliation for High-
B 2001, 64, 205416. Quality Molybdenum Disulfide Nanoflakes and Relevant Field-Effect
(580) Zhao, X.; Song, P.; Wang, C.; Riis-Jensen, A. C.; Fu, W.; Transistors Developed with Thermal Treatment. Front. Chem. 2021,
Deng, Y.; Wan, D.; Kang, L.; Ning, S.; Dan, J.; et al. Engineering 9, 650901.
Chem. Rev. 2023, 123, 3329−3442
(599) Huang, Z.; Alharbi, A.; Mayer, W.; Cuniberto, E.; Taniguchi, (615) Li, J.; Liu, W.; Chen, C.; Zhao, X.; Qiu, Z.; Xu, H.; Sheng, F.;
T.; Watanabe, K.; Shabani, J.; Shahrjerdi, D. Versatile Construction of Hu, Q.; Zheng, Y.; Lin, M.; et al. High Yield Electrochemical
vdW Heterostructures Using a Dual-Function Polymeric Film. Nat. Exfoliation Synthesis of Tin Selenide Quantum Dots for High-
Commun. 2020, 11, 3029. Performance Lithium-Ion Batteries. J. Mater. Chem. A 2019, 7,
(600) Magda, G. Z.; Peto, J.; Dobrik, G.; Hwang, C.; Biro, L. P.; 23958−23963.
Tapaszto, L. Exfoliation of Large-Area Transition Metal Chalcogenide (616) Zeng, Z.; Tan, C.; Huang, X.; Bao, S.; Zhang, H. Growth of
Single Layers. Sci. Rep. 2015, 5, 14714. Noble Metal Nanoparticles on Single-Layer TiS2 and TaS2 Nano-
(601) Velicky, M.; Donnelly, G. E.; Hendren, W. R.; McFarland, S.; sheets for Hydrogen Evolution Reaction. Energy Environ. Sci. 2014, 7,
Scullion, D.; DeBenedetti, W. J. I.; Correa, G. C.; Han, Y.; Wain, A. J.; 797−803.
Hines, M. A.; et al. Mechanism of Gold-Assisted Exfoliation of (617) Wang, M.; Xu, X.; Ge, Y.; Dong, P.; Baines, R.; Ajayan, P. M.;
Centimeter-Sized Transition-Metal Dichalcogenide Monolayers. ACS Ye, M.; Shen, J. Surface Tension Components Ratio: An Efficient
Nano 2018, 12, 10463−10472. Parameter for Direct Liquid Phase Exfoliation. ACS Appl. Mater.
(602) Gramling, H. M.; Towle, C. M.; Desai, S. B.; Sun, H.; Lewis, Interfaces 2017, 9, 9168−9175.
E. C.; Nguyen, V. D.; Ager, J. W.; Chrzan, D.; Yeatman, E. M.; Javey, (618) Shen, J.; Wu, J.; Wang, M.; Dong, P.; Xu, J.; Li, X.; Zhang, X.;
A.; et al. Spatially Precise Transfer of Patterned Monolayer WS2 and Yuan, J.; Wang, X.; Ye, M.; et al. Surface Tension Components Based
MoS2 with Features Larger Than 104 mm2 Directly from Multilayer Selection of Cosolvents for Efficient Liquid Phase Exfoliation of 2D
Sources. ACS Appl. Electron. Mater. 2019, 1, 407−416. Materials. Small 2016, 12, 2741−2749.
(603) Nguyen, V.; Gramling, H.; Towle, C.; Li, W.; Lien, D.-H.; (619) Halim, U.; Zheng, C. R.; Chen, Y.; Lin, Z.; Jiang, S.; Cheng,
Kim, H.; Chrzan, D. C.; Javey, A.; Xu, K.; Ager, J.; et al. Deterministic R.; Huang, Y.; Duan, X. A Rational Design of Cosolvent Exfoliation of
Assembly of Arrays of Lithographically Defined WS2 and MoS2 Layered Materials by Directly Probing Liquid-Solid Interaction. Nat.
Monolayer Features Directly from Multilayer Sources into vdW Commun. 2013, 4, 2213.
Heterostructures. J. Micro Nano-Manuf. 2019, 7, No. 041006. (620) Manna, K.; Hsieh, C.-Y.; Lo, S.-C.; Li, Y.-S.; Huang, H.-N.;
(604) Shim, J.; Bae, S.-H.; Kong, W.; Lee, D.; Qiao, K.; Nezich, D.; Chiang, W.-H. Graphene and Graphene-Analogue Nanosheets
Park Yong, J.; Zhao, R.; Sundaram, S.; Li, X.; et al. Controlled Crack Produced by Efficient Water-Assisted Liquid Exfoliation of Layered
Propagation for Atomic Precision Handling of Wafer-Scale Two- Materials. Carbon 2016, 105, 551−555.
Dimensional Materials. Science 2018, 362, 665−670. (621) Mansukhani, N. D.; Guiney, L. M.; Kim, P. J.; Zhao, Y.;
(605) Zhang, H.; Chen, X.; Wang, J.; Zhang, Y.; Wang, G.; Mao, Y.; Alducin, D.; Ponce, A.; Larios, E.; Yacaman, M. J.; Hersam, M. C.
Wang, Z.; Zhang, Y.; Gu, R.; Zhao, M. Solvent-Assisted Exfoliation for High-Concentration Aqueous Dispersions of Nanoscale 2D Materials
High-Quality Molybdenum Disulfide Nanoflakes and Relevant Field- Using Nonionic, Biocompatible Block Copolymers. Small 2016, 12,
Effect Transistors. J. Mater. Sci. 2022, 57, 11215−11225. 294−300.
(606) Paolucci, V.; D’Olimpio, G.; Lozzi, L.; Mio, A. M.; Ottaviano, (622) Coleman, J. N.; Lotya, M.; O’Neill, A.; Bergin Shane, D.; King
Paul, J.; Khan, U.; Young, K.; Gaucher, A.; De, S.; Smith Ronan, J.;
L.; Nardone, M.; Nicotra, G.; Le-Cornec, P.; Cantalini, C.; Politano,
et al. Two-Dimensional Nanosheets Produced by Liquid Exfoliation
A. Sustainable Liquid-Phase Exfoliation of Layered Materials with
of Layered Materials. Science 2011, 331, 568−571.
Nontoxic Polarclean Solvent. ACS Sustainable Chem. Eng. 2020, 8,
(623) Hernandez, Y.; Nicolosi, V.; Lotya, M.; Blighe, F. M.; Sun, Z.;
18830−18840.
De, S.; McGovern, I. T.; Holland, B.; Byrne, M.; Gun’Ko, Y. K.; et al.
(607) Prabukumar, C.; Sadiq, M. M. J.; Bhat, D. K.; Bhat, K. U.
High-Yield Production of Graphene by Liquid-Phase Exfoliation of
Effect of Solvent on the Morphology of MoS2 Nanosheets Prepared
Graphite. Nat. Nanotechnol. 2008, 3, 563−568.
by Ultrasonication-Assisted Exfoliation. AIP Conf. Proc. 2018, 1943, (624) Lotya, M.; Hernandez, Y.; King, P. J.; Smith, R. J.; Nicolosi,
No. 020084. V.; Karlsson, L. S.; Blighe, F. M.; De, S.; Wang, Z.; McGovern, I. T.;
(608) Oh, N. K.; Lee, H. J.; Choi, K.; Seo, J.; Kim, U.; Lee, J.; Choi, et al. Liquid Phase Production of Graphene by Exfoliation of Graphite
Y.; Jung, S.; Lee, J. H.; Shin, H. S.; et al. Nafion-Mediated Liquid- in Surfactant/Water Solutions. J. Am. Chem. Soc. 2009, 131, 3611−
Phase Exfoliation of Transition Metal Dichalcogenides and Direct 3620.
Application in Hydrogen Evolution Reaction. Chem. Mater. 2018, 30, (625) Cunningham, G.; Lotya, M.; Cucinotta, C. S.; Sanvito, S.;
4658−4666. Bergin, S. D.; Menzel, R.; Shaffer, M. S. P.; Coleman, J. N. Solvent
(609) Zhao, X.; Ma, X.; Sun, J.; Li, D.; Yang, X. Enhanced Catalytic Exfoliation of Transition Metal Dichalcogenides: Dispersibility of
Activities of Surfactant-Assisted Exfoliated WS2 Nanodots for Exfoliated Nanosheets Varies Only Weakly between Compounds.
Hydrogen Evolution. ACS Nano 2016, 10, 2159−2166. ACS Nano 2012, 6, 3468−3480.
(610) Narayan, R.; Lim, J.; Jeon, T.; Li, D. J.; Kim, S. O. Perylene (626) Du, W.; Jiang, X.; Zhu, L. From Graphite to Graphene: Direct
Tetracarboxylate Surfactant Assisted Liquid Phase Exfoliation of Liquid-Phase Exfoliation of Graphite to Produce Single- and Few-
Graphite into Graphene Nanosheets with Facile Re-Dispersibility in Layered Pristine Graphene. J. Mater. Chem. A 2013, 1, 10592−10606.
Aqueous/Organic Polar Solvents. Carbon 2017, 119, 555−568. (627) Hernandez, Y.; Lotya, M.; Rickard, D.; Bergin, S. D.;
(611) Zhu, X.; Su, Z.; Wu, C.; Cong, H.; Ai, X.; Yang, H.; Qian, J. Coleman, J. N. Measurement of Multicomponent Solubility
Exfoliation of MoS2 Nanosheets Enabled by a Redox-Potential- Parameters for Graphene Facilitates Solvent Discovery. Langmuir
Matched Chemical Lithiation Reaction. Nano Lett. 2022, 22, 2956− 2010, 26, 3208−3213.
2963. (628) Bergin, S. D.; Sun, Z.; Rickard, D.; Streich, P. V.; Hamilton, J.
(612) Zheng, J.; Zhang, H.; Dong, S.; Liu, Y.; Tai Nai, C.; Suk Shin, P.; Coleman, J. N. Multicomponent Solubility Parameters for Single-
H.; Young Jeong, H.; Liu, B.; Ping Loh, K. High Yield Exfoliation of Walled Carbon Nanotube−Solvent Mixtures. ACS Nano 2009, 3,
Two-Dimensional Chalcogenides Using Sodium Naphthalenide. Nat. 2340−2350.
Commun. 2014, 5, 2995. (629) Kim, S.; Park, W.; Kim, D.; Kang, J.; Lee, J.; Jang, H. Y.; Song,
(613) Tan, S. M.; Sofer, Z.; Luxa, J.; Pumera, M. Aromatic- S. H.; Cho, B.; Lee, D. Novel Exfoliation of High-Quality 2H-MoS2
Exfoliated Transition Metal Dichalcogenides: Implications for Nanoflakes for Solution-Processed Photodetector. Nanomaterials
Inherent Electrochemistry and Hydrogen Evolution. ACS Catal. 2020, 10, 1045.
2016, 6, 4594−4607. (630) Nakayasu, Y.; Yasui, Y.; Taniki, R.; Oizumi, K.; Kobayashi, H.;
(614) Yang, R.; Mei, L.; Zhang, Q.; Fan, Y.; Shin, H. S.; Voiry, D.; Nagamura, N.; Tomai, T.; Honma, I. One-Pot Rapid Synthesis of
Zeng, Z. High-Yield Production of Mono- or Few-Layer Transition Mo(S,Se)2 Nanosheets on Graphene for Highly Efficient Hydrogen
Metal Dichalcogenide Nanosheets by an Electrochemical Lithium Ion Evolution. ACS Sustainable Chem. Eng. 2018, 6, 11502−11510.
Intercalation-Based Exfoliation Method. Nat. Protoc. 2022, 17, 358− (631) Coleman, J. N. Liquid-Phase Exfoliation of Nanotubes and
377. Graphene. Adv. Funct. Mater. 2009, 19, 3680−3695.
Chem. Rev. 2023, 123, 3329−3442
(632) Tao, H.; Zhang, Y.; Gao, Y.; Sun, Z.; Yan, C.; Texter, J. (650) Shuai, J.; Yoo, H. D.; Liang, Y.; Li, Y.; Yao, Y.; Grabow, L. C.
Scalable Exfoliation and Dispersion of Two-Dimensional Materials - Density Functional Theory Study of Li, Na, and Mg Intercalation and
an Update. Phys. Chem. Chem. Phys. 2017, 19, 921−960. Diffusion in MoS2 with Controlled Interlayer Spacing. Mater. Res.
(633) Schiettecatte, P.; Rousaki, A.; Vandenabeele, P.; Geiregat, P.; Express 2016, 3, No. 064001.
Hens, Z. Liquid-Phase Exfoliation of Rhenium Disulfide by Solubility (651) Eng, A. Y. S.; Ambrosi, A.; Sofer, Z.; Š imek, P.; Pumera, M.
Parameter Matching. Langmuir 2020, 36, 15493−15500. Electrochemistry of Transition Metal Dichalcogenides: Strong
(634) Owens, D. K. Some Thermodynamic Aspects of Polymer Dependence on the Metal-to-Chalcogen Composition and Exfoliation
Adhesion. J. Appl. Polym. Sci. 1970, 14, 1725−1730. Method. ACS Nano 2014, 8, 12185−12198.
(635) Baraghani, S.; Abourahma, J.; Barani, Z.; Mohammadzadeh, (652) Ambrosi, A.; Sofer, Z.; Pumera, M. Lithium Intercalation
A.; Sudhindra, S.; Lipatov, A.; Sinitskii, A.; Kargar, F.; Balandin, A. A. Compound Dramatically Influences the Electrochemical Properties of
Printed Electronic Devices with Inks of TiS3 Quasi-One-Dimensional Exfoliated MoS2. Small 2015, 11, 605−612.
vdW Material. ACS Appl. Mater. Interfaces 2021, 13, 47033−47042. (653) Murphy, D. W.; Di Salvo, F. J.; Hull, G. W.; Waszczak, J. V.
(636) Oh, S.; Chae, S.; Kim, B. J.; Siddiqa, A. J.; Choi, K. H.; Jang, Convenient Preparation and Physical Properties of Lithium
W. S.; Lee, K. H.; Kim, H. Y.; Lee, D. K.; Kim, Y. M.; et al. Inorganic Intercalation Compounds of Group 4b and 5b Layered Transition
Molecular Chain Nb2Se9: Synthesis of Bulk Crystal and One-Atom- Metal Dichalcogenides. Inorg. Chem. 1976, 15, 17−21.
Thick Level Exfoliation. Phys. Status Solidi RRL 2018, 12, 1800451. (654) Samadi, M.; Sarikhani, N.; Zirak, M.; Zhang, H.; Zhang, H. L.;
(637) Yang, L.; Tao, Y.; Zhu, Y.; Akter, M.; Wang, K.; Pan, Z.; Zhao, Moshfegh, A. Z. Group 6 Transition Metal Dichalcogenide Nano-
Y.; Zhang, Q.; Xu, Y. Q.; Chen, R.; et al. Observation of materials: Synthesis, Applications and Future Perspectives. Nanoscale
Superdiffusive Phonon Transport in Aligned Atomic Chains. Nat. Horiz. 2018, 3, 90−204.
Nanotechnol. 2021, 16, 764−768. (655) Liang, Y.; Yoo, H. D.; Li, Y.; Shuai, J.; Calderon, H. A.; Robles
(638) Barani, Z.; Kargar, F.; Ghafouri, Y.; Ghosh, S.; Godziszewski, Hernandez, F. C.; Grabow, L. C.; Yao, Y. Interlayer-Expanded
K.; Baraghani, S.; Yashchyshyn, Y.; Cywinski, G.; Rumyantsev, S.; Molybdenum Disulfide Nanocomposites for Electrochemical Magne-
Salguero, T. T.; et al. Electrically Insulating Flexible Films with Quasi- sium Storage. Nano Lett. 2015, 15, 2194−2202.
1D vdW Fillers as Efficient Electromagnetic Shields in the GHz and (656) Fan, X.; Xu, P.; Zhou, D.; Sun, Y.; Li, Y. C.; Nguyen, M. A.;
Sub-THz Frequency Bands. Adv. Mater. 2021, 33, 2007286. Terrones, M.; Mallouk, T. E. Fast and Efficient Preparation of
(639) Barani, Z.; Kargar, F.; Ghafouri, Y.; Baraghani, S.; Sudhindra, Exfoliated 2H MoS2 Nanosheets by Sonication-Assisted Lithium
S.; Mohammadzadeh, A.; Salguero, T. T.; Balandin, A. A. Electro- Intercalation and Infrared Laser-Induced 1T to 2H Phase Reversion.
magnetic-Polarization-Selective Composites with Quasi-1D vdW Nano Lett. 2015, 15, 5956−5960.
Fillers: Nanoscale Material Functionality That Mimics Macroscopic (657) Zhang, P.; Yang, S.; Pineda-Gómez, R.; Ibarlucea, B.; Ma, J.;
Systems. ACS Appl. Mater. Interfaces 2021, 13, 21527−21533. Lohe, M. R.; Akbar, T. F.; Baraban, L.; Cuniberti, G.; Feng, X.
(640) May, P.; Khan, U.; Hughes, J. M.; Coleman, J. N. Role of
Electrochemically Exfoliated High-Quality 2H-MoS2 for Multiflake
Solubility Parameters in Understanding the Steric Stabilization of
Thin Film Flexible Biosensors. Small 2019, 15, 1901265.
Exfoliated Two-Dimensional Nanosheets by Adsorbed Polymers. J.
(658) Pritts, W. A.; Peters, D. G. Electrochemical Reduction of 1,4-
Phys. Chem. C 2012, 116, 11393−11400.
Dihalobutanes at Carbon Cathodes in Dimethylformamide. J.
(641) Hu, C. X.; Shin, Y.; Read, O.; Casiraghi, C. Dispersant-
Electroanal. Chem. 1995, 380, 147−160.
Assisted Liquid-Phase Exfoliation of 2D Materials Beyond Graphene.
(659) Wu, M.; Zhan, J.; Wu, K.; Li, Z.; Wang, L.; Geng, B.; Wang,
Nanoscale 2021, 13, 460−484.
L.; Pan, D. Metallic 1T MoS2 Nanosheet Arrays Vertically Grown on
(642) Varrla, E.; Backes, C.; Paton, K. R.; Harvey, A.; Gholamvand,
Z.; McCauley, J.; Coleman, J. N. Large-Scale Production of Size- Activated Carbon Fiber Cloth for Enhanced Li-Ion Storage
Controlled MoS2 Nanosheets by Shear Exfoliation. Chem. Mater. Performance. J. Mater. Chem. A 2017, 5, 14061−14069.
2015, 27, 1129−1139. (660) Jiang, H.; Ren, D.; Wang, H.; Hu, Y.; Guo, S.; Yuan, H.; Hu,
(643) Guardia, L.; Paredes, J. I.; Rozada, R.; Villar-Rodil, S.; P.; Zhang, L.; Li, C. 2D Monolayer MoS2−Carbon Interoverlapped
Martínez-Alonso, A.; Tascón, J. M. D. Production of Aqueous Superstructure: Engineering Ideal Atomic Interface for Lithium Ion
Dispersions of Inorganic Graphene Analogues by Exfoliation and Storage. Adv. Mater. 2015, 27, 3687−3695.
Stabilization with Non-Ionic Surfactants. RSC Adv. 2014, 4, 14115− (661) Abun, A.; Huang, B.-R.; Saravanan, A.; Kathiravan, D.; Hong,
14127. P.-D. Effect of Pmma on the Surface of Exfoliated MoS2 Nanosheets
(644) Guan, G.; Zhang, S.; Liu, S.; Cai, Y.; Low, M.; Teng, C. P.; and Their Highly Enhanced Ammonia Gas Sensing Properties at
Phang, I. Y.; Cheng, Y.; Duei, K. L.; Srinivasan, B. M.; et al. Protein Room Temperature. J. Alloys Compd. 2020, 832, 155005.
Induces Layer-by-Layer Exfoliation of Transition Metal Dichalcoge- (662) Zhang, S.; Wang, J.; Torad, N. L.; Xia, W.; Aslam, M. A.;
nides. J. Am. Chem. Soc. 2015, 137, 6152−6155. Kaneti, Y. V.; Hou, Z.; Ding, Z.; Da, B.; Fatehmulla, A.; et al. Rational
(645) Zhang, X.; Lai, Z.; Liu, Z.; Tan, C.; Huang, Y.; Li, B.; Zhao, Design of Nanoporous MoS2/VS2 Heteroarchitecture for Ultrahigh
M.; Xie, L.; Huang, W.; Zhang, H. A Facile and Universal Top-Down Performance Ammonia Sensors. Small 2020, 16, 1901718.
Method for Preparation of Monodisperse Transition-Metal Dichalco- (663) Tomer, V. K.; Malik, R.; Chaudhary, V.; Mishra, Y. K.; Kienle,
genide Nanodots. Angew. Chem., Int. Ed. 2015, 54, 5425−5428. L.; Ahuja, R.; Lin, L. Superior Visible Light Photocatalysis and Low-
(646) Wang, D.; Song, L.; Zhou, K.; Yu, X.; Hu, Y.; Wang, J. Operating Temperature Vocs Sensor Using Cubic Ag(0)-MoS2
Anomalous Nano-Barrier Effects of Ultrathin Molybdenum Disulfide Loaded g-CN 3D Porous Hybrid. Appl. Mater. Today 2019, 16,
Nanosheets for Improving the Flame Retardance of Polymer 193−203.
Nanocomposites. J. Mater. Chem. A 2015, 3, 14307−14317. (664) Ahmed, S.; Yi, J. Two-Dimensional Transition Metal
(647) Xuan, D.; Zhou, Y.; Nie, W.; Chen, P. Sodium Alginate- Dichalcogenides and Their Charge Carrier Mobilities in Field-Effect
Assisted Exfoliation of MoS2 and Its Reinforcement in Polymer Transistors. Nano-Micro Lett. 2017, 9, 50.
Nanocomposites. Carbohydr. Polym. 2017, 155, 40−48. (665) Chen, X.; Liu, C.; Mao, S. Environmental Analysis with 2D
(648) Zhao, M.; Chang, M. J.; Wang, Q.; Zhu, Z. T.; Zhai, X. P.; Transition-Metal Dichalcogenide-Based Field-Effect Transistors.
Zirak, M.; Moshfegh, A. Z.; Song, Y. L.; Zhang, H. L. Unexpected Nano-Micro Lett. 2020, 12, 95.
Optical Limiting Properties from MoS2 Nanosheets Modified by a (666) Gupta, U.; Rao, C. N. R. Hydrogen Generation by Water
Semiconductive Polymer. Chem. Commun. 2015, 51, 12262−12265. Splitting Using MoS2 and Other Transition Metal Dichalcogenides.
(649) Jeong, S.; Yoo, D.; Ahn, M.; Miro, P.; Heine, T.; Cheon, J. Nano Energy 2017, 41, 49−65.
Tandem Intercalation Strategy for Single-Layer Nanosheets as an (667) Hu, Z.; Wu, Z.; Han, C.; He, J.; Ni, Z.; Chen, W. Two-
Effective Alternative to Conventional Exfoliation Processes. Nat. Dimensional Transition Metal Dichalcogenides: Interface and Defect
Commun. 2015, 6, 5763. Engineering. Chem. Soc. Rev. 2018, 47, 3100−3128.
Chem. Rev. 2023, 123, 3329−3442
(668) Tedstone, A. A.; Lewis, D. J.; O’Brien, P. Synthesis, Properties, Aspect Ratio Control of Nanoribbons. Chem. Mater. 2007, 19, 3861−
and Applications of Transition Metal-Doped Layered Transition 3863.
Metal Dichalcogenides. Chem. Mater. 2016, 28, 1965−1974. (687) Li, Z.; Peng, X. Size/Shape-Controlled Synthesis of Colloidal
(669) Voiry, D.; Mohite, A.; Chhowalla, M. Phase Engineering of CdSe Quantum Disks: Ligand and Temperature Effects. J. Am. Chem.
Transition Metal Dichalcogenides. Chem. Soc. Rev. 2015, 44, 2702− Soc. 2011, 133, 6578−6586.
2712. (688) Almeida, G.; Dogan, S.; Bertoni, G.; Giannini, C.; Gaspari, R.;
(670) Jiao, Y.; Hafez, A. M.; Cao, D.; Mukhopadhyay, A.; Ma, Y.; Perissinotto, S.; Krahne, R.; Ghosh, S.; Manna, L. Colloidal
Zhu, H. Metallic MoS2 for High Performance Energy Storage and Monolayer Β-In2Se3 Nanosheets with High Photoresponsivity. J.
Energy Conversion. Small 2018, 14, 1800640. Am. Chem. Soc. 2017, 139, 3005−3011.
(671) Kang, J.; Sangwan, V. K.; Wood, J. D.; Hersam, M. C. (689) Wang, S.; Rong, Y.; Fan, Y.; Pacios, M.; Bhaskaran, H.; He, K.;
Solution-Based Processing of Monodisperse Two-Dimensional Nano- Warner, J. H. Shape Evolution of Monolayer MoS2 Crystals Grown by
materials. Acc. Chem. Res. 2017, 50, 943−951. Chemical Vapor Deposition. Chem. Mater. 2014, 26, 6371−6379.
(672) Backes, C.; Smith, R. J.; McEvoy, N.; Berner, N. C.; (690) Huang, L.; Thi, Q. H.; Zheng, F.; Chen, X.; Chu, Y. W.; Lee,
McCloskey, D.; Nerl, H. C.; O’Neill, A.; King, P. J.; Higgins, T.; C.-S.; Zhao, J.; Ly, T. H. Catalyzed Kinetic Growth in Two-
Hanlon, D.; et al. Edge and Confinement Effects Allow in Situ Dimensional MoS2. J. Am. Chem. Soc. 2020, 142, 13130−13135.
Measurement of Size and Thickness of Liquid-Exfoliated Nanosheets. (691) Zhao, J.; Yu, R.; Dai, S.; Zhu, J. Kinetical Faceting of the Low
Nat. Commun. 2014, 5, 4576. Index W Surfaces under Electrical Current. Surf. Sci. 2014, 625, 10−
(673) Kang, J.; Seo, J. W.; Alducin, D.; Ponce, A.; Yacaman, M. J.; 15.
Hersam, M. C. Thickness Sorting of Two-Dimensional Transition (692) Krug, J.; Dobbs, H. T. Current-Induced Faceting of Crystal
Metal Dichalcogenides via Copolymer-Assisted Density Gradient Surfaces. Phys. Rev. Lett. 1994, 73, 1947−1950.
Ultracentrifugation. Nat. Commun. 2014, 5, 5478. (693) Kim, M.; Seo, J.; Kim, J.; Moon, J. S.; Lee, J.; Kim, J.-H.; Kang,
(674) Backes, C.; Szydlowska, B. M.; Harvey, A.; Yuan, S.; Vega- J.; Park, H. High-Crystalline Monolayer Transition Metal Dichalco-
Mayoral, V.; Davies, B. R.; Zhao, P. L.; Hanlon, D.; Santos, E. J.; genides Films for Wafer-Scale Electronics. ACS Nano 2021, 15,
Katsnelson, M. I.; et al. Production of Highly Monolayer Enriched 3038−3046.
Dispersions of Liquid-Exfoliated Nanosheets by Liquid Cascade (694) Lin, Y.-C.; Yeh, C.-H.; Lin, H.-C.; Siao, M.-D.; Liu, Z.;
Centrifugation. ACS Nano 2016, 10, 1589−1601. Nakajima, H.; Okazaki, T.; Chou, M.-Y.; Suenaga, K.; Chiu, P.-W.
(675) Kang, J.; Sangwan, V. K.; Wood, J. D.; Liu, X.; Balla, I.; Lam, Stable 1T Tungsten Disulfide Monolayer and Its Junctions: Growth
D.; Hersam, M. C. Layer-by-Layer Sorting of Rhenium Disulfide via and Atomic Structures. ACS Nano 2018, 12, 12080−12088.
High-Density Isopycnic Density Gradient Ultracentrifugation. Nano (695) Jiang, H.; Zhang, P.; Wang, X.; Gong, Y. Synthesis of
Lett. 2016, 16, 7216−7223. Magnetic Two-Dimensional Materials by Chemical Vapor Deposition.
(676) Li, Z.; Zheng, S.; Zhang, Y.; Teng, R.; Huang, T.; Chen, C.; Nano Res. 2021, 14, 1789−1801.
Lu, G. Controlled Synthesis of Tellurium Nanowires and Nanotubes (696) Li, W.; Huang, J.; Han, B.; Xie, C.; Huang, X.; Tian, K.; Zeng,
via a Facile, Efficient, and Relatively Green Solution Phase Method. J. Y.; Zhao, Z.; Gao, P.; Zhang, Y.; et al. Molten-Salt-Assisted Chemical
Mater. Chem. A 2013, 1, 15046−15052.
Vapor Deposition Process for Substitutional Doping of Monolayer
(677) Pokhrel, D.; Bastola, E.; Phillips, A. B.; Heben, M. J.;
MoS2 and Effectively Altering the Electronic Structure and Phononic
Ellingson, R. J. Aspect Ratio Controlled Synthesis of Tellurium
Properties. Adv. Sci. 2020, 7, 2001080.
Nanowires for Photovoltaic Applications. Mater. Adv. 2020, 1, 2721−
(697) Wang, D.; Zhou, Y.; Zhang, H.; Zhang, R.; Dong, H.; Xu, R.;
2728.
Cheng, Z.; He, Y.; Wang, Z. Wafer-Scale Growth of Pristine and
(678) Qi, R.; Cheng, Y. Synthesis of Se Nanowires at Room
Doped Monolayer MoS2 Films for Electronic Device Applications.
Temperature Using Selenourea as Se Source. J. Mater. Sci.: Mater.
Electron. 2020, 31, 5843−5847. Inorg. Chem. 2020, 59, 17356−17363.
(679) Yan, W.; Burgos-Caminal, A.; Das Gupta, T.; Moser, J.-E.; (698) Park, J.; Choudhary, N.; Smith, J.; Lee, G.; Kim, M.; Choi, W.
Sorin, F. Direct Synthesis of Selenium Nanowire Mesh on a Solid Thickness Modulated MoS2 Grown by Chemical Vapor Deposition
Substrate and Insights into Ultrafast Photocarrier Dynamics. J. Phys. for Transparent and Flexible Electronic Devices. Appl. Phys. Lett.
Chem. C 2018, 122, 25134−25141. 2015, 106, No. 012104.
(680) Guo, J.; Xiang, R.; Cheng, T.; Maruyama, S.; Li, Y. One- (699) Samad, L.; Bladow, S. M.; Ding, Q.; Zhuo, J.; Jacobberger, R.
Dimensional vdW Heterostructures: A Perspective. ACS Nanosci. Au M.; Arnold, M. S.; Jin, S. Layer-Controlled Chemical Vapor
2022, 2, 3−11. Deposition Growth of MoS2 Vertical Heterostructures via vdW
(681) Qin, J.; Qiu, G.; Jian, J.; Zhou, H.; Yang, L.; Charnas, A.; Epitaxy. ACS Nano 2016, 10, 7039−7046.
Zemlyanov, D. Y.; Xu, C.-Y.; Xu, X.; Wu, W.; et al. Controlled (700) Serna, M. I.; Yoo, S. H.; Moreno, S.; Xi, Y.; Oviedo, J. P.;
Growth of a Large-Size 2D Selenium Nanosheet and Its Electronic Choi, H.; Alshareef, H. N.; Kim, M. J.; Minary-Jolandan, M.;
and Optoelectronic Applications. ACS Nano 2017, 11, 10222−10229. Quevedo-Lopez, M. A. Large-Area Deposition of MoS2 by Pulsed
(682) Kwak, J.; Kim, C.-E.; Min, Y.; Lee, J.-H.; Soon, A.; Jeong, U. Laser Deposition with in Situ Thickness Control. ACS Nano 2016, 10,
The Effect of Se Doping on the Growth of Te Nanorods. 6054−6061.
CrystEngComm 2015, 17, 5734−5743. (701) Mahler, B.; Hoepfner, V.; Liao, K.; Ozin, G. A. Colloidal
(683) Laocharoensuk, R.; Palaniappan, K.; Smith, N. A.; Dickerson, Synthesis of 1T-WS2 and 2H-WS2 Nanosheets: Applications for
R. M.; Werder, D. J.; Baldwin, J. K.; Hollingsworth, J. A. Flow-Based Photocatalytic Hydrogen Evolution. J. Am. Chem. Soc. 2014, 136,
Solution-Liquid-Solid Nanowire Synthesis. Nat. Nanotechnol. 2013, 8, 14121−14127.
660−666. (702) Voiry, D.; Yamaguchi, H.; Li, J.; Silva, R.; Alves, D. C.; Fujita,
(684) Xing, G.; Liu, X.; Hao, S.; Li, X.; Fan, L.; Li, Y. Diameter- and T.; Chen, M.; Asefa, T.; Shenoy, V. B.; Eda, G.; et al. Enhanced
Length-Controlled Synthesis of Ultrathin ZnS Nanowires and Their Catalytic Activity in Strained Chemically Exfoliated WS2 Nanosheets
Size-Dependent UV Absorption Properties, Photocatalytical Activities for Hydrogen Evolution. Nat. Mater. 2013, 12, 850−855.
and Band-Edge Energy Levels. Nanomaterials (Basel) 2019, 9, 220. (703) Yu, Y.; Nam, G. H.; He, Q.; Wu, X. J.; Zhang, K.; Yang, Z.;
(685) Patla, I.; Acharya, S.; Zeiri, L.; Israelachvili, J.; Efrima, S.; Chen, J.; Ma, Q.; Zhao, M.; Liu, Z.; et al. High Phase-Purity 1T’-
Golan, Y. Synthesis, Two-Dimensional Assembly, and Surface MoS2- and 1T’-MoSe2-Layered Crystals. Nat. Chem. 2018, 10, 638−
Pressure-Induced Coalescence of Ultranarrow PbS NWs. Nano Lett. 643.
2007, 7, 1459−1462. (704) Dubrovskii, V. G.; Sibirev, N. V.; Harmand, J. C.; Glas, F.
(686) Park, K. H.; Choi, J.; Kim, H. J.; Lee, J. B.; Son, S. U. Synthesis Growth Kinetics and Crystal Structure of Semiconductor Nanowires.
of Antimony Sulfide Nanotubes with Ultrathin Walls via Gradual Phys. Rev. B 2008, 78, 235301.
Chem. Rev. 2023, 123, 3329−3442
(705) Wallentin, J.; Kriegner, D.; Stangl, J.; Borgstrom, M. T. Au- (724) Empante, T. A.; Zhou, Y.; Klee, V.; Nguyen, A. E.; Lu, I. H.;
Seeded Growth of Vertical and in-Plane III-V Nanowires on Graphite Valentin, M. D.; Naghibi Alvillar, S. A.; Preciado, E.; Berges, A. J.;
Substrates. Nano Lett. 2014, 14, 1707−1713. Merida, C. S.; et al. Chemical Vapor Deposition Growth of Few-Layer
(706) Lehmann, S.; Wallentin, J.; Jacobsson, D.; Deppert, K.; Dick, MoTe2 in the 2H, 1T′, and 1T Phases: Tunable Properties of MoTe2
K. A. A General Approach for Sharp Crystal Phase Switching in InAs, Films. ACS Nano 2017, 11, 900−905.
GaAs, InP, and GaP Nanowires Using Only Group V Flow. Nano Lett. (725) Yoo, Y.; DeGregorio, Z. P.; Su, Y.; Koester, S. J.; Johns, J. E.
2013, 13, 4099−4105. In-Plane 2H-1T′ MoTe2 Homojunctions Synthesized by Flux-
(707) Glas, F.; Harmand, J. C.; Patriarche, G. Why Does Wurtzite Controlled Phase Engineering. Adv. Mater. 2017, 29, 1605461.
Form in Nanowires of III-V Zinc Blende Semiconductors? Phys. Rev. (726) Xu, X.; Chen, S.; Liu, S.; Cheng, X.; Xu, W.; Li, P.; Wan, Y.;
Lett. 2007, 99, 146101. Yang, S.; Gong, W.; Yuan, K.; et al. Millimeter-Scale Single-Crystalline
(708) Wang, F.; Buhro, W. E. Crystal-Phase Control by Solution- Semiconducting MoTe2 via Solid-to-Solid Phase Transformation. J.
Solid-Solid Growth of II-VI Quantum Wires. Nano Lett. 2016, 16, Am. Chem. Soc. 2019, 141, 2128−2134.
889−894. (727) Xu, X.; Pan, Y.; Liu, S.; Han, B.; Gu, P.; Li, S.; Xu, W.; Peng,
(709) Wang, F.; Buhro, W. E. Role of Precursor-Conversion Y.; Han, Z.; Chen, J.; et al. Seeded 2D Epitaxy of Large-Area Single-
Chemistry in the Crystal-Phase Control of Catalytically Grown Crystal Films of the vdW Semiconductor 2H MoTe2. Science 2021,
Colloidal Semiconductor Quantum Wires. ACS Nano 2017, 11, 372, 195−200.
12526−12535. (728) Wang, Z.; Shen, Y.; Ito, Y.; Zhang, Y.; Du, J.; Fujita, T.;
(710) Xia, J.; Wang, J.; Chao, D.; Chen, Z.; Liu, Z.; Kuo, J. L.; Yan, Hirata, A.; Tang, Z.; Chen, M. Synthesizing 1T−1H Two-Phase
J.; Shen, Z. X. Phase Evolution of Lithium Intercalation Dynamics in Mo1−xWxS2 Monolayers by Chemical Vapor Deposition. ACS Nano
2H-MoS2. Nanoscale 2017, 9, 7533−7540. 2018, 12, 1571−1579.
(711) Zhou, R.; Wang, H.; Chang, J.; Yu, C.; Dai, H.; Chen, Q.; (729) Park, J. C.; Yun, S. J.; Kim, H.; Park, J.-H.; Chae, S. H.; An, S.-
Zhou, J.; Yu, H.; Sun, G.; Huang, W. Ammonium Intercalation J.; Kim, J.-G.; Kim, S. M.; Kim, K. K.; Lee, Y. H. Phase-Engineered
Induced Expanded 1T-Rich Molybdenum Diselenides for Improved Synthesis of Centimeter-Scale 1T′- and 2H-Molybdenum Ditelluride
Lithium Ion Storage. ACS Appl. Mater. Interfaces 2021, 13, 17459− Thin Films. ACS Nano 2015, 9, 6548−6554.
17466. (730) Zhang, F.; Zhang, H.; Krylyuk, S.; Milligan, C. A.; Zhu, Y.;
(712) Jimenez Sandoval, S.; Yang, D.; Frindt, R. F.; Irwin, J. C. Zemlyanov, D. Y.; Bendersky, L. A.; Burton, B. P.; Davydov, A. V.;
Raman Study and Lattice Dynamics of Single Molecular Layers of Appenzeller, J. Electric-Field Induced Structural Transition in Vertical
MoS2. Phys. Rev. B: Condens. Matter Mater. Phys. 1991, 44, 3955− MoTe2- and Mo1−xWxTe2-Based Resistive Memories. Nat. Mater.
3962. 2019, 18, 55−61.
(713) Yang, D.; Sandoval, S. J.; Divigalpitiya, W. M.; Irwin, J. C.; (731) Wang, Y.; Xiao, J.; Zhu, H.; Li, Y.; Alsaid, Y.; Fong, K. Y.;
Frindt, R. F. Structure of Single-Molecular-Layer MoS2. Phys. Rev. B: Zhou, Y.; Wang, S.; Shi, W.; Wang, Y.; et al. Structural Phase
Condens. Matter Mater. Phys. 1991, 43, 12053−12056. Transition in Monolayer MoTe2 Driven by Electrostatic Doping.
(714) Klankowski, S. A.; Rojeski, R. A.; Cruden, B. A.; Liu, J.; Wu, J.; Nature 2017, 550, 487−491.
Li, J. A High-Performance Lithium-Ion Battery Anode Based on the (732) Li, Y.; Duerloo, K.-A. N.; Wauson, K.; Reed, E. J. Structural
Core−Shell Heterostructure of Silicon-Coated Vertically Aligned Semiconductor-to-Semimetal Phase Transition in Two-Dimensional
Carbon Nanofibers. J. Mater. Chem. A 2013, 1, 1055−1064. Materials Induced by Electrostatic Gating. Nat. Commun. 2016, 7,
(715) Wu, F.; Chen, J.; Chen, R.; Wu, S.; Li, L.; Chen, S.; Zhao, T. 10671.
Sulfur/Polythiophene with a Core/Shell Structure: Synthesis and (733) Johnson, V. L.; Anilao, A.; Koski, K. J. Pressure-Dependent
Electrochemical Properties of the Cathode for Rechargeable Lithium Phase Transition of 2D Layered Silicon Telluride (Si2Te3) and
Batteries. J. Phys. Chem. C 2011, 115, 6057−6063. Manganese Intercalated Silicon Telluride. Nano Res. 2019, 12, 2373−
(716) Chen, L.; Feng, H.; Zhang, R.; Wang, S.; Zhang, X.; Wei, Z.; 2377.
Zhu, Y.; Gu, M.; Zhao, C. Phase-Controlled Synthesis of 2H/3R- (734) Kappera, R.; Voiry, D.; Yalcin, S. E.; Branch, B.; Gupta, G.;
MoSe2 Nanosheets on P-Doped Carbon for Synergistic Hydrogen Mohite, A. D.; Chhowalla, M. Phase-Engineered Low-Resistance
Evolution. ACS Appl. Nano Mater. 2020, 3, 6516−6523. Contacts for Ultrathin MoS2 Transistors. Nat. Mater. 2014, 13, 1128−
(717) Keum, D. H.; Cho, S.; Kim, J. H.; Choe, D.-H.; Sung, H.-J.; 1134.
Kan, M.; Kang, H.; Hwang, J.-Y.; Kim, S. W.; Yang, H.; et al. Bandgap (735) Xia, Y.; Berry, J.; Haataja, M. P. Defect-Enabled Phase
Opening in Few-Layered Monoclinic MoTe2. Nat. Phys. 2015, 11, Programming of Transition Metal Dichalcogenide Monolayers. Nano
482−486. Lett. 2021, 21, 4676−4683.
(718) Sokolikova, M. S.; Mattevi, C. Direct Synthesis of Metastable (736) Yu, Y.; Yang, F.; Lu, X. F.; Yan, Y. J.; Cho, Y.-H.; Ma, L.; Niu,
Phases of 2D Transition Metal Dichalcogenides. Chem. Soc. Rev. 2020, X.; Kim, S.; Son, Y.-W.; Feng, D.; et al. Gate-Tunable Phase
49, 3952−3980. Transitions in Thin Flakes of 1T-TaS2. Nat. Nanotechnol. 2015, 10,
(719) Guo, C.; Li, H.; Zhao, W.; Pan, J.; Lin, T.; Xu, J.; Chen, M.; 270−276.
Huang, F. High-Quality Single-Layer Nanosheets of MS2 (M = Mo, (737) Cho, S.; Kim, S.; Kim, J. H.; Zhao, J.; Seok, J.; Keum, D. H.;
Nb, Ta, Ti) Directly Exfoliated from AMS2 (a = Li, Na, K) Crystals. J. Baik, J.; Choe, D.-H.; Chang, K. J.; Suenaga, K. Phase Patterning for
Mater. Chem. C 2017, 5, 5977−5983. Ohmic Homojunction Contact in MoTe2. Science 2015, 349, 625−
(720) Guo, C.; Pan, J.; Li, H.; Lin, T.; Liu, P.; Song, C.; Wang, D.; 628.
Mu, G.; Lai, X.; Zhang, H.; et al. Observation of Superconductivity in (738) Wang, P.; Yang, Y.; Pan, E.; Liu, F.; Ajayan, P. M.; Zhou, J.;
1T′-MoS2 Nanosheets. J. Mater. Chem. C 2017, 5, 10855−10860. Liu, Z. Emerging Phases of Layered Metal Chalcogenides. Small 2022,
(721) Zhou, L.; Zubair, A.; Wang, Z.; Zhang, X.; Ouyang, F.; Xu, K.; 18, 2105215.
Fang, W.; Ueno, K.; Li, J.; Palacios, T.; et al. Synthesis of High- (739) Zeng, Q.; Wang, H.; Fu, W.; Gong, Y.; Zhou, W.; Ajayan, P.
Quality Large-Area Homogenous 1T′ MoTe2 from Chemical Vapor M.; Lou, J.; Liu, Z. Band Engineering for Novel Two-Dimensional
Deposition. Adv. Mater. 2016, 28, 9526−9531. Atomic Layers. Small 2015, 11, 1868−1884.
(722) Kang, L.; Ye, C.; Zhao, X.; Zhou, X.; Hu, J.; Li, Q.; Liu, D.; (740) Shahmanesh, A.; Romanin, D.; Dabard, C.; Chee, S.-S.;
Das, C. M.; Yang, J.; Hu, D.; et al. Phase-Controllable Growth of Gréboval, C.; Methivier, C.; Silly, M. G.; Chaste, J.; Bugnet, M.;
Ultrathin 2D Magnetic Fete Crystals. Nat. Commun. 2020, 11, 3729. Pierucci, D.; et al. 2D Monolayer of the 1T’ Phase of Alloyed WSSe
(723) Yang, L.; Zhang, W.; Li, J.; Cheng, S.; Xie, Z.; Chang, H. from Colloidal Synthesis. J. Phys. Chem. C 2021, 125, 11058−11065.
Tellurization Velocity-Dependent Metallic−Semiconducting−Metal- (741) Xu, J.; Li, X.; Liu, W.; Sun, Y.; Ju, Z.; Yao, T.; Wang, C.; Ju,
lic Phase Evolution in Chemical Vapor Deposition Growth of Large- H.; Zhu, J.; Wei, S.; et al. Carbon Dioxide Electroreduction into
Area, Few-Layer MoTe2. ACS Nano 2017, 11, 1964−1972. Syngas Boosted by a Partially Delocalized Charge in Molybdenum
Chem. Rev. 2023, 123, 3329−3442
Sulfide Selenide Alloy Monolayers. Angew. Chem., Int. Ed. Engl. 2017, (759) Du, Z.; Yang, S.; Li, S.; Lou, J.; Zhang, S.; Wang, S.; Li, B.;
56, 9121−9125. Gong, Y.; Song, L.; Zou, X.; Ajayan, P. M. Conversion of Non-vdW
(742) Scheele, M.; Oeschler, N.; Veremchuk, I.; Reinsberg, K.-G.; Solids to 2D Transition-Metal Chalcogenides. Nature 2020, 577,
Kreuziger, A.-M.; Kornowski, A.; Broekaert, J.; Klinke, C.; Weller, H. 492−496.
ZT Enhancement in Solution-Grown Sb(2−X)BixTe3 Nanoplatelets. (760) Fu, S.; Kang, K.; Shayan, K.; Yoshimura, A.; Dadras, S.; Wang,
ACS Nano 2010, 4, 4283−4291. X.; Zhang, L.; Chen, S.; Liu, N.; Jindal, A.; et al. Enabling Room
(743) Lee, H. I.; Yu, H.; Rhee, C. K.; Sohn, Y. Electrochemical Temperature Ferromagnetism in Monolayer MoS2 via in Situ Iron-
Hydrogen Evolution and Co2 Reduction over Hierarchical MoSxSe2‑x Doping. Nat. Commun. 2020, 11, 2034.
Hybrid Nanostructures. Appl. Surf. Sci. 2019, 489, 976−982. (761) Pham, Y. T. H.; Liu, M.; Jimenez, V. O.; Yu, Z.; Kalappattil,
(744) Sun, Y.; Fujisawa, K.; Lin, Z.; Lei, Y.; Mondschein, J. S.; V.; Zhang, F.; Wang, K.; Williams, T.; Terrones, M.; Phan, M.-H.
Terrones, M.; Schaak, R. E. Low-Temperature Solution Synthesis of Tunable Ferromagnetism and Thermally Induced Spin Flip in
Transition Metal Dichalcogenide Alloys with Tunable Optical Vanadium-Doped Tungsten Diselenide Monolayers at Room
Properties. J. Am. Chem. Soc. 2017, 139, 11096−11105. Temperature. Adv. Mater. 2020, 32, 2003607.
(745) Zhao, Q.; Lu, Q.; Liu, Y.; Zhang, M. Two-Dimensional Dy (762) Luo, P.; Zhuge, F.; Zhang, Q.; Chen, Y.; Lv, L.; Huang, Y.; Li,
Doped MoS2 Ferromagnetic Sheets. Appl. Surf. Sci. 2019, 471, 118− H.; Zhai, T. Doping Engineering and Functionalization of Two-
123. Dimensional Metal Chalcogenides. Nanoscale Horiz. 2019, 4, 26−51.
(746) Yarali, M.; Zhong, Y.; Reed, S. N.; Wang, J.; Ulman, K. A.; (763) Zhang, X.; Cheng, H.; Zhang, H. Recent Progress in the
Charboneau, D. J.; Curley, J. B.; Hynek, D. J.; Pondick, J. V.; Yazdani, Preparation, Assembly, Transformation, and Applications of Layer-
S.; et al. Near-Unity Molecular Doping Efficiency in Monolayer MoS2. Structured Nanodisks Beyond Graphene. Adv. Mater. 2017, 29,
Adv. Electron. Mater. 2021, 7, 2000873. 1701704.
(747) Lei, S.; Wang, X.; Li, B.; Kang, J.; He, Y.; George, A.; Ge, L.; (764) Hyun, J. K.; Zhang, S.; Lauhon, L. J. Nanowire
Gong, Y.; Dong, P.; Jin, Z.; et al. Surface Functionalization of Two- Heterostructures. Annu. Rev. Mater. Res. 2013, 43, 451−479.
Dimensional Metal Chalcogenides by Lewis Acid−Base Chemistry. (765) Tan, C.; Zhang, H. Two-Dimensional Transition Metal
Nat. Nanotechnol. 2016, 11, 465−471. Dichalcogenide Nanosheet-Based Composites. Chem. Soc. Rev. 2015,
(748) Karthikeyan, J.; Komsa, H.-P.; Batzill, M.; Krasheninnikov, A. 44, 2713−2731.
V. Which Transition Metal Atoms Can Be Embedded into Two- (766) Versteegh, M. A.; Reimer, M. E.; Jons, K. D.; Dalacu, D.;
Dimensional Molybdenum Dichalcogenides and Add Magnetism? Poole, P. J.; Gulinatti, A.; Giudice, A.; Zwiller, V. Observation of
Nano Lett. 2019, 19, 4581−4587. Strongly Entangled Photon Pairs from a Nanowire Quantum Dot.
(749) Lin, Y.-C.; Dumcenco, D. O.; Komsa, H.-P.; Niimi, Y.; Nat. Commun. 2014, 5, 5298.
Krasheninnikov, A. V.; Huang, Y.-S.; Suenaga, K. Properties of (767) Ikonić, Z.; Srivastava, G. P.; Inkson, J. C. Electronic Structure
Individual Dopant Atoms in Single-Layer MoS2: Atomic Structure, of Twinning Superlattices. Surf. Sci. 1994, 307−309, 880−884.
(768) Xu, J.; Cui, J.; Guo, C.; Zhao, Z.; Jiang, R.; Xu, S.; Zhuang, Z.;
Migration, and Enhanced Reactivity. Adv. Mater. 2014, 26, 2857−
Huang, Y.; Wang, L.; Li, Y. Ultrasmall Cu7S4@MoS2 Hetero-
2861.
Nanoframes with Abundant Active Edge Sites for Ultrahigh-
(750) Zhu, Y.; Ramasse, Q. M.; Brorson, M.; Moses, P. G.; Hansen,
Performance Hydrogen Evolution. Angew. Chem., Int. Ed. Engl.
L. P.; Kisielowski, C. F.; Helveg, S. Visualizing the Stoichiometry of
2016, 55, 6502−6505.
Industrial-Style Co-Mo-S Catalysts with Single-Atom Sensitivity.
(769) Sun, X.; Deng, H.; Zhu, W.; Yu, Z.; Wu, C.; Xie, Y. Interface
Angew. Chem., Int. Ed. 2014, 53, 10723−10727.
Engineering in Two-Dimensional Heterostructures: Towards an
(751) Zhang, K.; Feng, S.; Wang, J.; Azcatl, A.; Lu, N.; Addou, R.;
Advanced Catalyst for Ullmann Couplings. Angew. Chem., Int. Ed.
Wang, N.; Zhou, C.; Lerach, J.; Bojan, V.; et al. Manganese Doping of
Engl. 2016, 55, 1704−1709.
Monolayer MoS2: The Substrate Is Critical. Nano Lett. 2015, 15, (770) Tan, C.; Zeng, Z.; Huang, X.; Rui, X.; Wu, X. J.; Li, B.; Luo,
6586−6591. Z.; Chen, J.; Chen, B.; Yan, Q.; et al. Liquid-Phase Epitaxial Growth
(752) Li, Q.; Zhao, X.; Deng, L.; Shi, Z.; Liu, S.; Wei, Q.; Zhang, L.; of Two-Dimensional Semiconductor Hetero-Nanostructures. Angew.
Cheng, Y.; Zhang, L.; Lu, H.; et al. Enhanced Valley Zeeman Splitting Chem., Int. Ed. Engl. 2015, 54, 1841−1845.
in Fe-Doped Monolayer MoS2. ACS Nano 2020, 14, 4636−4645. (771) Chen, J.; Wu, X. J.; Yin, L.; Li, B.; Hong, X.; Fan, Z.; Chen, B.;
(753) Gao, H.; Suh, J.; Cao, M. C.; Joe, A. Y.; Mujid, F.; Lee, K.-H.; Xue, C.; Zhang, H. One-Pot Synthesis of CdS Nanocrystals
Xie, S.; Poddar, P.; Lee, J.-U.; Kang, K.; et al. Tuning Electrical Hybridized with Single-Layer Transition-Metal Dichalcogenide
Conductance of MoS2 Monolayers through Substitutional Doping. Nanosheets for Efficient Photocatalytic Hydrogen Evolution. Angew.
Nano Lett. 2020, 20, 4095−4101. Chem., Int. Ed. Engl. 2015, 54, 1210−1214.
(754) Suh, J.; Tan, T. L.; Zhao, W.; Park, J.; Lin, D.-Y.; Park, T.-E.; (772) Schornbaum, J.; Winter, B.; Schießl, S. P.; Gannott, F.;
Kim, J.; Jin, C.; Saigal, N.; Ghosh, S.; et al. Reconfiguring Crystal and Katsukis, G.; Guldi, D. M.; Spiecker, E.; Zaumseil, J. Epitaxial Growth
Electronic Structures of MoS2 by Substitutional Doping. Nat. of PbSe Quantum Dots on MoS2 Nanosheets and Their near-Infrared
Commun. 2018, 9, 199. Photoresponse. Adv. Funct. Mater. 2014, 24, 5798−5806.
(755) Qin, Z.; Loh, L.; Wang, J.; Xu, X.; Zhang, Q.; Haas, B.; (773) Yin, X. L.; Li, L. L.; Jiang, W. J.; Zhang, Y.; Zhang, X.; Wan, L.
Alvarez, C.; Okuno, H.; Yong, J. Z.; Schultz, T.; et al. Growth of Nb- J.; Hu, J. S. MoS2/CdS Nanosheets-on-Nanorod Heterostructure for
Doped Monolayer WS2 by Liquid-Phase Precursor Mixing. ACS Nano Highly Efficient Photocatalytic H2 Generation under Visible Light
2019, 13, 10768−10775. Irradiation. ACS Appl. Mater. Interfaces 2016, 8, 15258−15266.
(756) Zhang, K.; Bersch, B. M.; Joshi, J.; Addou, R.; Cormier, C. R.; (774) Jeong, S.; Han, J. H.; Jang, J. T.; Seo, J. W.; Kim, J. G.; Cheon,
Zhang, C.; Xu, K.; Briggs, N. C.; Wang, K.; Subramanian, S.; et al. J. Transformative Two-Dimensional Layered Nanocrystals. J. Am.
Tuning the Electronic and Photonic Properties of Monolayer MoS2 Chem. Soc. 2011, 133, 14500−14503.
via in Situ Rhenium Substitutional Doping. Adv. Funct. Mater. 2018, (775) Zhou, W.; Yin, Z.; Du, Y.; Huang, X.; Zeng, Z.; Fan, Z.; Liu,
28, 1706950. H.; Wang, J.; Zhang, H. Synthesis of Few-Layer MoS2 Nanosheet-
(757) Duan, H.; Guo, P.; Wang, C.; Tan, H.; Hu, W.; Yan, W.; Ma, Coated TiO2 Nanobelt Heterostructures for Enhanced Photocatalytic
C.; Cai, L.; Song, L.; Zhang, W.; et al. Beating the Exclusion Rule Activities. Small 2013, 9, 140−147.
against the Coexistence of Robust Luminescence and Ferromagnetism (776) Chen, Y.; Song, B.; Tang, X.; Lu, L.; Xue, J. Ultrasmall Fe =
in Chalcogenide Monolayers. Nat. Commun. 2019, 10, 1584. O4 Nanoparticle/MoS2 Nanosheet Composites with Superior
(758) Tang, J.; Wei, Z.; Wang, Q.; Wang, Y.; Han, B.; Li, X.; Huang, Performances for Lithium Ion Batteries. Small 2014, 10, 1536−1543.
B.; Liao, M.; Liu, J.; Li, N.; et al. In Situ Oxygen Doping of Monolayer (777) Han, J. H.; Lee, S.; Yoo, D.; Lee, J. H.; Jeong, S.; Kim, J. G.;
MoS2 for Novel Electronics. Small 2020, 16, 2004276. Cheon, J. Unveiling Chemical Reactivity and Structural Trans-
Chem. Rev. 2023, 123, 3329−3442
formation of Two-Dimensional Layered Nanocrystals. J. Am. Chem. Hydrogen Evolution Reaction. J. Am. Chem. Soc. 2011, 133, 7296−
Soc. 2013, 135, 3736−3739. 7299.
(778) Xiang, Q.; Yu, J.; Jaroniec, M. Synergetic Effect of MoS2 and (796) Li, Y.; Zhuang, T. T.; Fan, F.; Voznyy, O.; Askerka, M.; Zhu,
Graphene as Cocatalysts for Enhanced Photocatalytic H2 Production H.; Wu, L.; Liu, G. Q.; Pan, Y. X.; Sargent, E. H.; et al. Pulsed Axial
Activity of TiO2 Nanoparticles. J. Am. Chem. Soc. 2012, 134, 6575− Epitaxy of Colloidal Quantum Dots in Nanowires Enables Facet-
6578. Selective Passivation. Nat. Commun. 2018, 9, 4947.
(779) Huang, Y.; Miao, Y.-E.; Zhang, L.; Tjiu, W. W.; Pan, J.; Liu, T. (797) Zhuang, T. T.; Li, Y.; Gao, X.; Wei, M.; Garcia de Arquer, F.
Synthesis of Few-Layered MoS2 Nanosheet-Coated Electrospun SnO2 P.; Todorovic, P.; Tian, J.; Li, G.; Zhang, C.; Li, X.; et al.
Nanotube Heterostructures for Enhanced Hydrogen Evolution Regioselective Magnetization in Semiconducting Nanorods. Nat.
Reaction. Nanoscale 2014, 6, 10673−10679. Nanotechnol. 2020, 15, 192−197.
(780) Chen, Y.; Lu, J.; Wen, S.; Lu, L.; Xue, J. Synthesis of Sno2/ (798) Sun, Y.; Wang, Y.; Chen, J. Y. C.; Fujisawa, K.; Holder, C. F.;
MoS2 Composites with Different Component Ratios and Their Miller, J. T.; Crespi, V. H.; Terrones, M.; Schaak, R. E. Interface-
Applications as Lithium Ion Battery Anodes. J. Mater. Chem. A 2014, Mediated Noble Metal Deposition on Transition Metal Dichalcoge-
2, 17857−17866. nide Nanostructures. Nat. Chem. 2020, 12, 284−293.
(781) Xu, X.; Fan, Z.; Ding, S.; Yu, D.; Du, Y. Fabrication of MoS2 (799) Gong, Y.; Yuan, H.; Wu, C.-L.; Tang, P.; Yang, S.-Z.; Yang, A.;
Nanosheet@TiO2 Nanotube Hybrid Nanostructures for Lithium Li, G.; Liu, B.; van de Groep, J.; Brongersma, M. L.; et al. Spatially
Storage. Nanoscale 2014, 6, 5245−5250. Controlled Doping of Two-Dimensional SnS2 through Intercalation
(782) Kim, J.; Byun, S.; Smith, A. J.; Yu, J.; Huang, J. Enhanced for Electronics. Nat. Nanotechnol. 2018, 13, 294−299.
Electrocatalytic Properties of Transition-Metal Dichalcogenides (800) Chen, K.; Wan, X.; Wen, J.; Xie, W.; Kang, Z.; Zeng, X.; Chen,
Sheets by Spontaneous Gold Nanoparticle Decoration. J. Phys. H.; Xu, J.-B. Electronic Properties of MoS2−WS2 Heterostructures
Chem. Lett. 2013, 4, 1227−1232. Synthesized with Two-Step Lateral Epitaxial Strategy. ACS Nano
(783) Huang, X.; Zeng, Z.; Bao, S.; Wang, M.; Qi, X.; Fan, Z.; 2015, 9, 9868−9876.
Zhang, H. Solution-Phase Epitaxial Growth of Noble Metal (801) Yoo, Y.; Degregorio, Z. P.; Johns, J. E. Seed Crystal
Nanostructures on Dispersible Single-Layer Molybdenum Disulfide Homogeneity Controls Lateral and Vertical Heteroepitaxy of
Nanosheets. Nat. Commun. 2013, 4, 1444. Monolayer MoS2 and WS2. J. Am. Chem. Soc. 2015, 137, 14281−
(784) Raza, F.; Yim, D.; Park, J. H.; Kim, H. I.; Jeon, S. J.; Kim, J. H. 14287.
Structuring Pd Nanoparticles on 2H-WS2 Nanosheets Induces (802) Huang, C.; Wu, S.; Sanchez, A. M.; Peters, J. J. P.; Beanland,
Excellent Photocatalytic Activity for Cross-Coupling Reactions R.; Ross, J. S.; Rivera, P.; Yao, W.; Cobden, D. H.; Xu, X. Lateral
under Visible Light. J. Am. Chem. Soc. 2017, 139, 14767−14774. Heterojunctions within Monolayer MoSe2−WSe2 Semiconductors.
(785) Zhang, X.; Zhao, R.; Wu, Q.; Li, W.; Shen, C.; Ni, L.; Yan, H.; Nat. Mater. 2014, 13, 1096−1101.
Diao, G.; Chen, M. Petal-Like MoS2 Nanosheets Space-Confined in (803) Zhang, T.; Jiang, B.; Xu, Z.; Mendes, R. G.; Xiao, Y.; Chen, L.;
Hollow Mesoporous Carbon Spheres for Enhanced Lithium Storage Fang, L.; Gemming, T.; Chen, S.; Rümmeli, M. H.; et al. Twinned
Performance. ACS Nano 2017, 11, 8429−8436. Growth Behaviour of Two-Dimensional Materials. Nat. Commun.
(786) Liao, L.; Zhu, J.; Bian, X.; Zhu, L.; Scanlon, M. D.; Girault, H. 2016, 7, 13911.
H.; Liu, B. MoS2 Formed on Mesoporous Graphene as a Highly (804) Zhang, Y.; Yin, L.; Chu, J.; Shifa, T. A.; Xia, J.; Wang, F.; Wen,
Active Catalyst for Hydrogen Evolution. Adv. Funct. Mater. 2013, 23, Y.; Zhan, X.; Wang, Z.; He, J. Edge-Epitaxial Growth of 2D NbS2-WS2
5326−5333. Lateral Metal-Semiconductor Heterostructures. Adv. Mater. 2018, 30,
(787) Wang, S.; Guan, B. Y.; Yu, L.; Lou, X. W. D. Rational Design 1803665.
of Three-Layered TiO2@Carbon@MoS2 Hierarchical Nanotubes for (805) Zhang, X.; Huangfu, L.; Gu, Z.; Xiao, S.; Zhou, J.; Nan, H.;
Enhanced Lithium Storage. Adv. Mater. 2017, 29, 1702724. Gu, X.; Ostrikov, K. Controllable Epitaxial Growth of Large-Area
(788) Yang, J.; Voiry, D.; Ahn, S. J.; Kang, D.; Kim, A. Y.; MoS2/WS2 Vertical Heterostructures by Confined-Space Chemical
Chhowalla, M.; Shin, H. S. Two-Dimensional Hybrid Nanosheets of Vapor Deposition. Nano Micro Small 2021, 17, 2007312
Tungsten Disulfide and Reduced Graphene Oxide as Catalysts for DOI: 10.1002/smll.202007312.
Enhanced Hydrogen Evolution. Angew. Chem., Int. Ed. Engl. 2013, 52, (806) Chen, T.; Ding, D.; Shi, J.; Wang, G.; Kou, L.; Zheng, X.; Ren,
13751−13754. X.; Liu, X.; Jin, C.; Zhong, J.; et al. Lateral and Vertical MoSe2−MoS2
(789) Yu, X. Y.; Hu, H.; Wang, Y.; Chen, H.; Lou, X. W. Ultrathin Heterostructures via Epitaxial Growth: Triggered by High-Temper-
MoS2 Nanosheets Supported on N-Doped Carbon Nanoboxes with ature Annealing and Precursor Concentration. J. Phys. Chem. Lett.
Enhanced Lithium Storage and Electrocatalytic Properties. Angew. 2019, 10, 5027−5035.
Chem., Int. Ed. Engl. 2015, 54, 7395−7398. (807) Zhou, X.; Zhou, N.; Li, C.; Song, H.; Zhang, Q.; Hu, X.; Gan,
(790) Li, D. J.; Maiti, U. N.; Lim, J.; Choi, D. S.; Lee, W. J.; Oh, Y.; L.; Li, H.; Lü, J.; Luo, J.; et al. Vertical Heterostructures Based on
Lee, G. Y.; Kim, S. O. Molybdenum Sulfide/N-Doped Cnt Forest SnSe2/MoS2 for High Performance Photodetectors. 2D Mater. 2017,
Hybrid Catalysts for High-Performance Hydrogen Evolution 4, No. 025048.
Reaction. Nano Lett. 2014, 14, 1228−1233. (808) Duan, X.; Wang, C.; Shaw, J. C.; Cheng, R.; Chen, Y.; Li, H.;
(791) Chen, Y. M.; Yu, X. Y.; Li, Z.; Paik, U.; Lou Xiong, W. Wu, X.; Tang, Y.; Zhang, Q.; Pan, A.; et al. Lateral Epitaxial Growth of
Hierarchical MoS2 Tubular Structures Internally Wired by Carbon Two-Dimensional Layered Semiconductor Heterojunctions. Nat.
Nanotubes as a Highly Stable Anode Material for Lithium-Ion Nanotechnol. 2014, 9, 1024−1030.
Batteries. Sci. Adv. 2016, 2, e1600021. (809) Zhang, R.; Li, M.; Li, L.; Wei, Z.; Jiao, F.; Geng, D.; Hu, W.
(792) Huang, X.; Huang, X. Coating Two-Dimensional Nanoma- The More, the Better−Recent Advances in Construction of 2D Multi-
terials with Metal-Organic Frameworks. ACS Nano 2014, 8, 8695− Heterostructures. Adv. Funct. Mater. 2021, 31, 2102049.
8701. (810) Fabbri, F.; Rotunno, E.; Cinquanta, E.; Campi, D.; Bonnini,
(793) Chang, K.; Chen, W. L-Cysteine-Assisted Synthesis of Layered E.; Kaplan, D.; Lazzarini, L.; Bernasconi, M.; Ferrari, C.; Longo, M.;
MoS2/Graphene Composites with Excellent Electrochemical Per- et al. Novel near-Infrared Emission from Crystal Defects in MoS2
formances for Lithium Ion Batteries. ACS Nano 2011, 5, 4720−4728. Multilayer Flakes. Nat. Commun. 2016, 7, 13044.
(794) Wang, Y.; Yu, L.; Lou, X. W. Synthesis of Highly Uniform (811) Lin, Z.; Carvalho, B. R.; Kahn, E.; Lv, R.; Rao, R.; Terrones,
Molybdenum-Glycerate Spheres and Their Conversion into Hier- H.; Pimenta, M. A.; Terrones, M. Defect Engineering of Two-
archical MoS2 Hollow Nanospheres for Lithium-Ion Batteries. Angew. Dimensional Transition Metal Dichalcogenides. 2D Mater. 2016, 3,
Chem., Int. Ed. Engl. 2016, 55, 7423−7426. No. 022002.
(795) Li, Y.; Wang, H.; Xie, L.; Liang, Y.; Hong, G.; Dai, H. MoS2 (812) Najmaei, S.; Liu, Z.; Zhou, W.; Zou, X.; Shi, G.; Lei, S.;
Nanoparticles Grown on Graphene: An Advanced Catalyst for the Yakobson, B. I.; Idrobo, J.-C.; Ajayan, P. M.; Lou, J. Vapour Phase
Chem. Rev. 2023, 123, 3329−3442
Growth and Grain Boundary Structure of Molybdenum Disulphide Point Defects in Monolayer Rhenium Disulfide. Phys. Rev. B 2014, 89,
Atomic Layers. Nat. Mater. 2013, 12, 754−759. 155433.
(813) Wang, S.; Lee, G.-D.; Lee, S.; Yoon, E.; Warner, J. H. Detailed (832) Pizzochero, M.; Yazyev, O. V. Points Defects in the 1T’ and
Atomic Reconstruction of Extended Line Defects in Monolayer MoS2. 2H Phases of Single-Layer MoS2: A Comparative First-Principles
ACS Nano 2016, 10, 5419−5430. Study. Phys. Rev. B 2017, 96, 245402.
(814) Lin, J.; Pantelides, S. T.; Zhou, W. Vacancy-Induced (833) Zheng, Y. J.; Chen, Y.; Huang, Y. L.; Gogoi, P. K.; Li, M.-Y.;
Formation and Growth of Inversion Domains in Transition-Metal Li, L.-J.; Trevisanutto, P. E.; Wang, Q.; Pennycook, S. J.; Wee, A. T.
Dichalcogenide Monolayer. ACS Nano 2015, 9, 5189−5197. S.; et al. Point Defects and Localized Excitons in 2D WSe2. ACS Nano
(815) Hong, J.; Hu, Z.; Probert, M.; Li, K.; Lv, D.; Yang, X.; Gu, L.; 2019, 13, 6050−6059.
Mao, N.; Feng, Q.; Xie, L.; et al. Exploring Atomic Defects in (834) González, C.; Biel, B.; Dappe, Y. J. Theoretical Character-
Molybdenum Disulphide Monolayers. Nat. Commun. 2015, 6, 6293. isation of Point Defects on a MoS2 Monolayer by Scanning
(816) Vancsó, P.; Magda, G. Z.; Pető , J.; Noh, J.-Y.; Kim, Y.-S.; Tunnelling Microscopy. Nanotechnology 2016, 27, 105702.
Hwang, C.; Biró, L. P.; Tapasztó, L. The Intrinsic Defect Structure of (835) Barja, S.; Refaely-Abramson, S.; Schuler, B.; Qiu, D. Y.; Pulkin,
Exfoliated MoS2 Single Layers Revealed by Scanning Tunneling A.; Wickenburg, S.; Ryu, H.; Ugeda, M. M.; Kastl, C.; Chen, C.; et al.
Microscopy. Sci. Rep. 2016, 6, 29726. Identifying Substitutional Oxygen as a Prolific Point Defect in
(817) Sharona, H. Defects in Multilayer MoS2 Grown by Pulsed Monolayer Transition Metal Dichalcogenides. Nat. Commun. 2019,
Laser Deposition and Their Impact on Electronic Structure. J. Appl. 10, 3382.
Phys. 2021, 130, No. 084303. (836) Zhussupbekov, K.; Ansari, L.; McManus, J. B.;
(818) Edelberg, D.; Rhodes, D.; Kerelsky, A.; Kim, B.; Wang, J.; Zhussupbekova, A.; Shvets, I. V.; Duesberg, G. S.; Hurley, P. K.;
Zangiabadi, A.; Kim, C.; Abhinandan, A.; Ardelean, J.; Scully, M.; Gity, F.; Ó Coileáin, C.; McEvoy, N. Imaging and Identification of
et al. Approaching the Intrinsic Limit in Transition Metal Diselenides Point Defects in PtTe2. npj 2D Mater. Appl. 2021, 5, 14.
via Point Defect Control. Nano Lett. 2019, 19, 4371−4379. (837) Calderon V, S.; Ferreira, R. V.; Taneja, D.; Jayanth, R. T.;
(819) Qiu, H.; Xu, T.; Wang, Z.; Ren, W.; Nan, H.; Ni, Z.; Chen, Q.; Zhou, L.; Ribeiro, R. M.; Akinwande, D.; Ferreira, P. J. Atomic
Yuan, S.; Miao, F.; Song, F.; et al. Hopping Transport through Defect- Electrostatic Maps of Point Defects in MoS2. Nano Lett. 2021, 21,
Induced Localized States in Molybdenum Disulphide. Nat. Commun. 10157−10164.
2013, 4, 2642. (838) Song, S. H.; Joo, M.-K.; Neumann, M.; Kim, H.; Lee, Y. H.
(820) Lu, C.-P.; Li, G.; Mao, J.; Wang, L.-M.; Andrei, E. Y. Bandgap, Probing Defect Dynamics in Monolayer MoS2 via Noise Nano-
Mid-Gap States, and Gating Effects in MoS2. Nano Lett. 2014, 14, spectroscopy. Nat. Commun. 2017, 8, 2121.
4628−4633. (839) Guo, Y.; Liu, D.; Robertson, J. Chalcogen Vacancies in
(821) Zhu, W.; Low, T.; Lee, Y.-H.; Wang, H.; Farmer, D. B.; Kong, Monolayer Transition Metal Dichalcogenides and Fermi Level
J.; Xia, F.; Avouris, P. Electronic Transport and Device Prospects of Pinning at Contacts. Appl. Phys. Lett. 2015, 106, 173106.
(840) Chen, Y.; Huang, S.; Ji, X.; Adepalli, K.; Yin, K.; Ling, X.;
Monolayer Molybdenum Disulphide Grown by Chemical Vapour
Wang, X.; Xue, J.; Dresselhaus, M.; Kong, J.; et al. Tuning Electronic
Deposition. Nat. Commun. 2014, 5, 3087.
Structure of Single Layer MoS2 through Defect and Interface
(822) Shakya, J.; Kumar, S.; Kanjilal, D.; Mohanty, T. Work
Engineering. ACS Nano 2018, 12, 2569−2579.
Function Modulation of Molybdenum Disulfide Nanosheets by
(841) Li, H.; Tsai, C.; Koh, A. L.; Cai, L.; Contryman, A. W.;
Introducing Systematic Lattice Strain. Sci. Rep. 2017, 7, 9576.
Fragapane, A. H.; Zhao, J.; Han, H. S.; Manoharan, H. C.; Abild-
(823) Lee, S. Y.; Kim, U. J.; Chung, J.; Nam, H.; Jeong, H. Y.; Han,
Pedersen, F.; Nørskov, J. K.; et al. Activating and Optimizing MoS2
G. H.; Kim, H.; Oh, H. M.; Lee, H.; Kim, H.; et al. Large Work
Basal Planes for Hydrogen Evolution through the Formation of
Function Modulation of Monolayer MoS2 by Ambient Gases. ACS Strained Sulphur Vacancies. Nat. Mater. 2016, 15, 48−53.
Nano 2016, 10, 6100−6107. (842) Ye, G.; Gong, Y.; Lin, J.; Li, B.; He, Y.; Pantelides, S. T.; Zhou,
(824) Hong, J.; Jin, C.; Yuan, J.; Zhang, Z. Atomic Defects in Two- W.; Vajtai, R.; Ajayan, P. M. Defects Engineered Monolayer MoS2 for
Dimensional Materials: From Single-Atom Spectroscopy to Function- Improved Hydrogen Evolution Reaction. Nano Lett. 2016, 16, 1097−
alities in Opto-/Electronics, Nanomagnetism, and Catalysis. Adv. 1103.
Mater. 2017, 29, 1606434. (843) Han, S. W.; Hwang, Y. H.; Kim, S.-H.; Yun, W. S.; Lee, J. D.;
(825) Han, S. A.; Kim, T.-H.; Kim, S. K.; Lee, K. H.; Park, H.-J.; Lee, Park, M. G.; Ryu, S.; Park, J. S.; Yoo, D.-H.; Yoon, S.-P.; Hong, S. C.;
J.-H.; Kim, S.-W. Point-Defect-Passivated MoS2 Nanosheet-Based et al. Controlling Ferromagnetic Easy Axis in a Layered MoS2 Single
High Performance Piezoelectric Nanogenerator. Adv. Mater. 2018, 30, Crystal. Phys. Rev. Lett. 2013, 110, 247201.
1800342. (844) Komsa, H.-P.; Kotakoski, J.; Kurasch, S.; Lehtinen, O.; Kaiser,
(826) Yuan, S.; Roldán, R.; Katsnelson, M. I.; Guinea, F. Effect of U.; Krasheninnikov, A. V. Two-Dimensional Transition Metal
Point Defects on the Optical and Transport Properties of MoS2 and Dichalcogenides under Electron Irradiation: Defect Production and
WS2. Phys. Rev. B 2014, 90, No. 041402. Doping. Phys. Rev. Lett. 2012, 109, No. 035503.
(827) He, Y.-M.; Clark, G.; Schaibley, J. R.; He, Y.; Chen, M.-C.; (845) Bertolazzi, S.; Bonacchi, S.; Nan, G.; Pershin, A.; Beljonne, D.;
Wei, Y.-J.; Ding, X.; Zhang, Q.; Yao, W.; Xu, X.; et al. Single Quantum Samorì, P. Engineering Chemically Active Defects in Monolayer MoS2
Emitters in Monolayer Semiconductors. Nat. Nanotechnol. 2015, 10, Transistors via Ion-Beam Irradiation and Their Healing via Vapor
497−502. Deposition of Alkanethiols. Adv. Mater. 2017, 29, 1606760.
(828) Koperski, M.; Nogajewski, K.; Arora, A.; Cherkez, V.; Mallet, (846) Fox, D. S.; Zhou, Y.; Maguire, P.; O’Neill, A.; Ó ’Coileáin, C.;
P.; Veuillen, J. Y.; Marcus, J.; Kossacki, P.; Potemski, M. Single Gatensby, R.; Glushenkov, A. M.; Tao, T.; Duesberg, G. S.; Shvets, I.
Photon Emitters in Exfoliated WSe2 Structures. Nat. Nanotechnol. V.; et al. Nanopatterning and Electrical Tuning of MoS2 Layers with a
2015, 10, 503−506. Subnanometer Helium Ion Beam. Nano Lett. 2015, 15, 5307−5313.
(829) Srivastava, A.; Sidler, M.; Allain, A. V.; Lembke, D. S.; Kis, A.; (847) Lu, W.; Birmingham, B.; Zhang, Z. Defect Engineering on
Imamoğlu, A. Optically Active Quantum Dots in Monolayer WSe2. MoS2 Surface with Argon Ion Bombardments and Thermal
Nat. Nanotechnol. 2015, 10, 491−496. Annealing. Appl. Surf. Sci. 2020, 532, 147461.
(830) Ou, Y.; Kang, Z.; Liao, Q.; Gao, S.; Zhang, Z.; Zhang, Y. Point (848) Tao, L.; Duan, X.; Wang, C.; Duan, X.; Wang, S. Plasma-
Defect Induced Intervalley Scattering for the Enhancement of Engineered MoS2 Thin-Film as an Efficient Electrocatalyst for
Interlayer Electron Transport in Bilayer MoS2 Homojunctions. Hydrogen Evolution Reaction. Chem. Commun. 2015, 51, 7470−
Nanoscale 2020, 12, 9859−9865. 7473.
(831) Horzum, S.; Ç akır, D.; Suh, J.; Tongay, S.; Huang, Y. S.; Ho, (849) Ryder, C. R.; Wood, J. D.; Wells, S. A.; Hersam, M. C.
C. H.; Wu, J.; Sahin, H.; Peeters, F. M. Formation and Stability of Chemically Tailoring Semiconducting Two-Dimensional Transition
Chem. Rev. 2023, 123, 3329−3442
Metal Dichalcogenides and Black Phosphorus. ACS Nano 2016, 10, Generation from Artificially Stacked Transition Metal Dichalcogenide
3900−3917. Twisted Bilayers. ACS Nano 2014, 8, 2951−2958.
(850) He, Z.; Zhao, R.; Chen, X.; Chen, H.; Zhu, Y.; Su, H.; Huang, (868) Yin, X.; Ye, Z.; Chenet, D. A.; Ye, Y.; O’Brien, K.; Hone, J. C.;
S.; Xue, J.; Dai, J.; Cheng, S.; et al. Defect Engineering in Single-Layer Zhang, X. Edge Nonlinear Optics on a MoS2 Atomic Monolayer.
MoS2 Using Heavy Ion Irradiation. ACS Appl. Mater. Interfaces 2018, Science 2014, 344, 488−490.
10, 42524−42533. (869) Fan, X.; Siris, R.; Hartwig, O.; Duesberg, G. S.; Niklaus, F.
(851) Hui, Y. Y.; Liu, X.; Jie, W.; Chan, N. Y.; Hao, J.; Hsu, Y.-T.; Li, Rapid and Large-Area Visualization of Grain Boundaries in MoS2 on
L.-J.; Guo, W.; Lau, S. P. Exceptional Tunability of Band Energy in a SiO2 Using Vapor Hydrofluoric Acid. ACS Appl. Mater. Interfaces
Compressively Strained Trilayer MoS2 Sheet. ACS Nano 2013, 7, 2020, 12, 34049−34057.
7126−7131. (870) Prado, M. C.; Nascimento, R.; Faria, B. E. N.; Matos, M. J. S.;
(852) Zhao, G.-Y.; Deng, H.; Tyree, N.; Guy, M.; Lisfi, A.; Peng, Q.; Chacham, H.; Neves, B. R. A. Nanometre-Scale Identification of
Yan, J.-A.; Wang, C.; Lan, Y. Recent Progress on Irradiation-Induced Grain Boundaries in MoS2 through Molecular Decoration. Nano-
Defect Engineering of Two-Dimensional 2H-MoS2 Few Layers. technology 2015, 26, 475702.
Applied Sciences 2019, 9, 678. (871) Kim, D. W.; Ok, J. M.; Jung, W.-B.; Kim, J.-S.; Kim, S. J.;
(853) Dang, K. Q.; Spearot, D. E. Effect of Point and Grain Choi, H. O.; Kim, Y. H.; Jung, H.-T. Direct Observation of
Boundary Defects on the Mechanical Behavior of Monolayer MoS2 Molybdenum Disulfide, MoS2, Domains by Using a Liquid Crystalline
under Tension via Atomistic Simulations. J. Appl. Phys. 2014, 116, Texture Method. Nano Lett. 2015, 15, 229−234.
No. 013508. (872) Ly, T. H.; Perello, D. J.; Zhao, J.; Deng, Q.; Kim, H.; Han, G.
(854) Wu, J.; Cao, P.; Zhang, Z.; Ning, F.; Zheng, S.-S.; He, J.; H.; Chae, S. H.; Jeong, H. Y.; Lee, Y. H. Misorientation-Angle-
Zhang, Z. Grain-Size-Controlled Mechanical Properties of Poly- Dependent Electrical Transport across Molybdenum Disulfide Grain
crystalline Monolayer MoS2. Nano Lett. 2018, 18, 1543−1552. Boundaries. Nat. Commun. 2016, 7, 10426.
(855) Son, D.-Y.; Lee, J.-W.; Choi, Y. J.; Jang, I.-H.; Lee, S.; Yoo, P. (873) Wang, X.; Wang, B.; Zhang, Q.; Sun, Y.; Wang, E.; Luo, H.;
J.; Shin, H.; Ahn, N.; Choi, M.; Kim, D.; et al. Self-Formed Grain Wu, Y.; Gu, L.; Li, H.; Liu, K. Grain-Boundary Engineering of
Boundary Healing Layer for Highly Efficient CH3NH3PbI3 Perovskite Monolayer MoS2 for Energy-Efficient Lateral Synaptic Devices. Adv.
Solar Cells. Nat. Energy 2016, 1, 16081. Mater. 2021, 33, 2102435.
(856) Li, C.; Wu, Y.; Poplawsky, J.; Pennycook, T. J.; Paudel, N.; (874) Zhao, X.; Ji, Y.; Chen, J.; Fu, W.; Dan, J.; Liu, Y.; Pennycook,
Yin, W.; Haigh, S. J.; Oxley, M. P.; Lupini, A. R.; Al-Jassim, M.; et al. S. J.; Zhou, W.; Loh, K. P. Healing of Planar Defects in 2D Materials
Grain-Boundary-Enhanced Carrier Collection in CdTe Solar Cells. via Grain Boundary Sliding. Adv. Mater. 2019, 31, 1900237.
Phys. Rev. Lett. 2014, 112, 156103. (875) Zheng, F.; Huang, L.; Wong, L.-W.; Han, J.; Cai, Y.; Wang,
(857) Guo, C. F.; Sun, T.; Liu, Q.; Suo, Z.; Ren, Z. Highly N.; Deng, Q.; Ly, T. H.; Zhao, J. The Mobile and Pinned Grain
Stretchable and Transparent Nanomesh Electrodes Made by Grain Boundaries in 2D Monoclinic Rhenium Disulfide. Adv. Sci. 2020, 7,
Boundary Lithography. Nat. Commun. 2014, 5, 3121. 2001742.
(858) Sangwan, V. K.; Jariwala, D.; Kim, I. S.; Chen, K.-S.; Marks, T. (876) Chua, R.; Yang, J.; He, X.; Yu, X.; Yu, W.; Bussolotti, F.;
J.; Lauhon, L. J.; Hersam, M. C. Gate-Tunable Memristive Wong, P. K. J.; Loh, K. P.; Breese, M. B. H.; Goh, K. E. J.; et al. Can
Phenomena Mediated by Grain Boundaries in Single-Layer MoS2. Reconstructed Se-Deficient Line Defects in Monolayer VSe2 Induce
Nat. Nanotechnol. 2015, 10, 403−406. Magnetism? Adv. Mater. 2020, 32, 2000693.
(859) Feng, X.; Jiang, K.; Fan, S.; Kanan, M. W. Grain-Boundary- (877) He, Y.; Tang, P.; Hu, Z.; He, Q.; Zhu, C.; Wang, L.; Zeng, Q.;
Dependent Co2 Electroreduction Activity. J. Am. Chem. Soc. 2015, Golani, P.; Gao, G.; Fu, W.; et al. Engineering Grain Boundaries at
137, 4606−4609. The 2D Limit for the hydrogen Evolution Reaction. Nat. Commun.
(860) Li, G.; Zhang, D.; Qiao, Q.; Yu, Y.; Peterson, D.; Zafar, A.; 2020, 11, 57.
Kumar, R.; Curtarolo, S.; Hunte, F.; Shannon, S.; et al. All the (878) Huang, Y. L.; Chen, Y.; Zhang, W.; Quek, S. Y.; Chen, C.-H.;
Catalytic Active Sites of MoS2 for Hydrogen Evolution. J. Am. Chem. Li, L.-J.; Hsu, W.-T.; Chang, W.-H.; Zheng, Y. J.; Chen, W.; et al.
Soc. 2016, 138, 16632−16638. Bandgap Tunability at Single-Layer Molybdenum Disulphide Grain
(861) Cheng, J.; Jiang, T.; Ji, Q.; Zhang, Y.; Li, Z.; Shan, Y.; Zhang, Boundaries. Nat. Commun. 2015, 6, 6298.
Y.; Gong, X.; Liu, W.; Wu, S. Kinetic Nature of Grain Boundary (879) Zhang, W.; Lin, Y.; Wang, Q.; Li, W.; Wang, Z.; Song, J.; Li,
Formation in as-Grown MoS2 Monolayers. Adv. Mater. 2015, 27, X.; Zhang, L.; Zhu, L.; Xu, X. Well-Hidden Grain Boundary in the
4069−4074. Monolayer MoS2 Formed by a Two-Dimensional Core−Shell Growth
(862) Man, P.; Srolovitz, D.; Zhao, J.; Ly, T. H. Functional Grain Mode. ACS Nano 2017, 11, 10608−10615.
Boundaries in Two-Dimensional Transition-Metal Dichalcogenides. (880) Zhang, C.; Chuu, C.-P.; Ren, X.; Li, M.-Y.; Li, L.-J.; Jin, C.;
Acc. Chem. Res. 2021, 54, 4191−4202. Chou, M.-Y.; Shih, C.-K. Interlayer Couplings, Moiré Patterns, and
(863) Wu, J.; Gong, H.; Zhang, Z.; He, J.; Ariza, P.; Ortiz, M.; 2D Electronic Superlattices in MoS2/WSe2 Hetero-Bilayers. Sci. Adv.
Zhang, Z. Topology and Polarity of Dislocation Cores Dictate the 2017, 3, e1601459.
Mechanical Strength of Monolayer MoS2. Appl. Mater. Today 2019, (881) Schouteden, K.; Li, Z.; Chen, T.; Song, F.; Partoens, B.; Van
15, 34−42. Haesendonck, C.; Park, K. Moiré Superlattices at the Topological
(864) Karvonen, L.; Säynätjoki, A.; Huttunen, M. J.; Autere, A.; Insulator Bi2Te3. Sci. Rep. 2016, 6, 20278.
Amirsolaimani, B.; Li, S.; Norwood, R. A.; Peyghambarian, N.; (882) Cao, Y.; Fatemi, V.; Fang, S.; Watanabe, K.; Taniguchi, T.;
Lipsanen, H.; Eda, G.; et al. Rapid Visualization of Grain Boundaries Kaxiras, E.; Jarillo-Herrero, P. Unconventional Superconductivity in
in Monolayer MoS2 by Multiphoton Microscopy. Nat. Commun. Magic-Angle Graphene Superlattices. Nature 2018, 556, 43−50.
2017, 8, 15714. (883) Sharpe, A. L.; Fox, E. J.; Barnard, A. W.; Finney, J.; Watanabe,
(865) Park, S.; Kim, M. S.; Kim, H.; Lee, J.; Han, G. H.; Jung, J.; K.; Taniguchi, T.; Kastner, M. A.; Goldhaber-Gordon, D. Emergent
Kim, J. Spectroscopic Visualization of Grain Boundaries of Monolayer Ferromagnetism near Three-Quarters Filling in Twisted Bilayer
Molybdenum Disulfide by Stacking Bilayers. ACS Nano 2015, 9, Graphene. Science 2019, 365, 605−608.
11042−11048. (884) Sunku, S. S.; Ni, G. X.; Jiang, B. Y.; Yoo, H.; Sternbach, A.;
(866) Kim, M. S.; Yun, S. J.; Lee, Y.; Seo, C.; Han, G. H.; Kim, K. K.; McLeod, A. S.; Stauber, T.; Xiong, L.; Taniguchi, T.; Watanabe, K.
Lee, Y. H.; Kim, J. Biexciton Emission from Edges and Grain Photonic Crystals for Nano-Light in Moiré Graphene Superlattices.
Boundaries of Triangular WS2 Monolayers. ACS Nano 2016, 10, Science 2018, 362, 1153−1156.
2399−2405. (885) Bai, Y.; Zhou, L.; Wang, J.; Wu, W.; McGilly, L. J.; Halbertal,
(867) Hsu, W.-T.; Zhao, Z.-A.; Li, L.-J.; Chen, C.-H.; Chiu, M.-H.; D.; Lo, C. F. B.; Liu, F.; Ardelean, J.; Rivera, P.; et al. Excitons in
Chang, P.-S.; Chou, Y.-C.; Chang, W.-H. Second Harmonic Strain-Induced One-Dimensional Moiré Potentials at Transition
Chem. Rev. 2023, 123, 3329−3442
Metal Dichalcogenide Heterojunctions. Nat. Mater. 2020, 19, 1068− Transistor with Low Schottky Barrier Contact by Using Atomic Thick
1073. h-BN as a Tunneling Layer. Adv. Mater. 2016, 28, 8302−8308.
(886) Jiang, Z.; Zhou, W.; Hong, A.; Guo, M.; Luo, X.; Yuan, C. (906) Baugher, B. W. H.; Churchill, H. O. H.; Yang, Y.; Jarillo-
MoS2 Moiré Superlattice for Hydrogen Evolution Reaction. ACS Herrero, P. Intrinsic Electronic Transport Properties of High-Quality
Energy Lett. 2019, 4, 2830−2835. Monolayer and Bilayer MoS2. Nano Lett. 2013, 13, 4212−4216.
(887) Tran, K.; Moody, G.; Wu, F.; Lu, X.; Choi, J.; Kim, K.; Rai, A.; (907) Li, S.-L.; Wakabayashi, K.; Xu, Y.; Nakaharai, S.; Komatsu, K.;
Sanchez, D. A.; Quan, J.; Singh, A.; et al. Evidence for Moiré Excitons Li, W.-W.; Lin, Y.-F.; Aparecido-Ferreira, A.; Tsukagoshi, K.
in vdW Heterostructures. Nature 2019, 567, 71−75. Thickness-Dependent Interfacial Coulomb Scattering in Atomically
(888) Li, X.; Lin, M.-W.; Lin, J.; Huang, B.; Puretzky, A. A.; Ma, C.; Thin Field-Effect Transistors. Nano Lett. 2013, 13, 3546−3552.
Wang, K.; Zhou, W.; Pantelides, S. T.; Chi, M.; Kravchenko, I.; et al. (908) Huang, Y.-T.; Chen, Y.-H.; Ho, Y.-J.; Huang, S.-W.; Chang,
Two-Dimensional GaSe/MoSe2 Misfit Bilayer Heterojunctions by Y.-R.; Watanabe, K.; Taniguchi, T.; Chiu, H.-C.; Liang, C.-T.; Sankar,
vdW Epitaxy. Sci. Adv. 2016, 2, e1501882. R.; et al. High-Performance InSe Transistors with Ohmic Contact
(889) Yang, T.; Zheng, B.; Wang, Z.; Xu, T.; Pan, C.; Zou, J.; Zhang, Enabled by Nonrectifying Barrier-Type Indium Electrodes. ACS Appl.
X.; Qi, Z.; Liu, H.; Feng, Y.; et al. vdW Epitaxial Growth and Mater. Interfaces 2018, 10, 33450−33456.
Optoelectronics of Large-Scale WSe2/SnS2 Vertical Bilayer P−N (909) Li, M.; Lin, C.-Y.; Yang, S.-H.; Chang, Y.-M.; Chang, J.-K.;
Junctions. Nat. Commun. 2017, 8, 1906. Yang, F.-S.; Zhong, C.; Jian, W.-B.; Lien, C.-H.; Ho, C.-H.; et al. High
(890) Choi, J.; Hsu, W.-T.; Lu, L.-S.; Sun, L.; Cheng, H.-Y.; Lee, M.- Mobilities in Layered InSe Transistors with Indium-Encapsulation-
H.; Quan, J.; Tran, K.; Wang, C.-Y.; Staab, M.; et al. Moiré Potential Induced Surface Charge Doping. Adv. Mater. 2018, 30, 1803690.
Impedes Interlayer Exciton Diffusion in vdW Heterostructures. Sci. (910) Zou, X.; Wang, J.; Chiu, C.-H.; Wu, Y.; Xiao, X.; Jiang, C.;
Adv. 2020, 6, eaba8866. Wu, W.-W.; Mai, L.; Chen, T.; Li, J.; et al. Interface Engineering for
(891) Hsu, W.-T.; Lu, L.-S.; Wu, P.-H.; Lee, M.-H.; Chen, P.-J.; Wu, High-Performance Top-Gated MoS2 Field-Effect Transistors. Adv.
P.-Y.; Chou, Y.-C.; Jeng, H.-T.; Li, L.-J.; Chu, M.-W.; et al. Negative Mater. 2014, 26, 6255−6261.
Circular Polarization Emissions from WSe2/MoSe2 Commensurate (911) Yu, S.; Kim, J. S.; Jeon, P. J.; Ahn, J.; Park, J. C.; Im, S.
Heterobilayers. Nat. Commun. 2018, 9, 1356. Transition Metal Dichalcogenide-Based Transistor Circuits for Gray
(892) Ovchinnikov, D.; Allain, A.; Huang, Y.-S.; Dumcenco, D.; Kis, Scale Organic Light-Emitting Displays. Adv. Funct. Mater. 2017, 27,
A. Electrical Transport Properties of Single-Layer WS2. ACS Nano 1603682.
2014, 8, 8174−8181. (912) Sasabe, H.; Kido, J. Development of High Performance Oleds
(893) Lembke, D.; Bertolazzi, S.; Kis, A. Single-Layer MoS2 for General Lighting. J. Mater. Chem. C 2013, 1, 1699−1707.
Electronics. Acc. Chem. Res. 2015, 48, 100−110. (913) Choi, M.; Bae, S.-R.; Hu, L.; Hoang, A. T.; Kim, S. Y.; Ahn, J.-
(894) Yoon, Y.; Ganapathi, K.; Salahuddin, S. How Good Can H. Full-Color Active-Matrix Organic Light-Emitting Diode Display on
Monolayer MoS2 Transistors Be? Nano Lett. 2011, 11, 3768−3773. Human Skin Based on a Large-Area MoS2 Backplane. Sci. Adv. 2020,
(895) Liu, L.; Lu, Y.; Guo, J. On Monolayer MoS2 Field-Effect 6, eabb5898.
Transistors at the Scaling Limit. IEEE Trans. Electron Devices 2013, (914) Liu, Y.; Guo, J.; Zhu, E.; Liao, L.; Lee, S.-J.; Ding, M.; Shakir,
60, 4133−4139. I.; Gambin, V.; Huang, Y.; Duan, X. Approaching the Schottky−Mott
(896) Liu, Y.; Duan, X.; Shin, H.-J.; Park, S.; Huang, Y.; Duan, X. Limit in vdW Metal−Semiconductor Junctions. Nature 2018, 557,
Promises and Prospects of Two-Dimensional Transistors. Nature 696−700.
2021, 591, 43−53. (915) Huh, W.; Lee, D.; Lee, C.-H. Memristors Based on 2D
(897) Migita, S.; Morita, Y.; Matsukawa, T.; Masahara, M.; Ota, H. Materials as an Artificial Synapse for Neuromorphic Electronics. Adv.
Experimental Demonstration of Ultrashort-Channel (3 nm) Junction- Mater. 2020, 32, 2002092.
less Fets Utilizing Atomically Sharp V-Grooves on Soi. IEEE Trans. (916) Bertolazzi, S.; Bondavalli, P.; Roche, S.; San, T.; Choi, S.-Y.;
Nanotechnol. 2014, 13, 208−215. Colombo, L.; Bonaccorso, F.; Samorì, P. Nonvolatile Memories Based
(898) Jiang, J.; Doan, M.-H.; Sun, L.; Kim, H.; Yu, H.; Joo, M.-K.; on Graphene and Related 2D Materials. Adv. Mater. 2019, 31,
Park, S. H.; Yang, H.; Duong, D. L.; Lee, Y. H. Ultrashort Vertical- 1806663.
Channel vdW Semiconductor Transistors. Adv. Sci. 2020, 7, 1902964. (917) Strukov, D. B.; Snider, G. S.; Stewart, D. R.; Williams, R. S.
(899) Li, S.-L.; Tsukagoshi, K.; Orgiu, E.; Samorì, P. Charge The Missing Memristor Found. Nature 2008, 453, 80−83.
Transport and Mobility Engineering in Two-Dimensional Transition (918) Yang, J. J.; Pickett, M. D.; Li, X.; Ohlberg, D. A. A.; Stewart,
Metal Chalcogenide Semiconductors. Chem. Soc. Rev. 2016, 45, 118− D. R.; Williams, R. S. Memristive Switching Mechanism for Metal/
151. Oxide/Metal Nanodevices. Nat. Nanotechnol. 2008, 3, 429−433.
(900) Radisavljevic, B.; Kis, A. Mobility Engineering and a Metal− (919) Waser, R.; Dittmann, R.; Staikov, G.; Szot, K. Redox-Based
Insulator Transition in Monolayer MoS2. Nat. Mater. 2013, 12, 815− Resistive Switching Memories − Nanoionic Mechanisms, Prospects,
820. and Challenges. Adv. Mater. 2009, 21, 2632−2663.
(901) Schmidt, H.; Wang, S.; Chu, L.; Toh, M.; Kumar, R.; Zhao, (920) Yang, J. J.; Strukov, D. B.; Stewart, D. R. Memristive Devices
W.; Castro Neto, A. H.; Martin, J.; Adam, S.; Ö zyilmaz, B.; et al. for Computing. Nat. Nanotechnol. 2013, 8, 13−24.
Transport Properties of Monolayer MoS2 Grown by Chemical Vapor (921) Arnold, A. J.; Razavieh, A.; Nasr, J. R.; Schulman, D. S.;
Deposition. Nano Lett. 2014, 14, 1909−1913. Eichfeld, C. M.; Das, S. Mimicking Neurotransmitter Release in
(902) Patil, V.; Kim, J.; Agrawal, K.; Park, T.; Yi, J.; Aoki, N.; Chemical Synapses via Hysteresis Engineering in MoS2 Transistors.
Watanabe, K.; Taniguchi, T.; Kim, G.-H. High Mobility Field-Effect ACS Nano 2017, 11, 3110−3118.
Transistors Based on MoS2 Crystals Grown by the Flux Method. (922) Bao, L.; Zhu, J.; Yu, Z.; Jia, R.; Cai, Q.; Wang, Z.; Xu, L.; Wu,
Nanotechnology 2021, 32, 325603. Y.; Yang, Y.; Cai, Y.; et al. Dual-Gated MoS2 Neuristor for
(903) Kim, T.; Fan, S.; Lee, S.; Joo, M.-K.; Lee, Y. H. High-Mobility Neuromorphic Computing. ACS Appl. Mater. Interfaces 2019, 11,
Junction Field-Effect Transistor via Graphene/MoS2 Heterointerface. 41482−41489.
Sci. Rep. 2020, 10, 13101. (923) Zhao, X.; Ning, S.; Fu, W.; Pennycook, S. J.; Loh, K. P.
(904) Kim, S.; Konar, A.; Hwang, W.-S.; Lee, J. H.; Lee, J.; Yang, J.; Differentiating Polymorphs in Molybdenum Disulfide via Electron
Jung, C.; Kim, H.; Yoo, J.-B.; Choi, J.-Y.; et al. High-Mobility and Microscopy. Adv. Mater. 2018, 30, 1802397.
Low-Power Thin-Film Transistors Based on Multilayer MoS2 (924) Kwon, K. C.; Baek, J. H.; Hong, K.; Kim, S. Y.; Jang, H. W.
Crystals. Nat. Commun. 2012, 3, 1011. Memristive Devices Based on Two-Dimensional Transition Metal
(905) Wang, J.; Yao, Q.; Huang, C.-W.; Zou, X.; Liao, L.; Chen, S.; Chalcogenides for Neuromorphic Computing. Nano-Micro Lett. 2022,
Fan, Z.; Zhang, K.; Wu, W.; Xiao, X.; et al. High Mobility MoS2 14, 58.
Chem. Rev. 2023, 123, 3329−3442
(925) Zhang, Z.; Wang, S.; Liu, C.; Xie, R.; Hu, W.; Zhou, P. All-in- (944) Deng, W.; Chen, Y.; You, C.; An, B.; Liu, B.; Li, S.; Zhang, Y.;
One Two-Dimensional Retinomorphic Hardware Device for Motion Yan, H.; Sun, L. Visible-Infrared Dual-Mode MoS2-Graphene-MoS2
Detection and Recognition. Nat. Nanotechnol. 2022, 17, 27−32. Phototransistor with High Ratio of Iph/Idark. 2D Mater. 2018, 5,
(926) Zhu, Y.; Wu, C.; Xu, Z.; Liu, Y.; Hu, H.; Guo, T.; Kim, T. W.; No. 045027.
Chai, Y.; Li, F. Light-Emitting Memristors for Optoelectronic (945) Meng, J.; Song, H.-D.; Li, C.-Z.; Jin, Y.; Tang, L.; Liu, D.;
Artificial Efferent Nerve. Nano Lett. 2021, 21, 6087−6094. Liao, Z.-M.; Xiu, F.; Yu, D.-P. Lateral Graphene P−N Junctions
(927) Emboras, A.; Alabastri, A.; Lehmann, P.; Portner, K.; Formed by the Graphene/MoS2 Hybrid Interface. Nanoscale 2015, 7,
Weilenmann, C.; Ma, P.; Cheng, B.; Lewerenz, M.; Passerini, E.; 11611−11619.
Koch, U.; et al. Opto-Electronic Memristors: Prospects and (946) Choi, M. S.; Qu, D.; Lee, D.; Liu, X.; Watanabe, K.;
Challenges in Neuromorphic Computing. Appl. Phys. Lett. 2020, Taniguchi, T.; Yoo, W. J. Lateral MoS2 P−N Junction Formed by
117, 230502. Chemical Doping for Use in High-Performance Optoelectronics. ACS
(928) Zhu, X.; Li, D.; Liang, X.; Lu, W. D. Ionic Modulation and Nano 2014, 8, 9332−9340.
Ionic Coupling Effects in MoS2 Devices for Neuromorphic (947) Pak, J.; Lee, I.; Cho, K.; Kim, J.-K.; Jeong, H.; Hwang, W.-T.;
Computing. Nat. Mater. 2019, 18, 141−148. Ahn, G. H.; Kang, K.; Yu, W. J.; Javey, A.; et al. Intrinsic
(929) Cheng, P.; Sun, K.; Hu, Y. H. Memristive Behavior and Ideal Optoelectronic Characteristics of MoS2 Phototransistors via a Fully
Memristor of 1T Phase MoS2 Nanosheets. Nano Lett. 2016, 16, 572− Transparent vdW Heterostructure. ACS Nano 2019, 13, 9638−9646.
576. (948) De Fazio, D.; Goykhman, I.; Yoon, D.; Bruna, M.; Eiden, A.;
(930) Yan, X.; Zhao, Q.; Chen, A. P.; Zhao, J.; Zhou, Z.; Wang, J.; Milana, S.; Sassi, U.; Barbone, M.; Dumcenco, D.; Marinov, K.; et al.
Wang, H.; Zhang, L.; Li, X.; Xiao, Z.; et al. Vacancy-Induced Synaptic High Responsivity, Large-Area Graphene/MoS2 Flexible Photo-
Behavior in 2D WS2 Nanosheet−Based Memristor for Low-Power detectors. ACS Nano 2016, 10, 8252−8262.
Neuromorphic Computing. Small 2019, 15, 1901423. (949) Paul, K. K.; Mawlong, L. P. L.; Giri, P. K. Trion-Inhibited
(931) Tang, B.; Veluri, H.; Li, Y.; Yu, Z. G.; Waqar, M.; Leong, J. F.; Strong Excitonic Emission and Broadband Giant Photoresponsivity
Sivan, M.; Zamburg, E.; Zhang, Y.-W.; Wang, J.; et al. Wafer-Scale from Chemical Vapor-Deposited Monolayer MoS2 Grown in Situ on
Solution-Processed 2D Material Analog Resistive Memory Array for TiO2 Nanostructure. ACS Appl. Mater. Interfaces 2018, 10, 42812−
Memory-Based Computing. Nat. Commun. 2022, 13, 3037. 42825.
(932) Dasgupta, N. P.; Sun, J.; Liu, C.; Brittman, S.; Andrews, S. C.; (950) Zhang, K.; Zhang, T.; Cheng, G.; Li, T.; Wang, S.; Wei, W.;
Lim, J.; Gao, H.; Yan, R.; Yang, P. 25th Anniversary Article: Zhou, X.; Yu, W.; Sun, Y.; Wang, P.; et al. Interlayer Transition and
Semiconductor Nanowires − Synthesis, Characterization, and Infrared Photodetection in Atomically Thin Type-II MoTe2/MoS2
Applications. Adv. Mater. 2014, 26, 2137−2184. vdW Heterostructures. ACS Nano 2016, 10, 3852−3858.
(933) Guo, C.; Guo, W.; Xu, H.; Zhang, L.; Chen, G.; D’Olimpio, (951) Nourbakhsh, A.; Zubair, A.; Dresselhaus, M. S.; Palacios, T.
G.; Kuo, C.-N.; Lue, C. S.; Wang, L.; Politano, A.; et al. Ultrasensitive Transport Properties of a MoS2/WSe2 Heterojunction Transistor and
Ambient-Stable SnSe2-Based Broadband Photodetectors for Room- Its Potential for Application. Nano Lett. 2016, 16, 1359−1366.
Temperature IR/THz Energy Conversion and Imaging. 2D Mater. (952) Roy, T.; Tosun, M.; Cao, X.; Fang, H.; Lien, D.-H.; Zhao, P.;
2020, 7, No. 035026. Chen, Y.-Z.; Chueh, Y.-L.; Guo, J.; Javey, A. Dual-Gated MoS2/WSe2
(934) Kufer, D.; Konstantatos, G. Highly Sensitive, Encapsulated vdW Tunnel Diodes and Transistors. ACS Nano 2015, 9, 2071−2079.
MoS2 Photodetector with Gate Controllable Gain and Speed. Nano (953) Doan, M.-H.; Jin, Y.; Adhikari, S.; Lee, S.; Zhao, J.; Lim, S. C.;
Lett. 2015, 15, 7307−7313. Lee, Y. H. Charge Transport in MoS2/WSe2 vdW Heterostructure
(935) Choi, W.; Cho, M. Y.; Konar, A.; Lee, J. H.; Cha, G.-B.; Hong, with Tunable Inversion Layer. ACS Nano 2017, 11, 3832−3840.
S. C.; Kim, S.; Kim, J.; Jena, D.; Joo, J.; et al. High-Detectivity (954) Li, H.; Ye, L.; Xu, J. High-Performance Broadband Floating-
Multilayer MoS2 Phototransistors with Spectral Response from Base Bipolar Phototransistor Based on WSe2/BP/MoS2 Hetero-
Ultraviolet to Infrared. Adv. Mater. 2012, 24, 5832−5836. structure. ACS Photonics 2017, 4, 823−829.
(936) Lee, H. S.; Min, S.-W.; Chang, Y.-G.; Park, M. K.; Nam, T.; (955) Lee, C.-H.; Lee, G.-H.; van der Zande, A. M.; Chen, W.; Li,
Kim, H.; Kim, J. H.; Ryu, S.; Im, S. MoS2 Nanosheet Phototransistors Y.; Han, M.; Cui, X.; Arefe, G.; Nuckolls, C.; Heinz, T. F.; et al.
with Thickness-Modulated Optical Energy Gap. Nano Lett. 2012, 12, Atomically Thin P−N Junctions with vdW Heterointerfaces. Nat.
3695−3700. Nanotechnol. 2014, 9, 676−681.
(937) Kufer, D.; Nikitskiy, I.; Lasanta, T.; Navickaite, G.; Koppens, (956) Zhang, K.; Zhai, J.; Wang, Z. L. A Monolayer Mos2 P-N
F. H. L.; Konstantatos, G. Hybrid 2D−0D MoS2−PbS Quantum Dot Homogenous Photodiode with Enhanced Photoresponse by Piezo-
Photodetectors. Adv. Mater. 2015, 27, 176−180. Phototronic Effect. 2D Mater. 2018, 5, No. 035038.
(938) Huo, N.; Konstantatos, G. Ultrasensitive All-2D MoS2 (957) Lei, S.; Ge, L.; Najmaei, S.; George, A.; Kappera, R.; Lou, J.;
Phototransistors Enabled by an out-of-Plane MoS2 PN Homojunc- Chhowalla, M.; Yamaguchi, H.; Gupta, G.; Vajtai, R.; et al. Evolution
tion. Nat. Commun. 2017, 8, 572. of the Electronic Band Structure and Efficient Photo-Detection in
(939) Kim, S.-G.; Kim, S.-H.; Park, J.; Kim, G.-S.; Park, J.-H.; Atomic Layers of InSe. ACS Nano 2014, 8, 1263−1272.
Saraswat, K. C.; Kim, J.; Yu, H.-Y. Infrared Detectable MoS2 (958) Jang, H.; Seok, Y.; Choi, Y.; Cho, S.-H.; Watanabe, K.;
Phototransistor and Its Application to Artificial Multilevel Optic- Taniguchi, T.; Lee, K. High-Performance near-Infrared Photo-
Neural Synapse. ACS Nano 2019, 13, 10294−10300. detectors Based on Surface-Doped InSe. Adv. Funct. Mater. 2021,
(940) Zhang, Q.; Bao, W.; Gong, A.; Gong, T.; Ma, D.; Wan, J.; Dai, 31, 2006788.
J.; Munday, J. N.; He, J.-H.; Hu, L.; et al. A Highly Sensitive, Highly (959) Zhao, Q.; Wang, W.; Carrascoso-Plana, F.; Jie, W.; Wang, T.;
Transparent, Gel-Gated MoS2 Phototransistor on Biodegradable Castellanos-Gomez, A.; Frisenda, R. The Role of Traps in the
Nanopaper. Nanoscale 2016, 8, 14237−14242. Photocurrent Generation Mechanism in Thin InSe Photodetectors.
(941) Lopez-Sanchez, O.; Lembke, D.; Kayci, M.; Radenovic, A.; Mater. Horiz. 2020, 7, 252−262.
Kis, A. Ultrasensitive Photodetectors Based on Monolayer MoS2. Nat. (960) Tamalampudi, S. R.; Lu, Y.-Y.; U, R. K.; Sankar, R.; Liao, C.-
Nanotechnol. 2013, 8, 497−501. D.; B, K. M.; Cheng, C.-H.; Chou, F. C.; Chen, Y.-T. High
(942) Lee, Y. T.; Kang, J.-H.; Kwak, K.; Ahn, J.; Choi, H. T.; Ju, B.- Performance and Bendable Few-Layered InSe Photodetectors with
K.; Shokouh, S. H.; Im, S.; Park, M.-C.; Hwang, D. K. High- Broad Spectral Response. Nano Lett. 2014, 14, 2800−2806.
Performance 2D MoS2 Phototransistor for Photo Logic Gate and (961) Mudd, G. W.; Svatek, S. A.; Hague, L.; Makarovsky, O.;
Image Sensor. ACS Photonics 2018, 5, 4745−4750. Kudrynskyi, Z. R.; Mellor, C. J.; Beton, P. H.; Eaves, L.; Novoselov, K.
(943) Yore, A. E.; Smithe, K. K. H.; Jha, S.; Ray, K.; Pop, E.; Newaz, S.; Kovalyuk, Z. D.; et al. High Broad-Band Photoresponsivity of
A. K. M. Large Array Fabrication of High Performance Monolayer Mechanically Formed InSe−Graphene vdW Heterostructures. Adv.
MoS2 Photodetectors. Appl. Phys. Lett. 2017, 111, No. 043110. Mater. 2015, 27, 3760−3766.
Chem. Rev. 2023, 123, 3329−3442
(962) Liu, B.; Tang, B.; Lv, F.; Zeng, Y.; Liao, J.; Wang, S.; Chen, Q. (981) Rowland, C. E.; Fedin, I.; Zhang, H.; Gray, S. K.; Govorov, A.
Photodetector Based on Heterostructure of Two-Dimensional WSe2/ O.; Talapin, D. V.; Schaller, R. D. Picosecond Energy Transfer and
In2Se3. Nanotechnology 2020, 31, No. 065203. Multiexciton Transfer Outpaces Auger Recombination in Binary
(963) Feng, W.; Gao, F.; Hu, Y.; Dai, M.; Li, H.; Wang, L.; Hu, P. CdSe Nanoplatelet Solids. Nat. Mater. 2015, 14, 484−489.
High-Performance and Flexible Photodetectors Based on Chemical (982) Scott, R.; Heckmann, J.; Prudnikau, A. V.; Antanovich, A.;
Vapor Deposition Grown Two-Dimensional In2Se3 Nanosheets. Mikhailov, A.; Owschimikow, N.; Artemyev, M.; Climente, J. I.;
Nanotechnology 2018, 29, 445205. Woggon, U.; Grosse, N. B.; et al. Directed Emission of CdSe
(964) Island, J. O.; Blanter, S. I.; Buscema, M.; van der Zant, H. S. J.; Nanoplatelets Originating from Strongly Anisotropic 2D Electronic
Castellanos-Gomez, A. Gate Controlled Photocurrent Generation Structure. Nat. Nanotechnol. 2017, 12, 1155−1160.
Mechanisms in High-Gain In2Se3 Phototransistors. Nano Lett. 2015, (983) Kung, S.-C.; van der Veer, W. E.; Yang, F.; Donavan, K. C.;
15, 7853−7858. Penner, R. M. 20 ms Photocurrent Response from Lithographically
(965) Zhou, J.; Zeng, Q.; Lv, D.; Sun, L.; Niu, L.; Fu, W.; Liu, F.; Patterned Nanocrystalline Cadmium Selenide Nanowires. Nano Lett.
Shen, Z.; Jin, C.; Liu, Z. Controlled Synthesis of High-Quality 2010, 10, 1481−1485.
Monolayered Α-In2Se3 via Physical Vapor Deposition. Nano Lett. (984) Fang, X.; Bando, Y.; Liao, M.; Gautam, U. K.; Zhi, C.; Dierre,
2015, 15, 6400−6405. B.; Liu, B.; Zhai, T.; Sekiguchi, T.; Koide, Y.; et al. Single-Crystalline
(966) Hu, P.; Wen, Z.; Wang, L.; Tan, P.; Xiao, K. Synthesis of Few- ZnS Nanobelts as Ultraviolet-Light Sensors. Adv. Mater. 2009, 21,
Layer GaSe Nanosheets for High Performance Photodetectors. ACS 2034−2039.
Nano 2012, 6, 5988−5994. (985) Britnell, L.; Ribeiro, R. M.; Eckmann, A.; Jalil, R.; Belle, B. D.;
(967) Lu, R.; Liu, J.; Luo, H.; Chikan, V.; Wu, J. Z. Graphene/GaSe- Mishchenko, A.; Kim, Y. J.; Gorbachev, R. V.; Georgiou, T.; Morozov,
Nanosheet Hybrid: Towards High Gain and Fast Photoresponse. Sci. S. V.; et al. Strong Light-Matter Interactions in Heterostructures of
Rep. 2016, 6, 19161. Atomically Thin Films. Science 2013, 340, 1311−1314.
(968) Lei, S.; Ge, L.; Liu, Z.; Najmaei, S.; Shi, G.; You, G.; Lou, J.; (986) Withers, F.; Del Pozo-Zamudio, O.; Mishchenko, A.; Rooney,
Vajtai, R.; Ajayan, P. M. Synthesis and Photoresponse of Large GaSe A. P.; Gholinia, A.; Watanabe, K.; Taniguchi, T.; Haigh, S. J.; Geim, A.
Atomic Layers. Nano Lett. 2013, 13, 2777−2781. K.; Tartakovskii, A. I.; et al. Light-Emitting Diodes by Band-Structure
(969) Wang, Z.; Safdar, M.; Mirza, M.; Xu, K.; Wang, Q.; Huang, Y.; Engineering in vdW Heterostructures. Nat. Mater. 2015, 14, 301−
Wang, F.; Zhan, X.; He, J. High-Performance Flexible Photodetectors 306.
Based on Gate Nanosheets. Nanoscale 2015, 7, 7252−7258. (987) Ross, J. S.; Klement, P.; Jones, A. M.; Ghimire, N. J.; Yan, J.;
(970) Liu, F.; Shimotani, H.; Shang, H.; Kanagasekaran, T.; Mandrus, D. G.; Taniguchi, T.; Watanabe, K.; Kitamura, K.; Yao, W.;
Zólyomi, V.; Drummond, N.; Fal’ko, V. I.; Tanigaki, K. High- et al. Electrically Tunable Excitonic Light-Emitting Diodes Based on
Sensitivity Photodetectors Based on Multilayer Gate Flakes. ACS Monolayer WSe2 P−N Junctions. Nat. Nanotechnol. 2014, 9, 268−
Nano 2014, 8, 752−760. 272.
(971) Mahdi, M. S.; Ibrahim, K.; Hmood, A.; Ahmed, N. M.; Azzez, (988) Furchi, M. M.; Pospischil, A.; Libisch, F.; Burgdörfer, J.;
S. A.; Mustafa, F. I. A Highly Sensitive Flexible Sns Thin Film Mueller, T. Photovoltaic Effect in an Electrically Tunable vdW
Photodetector in the Ultraviolet to near Infrared Prepared by Heterojunction. Nano Lett. 2014, 14, 4785−4791.
Chemical Bath Deposition. RSC Adv. 2016, 6, 114980−114988. (989) Pospischil, A.; Furchi, M. M.; Mueller, T. Solar-Energy
(972) Tian, H.; Fan, C.; Liu, G.; Yuan, S.; Zhang, Y.; Wang, M.; Li, Conversion and Light Emission in an Atomic Monolayer P−N Diode.
E. Ultrafast Broadband Photodetector Based on Sns Synthesized by Nat. Nanotechnol. 2014, 9, 257−261.
Hydrothermal Method. Appl. Surf. Sci. 2019, 487, 1043−1048. (990) Sundaram, R. S.; Engel, M.; Lombardo, A.; Krupke, R.;
(973) Chen, J.; Xu, J.; Shi, S.; Cao, R.; Liu, D.; Bu, Y.; Yang, P.; Xu, Ferrari, A. C.; Avouris, P.; Steiner, M. Electroluminescence in Single
J.; Zhang, X.; Li, L. Novel Self-Powered Photodetector with Binary Layer MoS2. Nano Lett. 2013, 13, 1416−1421.
Photoswitching Based on SnSx/TiO2 Heterojunctions. ACS Appl. (991) Zhang, Y. J.; Oka, T.; Suzuki, R.; Ye, J. T.; Iwasa, Y.
Mater. Interfaces 2020, 12, 23145−23154. Electrically Switchable Chiral Light-Emitting Transistor. Science 2014,
(974) Yu, P.; Yu, X.; Lu, W.; Lin, H.; Sun, L.; Du, K.; Liu, F.; Fu, W.; 344, 725−728.
Zeng, Q.; Shen, Z.; et al. Fast Photoresponse from 1T Tin Diselenide (992) Withers, F.; Del Pozo-Zamudio, O.; Schwarz, S.; Dufferwiel,
Atomic Layers. Adv. Funct. Mater. 2016, 26, 137−145. S.; Walker, P. M.; Godde, T.; Rooney, A. P.; Gholinia, A.; Woods, C.
(975) Zhou, X.; Gan, L.; Tian, W.; Zhang, Q.; Jin, S.; Li, H.; Bando, R.; Blake, P.; et al. WSe2 Light-Emitting Tunneling Transistors with
Y.; Golberg, D.; Zhai, T. Ultrathin SnSe2 Flakes Grown by Chemical Enhanced Brightness at Room Temperature. Nano Lett. 2015, 15,
Vapor Deposition for High-Performance Photodetectors. Adv. Mater. 8223−8228.
2015, 27, 8035−8041. (993) Baugher, B. W. H.; Churchill, H. O. H.; Yang, Y.; Jarillo-
(976) Su, G.; Hadjiev, V. G.; Loya, P. E.; Zhang, J.; Lei, S.; Herrero, P. Optoelectronic Devices Based on Electrically Tunable P−
Maharjan, S.; Dong, P.; M. Ajayan, P.; Lou, J.; Peng, H. Chemical N Diodes in a Monolayer Dichalcogenide. Nat. Nanotechnol. 2014, 9,
Vapor Deposition of Thin Crystals of Layered Semiconductor SnS2 262−267.
for Fast Photodetection Application. Nano Lett. 2015, 15, 506−513. (994) Ye, Y.; Ye, Z.; Gharghi, M.; Zhu, H.; Zhao, M.; Wang, Y.; Yin,
(977) Fan, C.; Liu, Z.; Yuan, S.; Meng, X.; An, X.; Jing, Y.; Sun, C.; X.; Zhang, X. Exciton-Dominant Electroluminescence from a Diode
Zhang, Y.; Zhang, Z.; Wang, M.; et al. Enhanced Photodetection of Monolayer MoS2. Appl. Phys. Lett. 2014, 104, 193508.
Performance of Photodetectors Based on Indium-Doped Tin (995) Jo, S.; Ubrig, N.; Berger, H.; Kuzmenko, A. B.; Morpurgo, A.
Disulfide Few Layers. ACS Appl. Mater. Interfaces 2021, 13, 35889− F. Mono- and Bilayer WS2 Light-Emitting Transistors. Nano Lett.
35896. 2014, 14, 2019−2025.
(978) Gupta, S. U.; Dalvaniya, A. G.; Patel, N. F.; Bhakhar, S. A.; (996) Ponomarev, E.; Gutiérrez-Lezama, I.; Ubrig, N.; Morpurgo, A.
Nair, S.; Joy, J.; Patel, K. D.; Solanki, G. K.; Pathak, V. M.; Som, N. F. Ambipolar Light-Emitting Transistors on Chemical Vapor
N.; et al. Optical Switching Device Based on a Crystalline SnSe2 Deposited Monolayer MoS2. Nano Lett. 2015, 15, 8289−8294.
Photodetector in Diverse Conditions. ACS Appl. Electron. Mater. (997) Clark, G.; Schaibley, J. R.; Ross, J.; Taniguchi, T.; Watanabe,
2021, 3, 4859−4869. K.; Hendrickson, J. R.; Mou, S.; Yao, W.; Xu, X. Single Defect Light-
(979) Shalev, E.; Oksenberg, E.; Rechav, K.; Popovitz-Biro, R.; Emitting Diode in a vdW Heterostructure. Nano Lett. 2016, 16,
Joselevich, E. Guided CdSe Nanowires Parallelly Integrated into Fast 3944−3948.
Visible-Range Photodetectors. ACS Nano 2017, 11, 213−220. (998) Cheng, R.; Li, D.; Zhou, H.; Wang, C.; Yin, A.; Jiang, S.; Liu,
(980) Zhao, W.; Liu, L.; Xu, M.; Wang, X.; Zhang, T.; Wang, Y.; Y.; Chen, Y.; Huang, Y.; Duan, X. Electroluminescence and
Zhang, Z.; Qin, S.; Liu, Z. Single CdS Nanorod for High Responsivity Photocurrent Generation from Atomically Sharp WSe2 /MoS2
UV−Visible Photodetector. Adv. Opt. Mater. 2017, 5, 1700159. Heterojunction P−N Diodes. Nano Lett. 2014, 14, 5590−5597.
Chem. Rev. 2023, 123, 3329−3442
(999) Liu, X.; Galfsky, T.; Sun, Z.; Xia, F.; Lin, E.-c.; Lee, Y.-H.; (1018) Memaran, S.; Pradhan, N. R.; Lu, Z.; Rhodes, D.; Ludwig, J.;
Kéna-Cohen, S.; Menon, V. M. Strong Light−Matter Coupling in Zhou, Q.; Ogunsolu, O.; Ajayan, P. M.; Smirnov, D.; Fernández-
Two-Dimensional Atomic Crystals. Nat. Photonics 2015, 9, 30−34. Domínguez, A. I.; et al. Pronounced Photovoltaic Response from
(1000) Dufferwiel, S.; Schwarz, S.; Withers, F.; Trichet, A. A. P.; Li, Multilayered Transition-Metal Dichalcogenides PN-Junctions. Nano
F.; Sich, M.; Del Pozo-Zamudio, O.; Clark, C.; Nalitov, A.; Lett. 2015, 15, 7532−7538.
Solnyshkov, D. D.; et al. Exciton−Polaritons in vdW Heterostructures (1019) Jariwala, D.; Davoyan, A. R.; Wong, J.; Atwater, H. A. vdW
Embedded in Tunable Microcavities. Nat. Commun. 2015, 6, 8579. Materials for Atomically-Thin Photovoltaics: Promise and Outlook.
(1001) Wu, S.; Buckley, S.; Schaibley, J. R.; Feng, L.; Yan, J.; ACS Photonics 2017, 4, 2962−2970.
Mandrus, D. G.; Hatami, F.; Yao, W.; Vučković, J.; Majumdar, A.; (1020) Kaltenbrunner, M.; Adam, G.; Głowacki, E. D.; Drack, M.;
et al. Monolayer Semiconductor Nanocavity Lasers with Ultralow Schwödiauer, R.; Leonat, L.; Apaydin, D. H.; Groiss, H.; Scharber, M.
Thresholds. Nature 2015, 520, 69−72. C.; White, M. S.; et al. Flexible High Power-Per-Weight Perovskite
(1002) Ye, Y.; Wong, Z. J.; Lu, X.; Ni, X.; Zhu, H.; Chen, X.; Wang, Solar Cells with Chromium Oxide−Metal Contacts for Improved
Y.; Zhang, X. Monolayer Excitonic Laser. Nat. Photonics 2015, 9, Stability in Air. Nat. Mater. 2015, 14, 1032−1039.
733−737. (1021) Nassiri Nazif, K.; Daus, A.; Hong, J.; Lee, N.; Vaziri, S.;
(1003) Salehzadeh, O.; Djavid, M.; Tran, N. H.; Shih, I.; Mi, Z. Kumar, A.; Nitta, F.; Chen, M. E.; Kananian, S.; Islam, R.; et al. High-
Optically Pumped Two-Dimensional MoS2 Lasers Operating at Specific-Power Flexible Transition Metal Dichalcogenide Solar Cells.
Room-Temperature. Nano Lett. 2015, 15, 5302−5306. Nat. Commun. 2021, 12, 7034.
(1004) Liu, C.-H.; Clark, G.; Fryett, T.; Wu, S.; Zheng, J.; Hatami, (1022) Akama, T.; Okita, W.; Nagai, R.; Li, C.; Kaneko, T.; Kato, T.
F.; Xu, X.; Majumdar, A. Nanocavity Integrated vdW Heterostructure Schottky Solar Cell Using Few-Layered Transition Metal Dichalco-
Light-Emitting Tunneling Diode. Nano Lett. 2017, 17, 200−205. genides toward Large-Scale Fabrication of Semitransparent and
(1005) Hwangbo, S.; Hu, L.; Hoang, A. T.; Choi, J. Y.; Ahn, J.-H. Flexible Power Generator. Sci. Rep. 2017, 7, 11967.
Wafer-Scale Monolithic Integration of Full-Colour Micro-Led Display (1023) Hinnemann, B.; Moses, P. G.; Bonde, J.; Jo̷ rgensen, K. P.;
Using MoS2 Transistor. Nat. Nanotechnol. 2022, 17, 500−506. Nielsen, J. H.; Horch, S.; Chorkendorff, I.; No̷ rskov, J. K. Biomimetic
(1006) Diroll, B. T.; Talapin, D. V.; Schaller, R. D. Violet-to-Blue Hydrogen Evolution: MoS2 Nanoparticles as Catalyst for Hydrogen
Gain and Lasing from Colloidal CdS Nanoplatelets: Low-Threshold Evolution. J. Am. Chem. Soc. 2005, 127, 5308−5309.
Stimulated Emission Despite Low Photoluminescence Quantum (1024) Tsai, C.; Chan, K.; Nørskov, J. K.; Abild-Pedersen, F.
Yield. ACS Photonics 2017, 4, 576−583. Theoretical Insights into the Hydrogen Evolution Activity of Layered
̇
(1007) Izmir, M.; Sharma, A.; Shendre, S.; Durmusoglu, E. G.; Transition Metal Dichalcogenides. Surf. Sci. 2015, 640, 133−140.
Sharma, V. K.; Shabani, F.; Baruj, H. D.; Delikanli, S.; Sharma, M.; (1025) Zhu, H.; Zhang, J.; Yanzhang, R.; Du, M.; Wang, Q.; Gao,
Demir, H. V. Blue-Emitting CdSe Nanoplatelets Enabled by Sulfur- G.; Wu, J.; Wu, G.; Zhang, M.; Liu, B.; et al. When Cubic Cobalt
Alloyed Heterostructures for Light-Emitting Diodes with Low Turn- Sulfide Meets Layered Molybdenum Disulfide: A Core-Shell System
on Voltage. ACS Appl. Nano Mater. 2022, 5, 1367−1376.
toward Synergetic Electrocatalytic Water Splitting. Adv. Mater. 2015,
(1008) Wen, Z.; Liu, P.; Ma, J.; Jia, S.; Xiao, X.; Ding, S.; Tang, H.;
27, 4752−4759.
Yang, H.; Zhang, C.; Qu, X.; et al. High-Performance Ultrapure Green
(1026) Guo, X.; Ji, J.; Jiang, Q.; Zhang, L.; Ao, Z.; Fan, X.; Wang, S.;
CdSe/CdS Core/Crown Nanoplatelet Light-Emitting Diodes by
Li, Y.; Zhang, F.; Zhang, G.; et al. Few-Layered Trigonal WS2
Suppressing Nonradiative Energy Transfer. Adv. Electron. Mater.
Nanosheet-Coated Graphite Foam as an Efficient Free-Standing
2021, 7, 2000965.
Electrode for a Hydrogen Evolution Reaction. ACS Appl. Mater.
(1009) Guo, Y.; Gao, F.; Huang, P.; Wu, R.; Gu, W.; Wei, J.; Liu, F.;
Li, H. Light-Emitting Diodes Based on Two-Dimensional Nano- Interfaces 2017, 9, 30591−30598.
(1027) Han, X.; Tong, X.; Liu, X.; Chen, A.; Wen, X.; Yang, N.;
platelets. Energy Mater. Adv. 2022, 2022, 9857943.
(1010) van der Bok, J. C.; Dekker, D. M.; Peerlings, M. L. J.; Guo, X.-Y. Hydrogen Evolution Reaction on Hybrid Catalysts of
Salzmann, B. B. V.; Meijerink, A. Luminescence Line Broadening of Vertical MoS2 Nanosheets and Hydrogenated Graphene. ACS Catal.
CdSe Nanoplatelets and Quantum Dots for Application in W-Leds. J. 2018, 8, 1828−1836.
Phys. Chem. C 2020, 124, 12153−12160. (1028) Seo, B.; Jung, G. Y.; Kim, J. H.; Shin, T. J.; Jeong, H. Y.;
(1011) She, C.; Fedin, I.; Dolzhnikov, D. S.; Dahlberg, P. D.; Engel, Kwak, S. K.; Joo, S. H. Preferential Horizontal Growth of Tungsten
G. S.; Schaller, R. D.; Talapin, D. V. Red, Yellow, Green, and Blue Sulfide on Carbon and Insight into Active Sulfur Sites for the
Amplified Spontaneous Emission and Lasing Using Colloidal CdSe Hydrogen Evolution Reaction. Nanoscale 2018, 10, 3838−3848.
Nanoplatelets. ACS Nano 2015, 9, 9475−9485. (1029) Yin, X.; Yan, Y.; Miao, M.; Zhan, K.; Li, P.; Yang, J.; Zhao,
(1012) Bernardi, M.; Palummo, M.; Grossman, J. C. Extraordinary B.; Xia, B. Y. Quasi-Emulsion Confined Synthesis of Edge-Rich
Sunlight Absorption and One Nanometer Thick Photovoltaics Using Ultrathin MoS2 Nanosheets/Graphene Hybrid for Enhanced Hydro-
Two-Dimensional Monolayer Materials. Nano Lett. 2013, 13, 3664− gen Evolution. Chemistry 2018, 24, 556−560.
3670. (1030) Zhao, L.; Hong, C.; Lin, L.; Wu, H.; Su, Y.; Zhang, X.; Liu,
(1013) Tsuboi, Y.; Wang, F.; Kozawa, D.; Funahashi, K.; Mouri, S.; A. Controllable Nanoscale Engineering of Vertically Aligned MoS2
Miyauchi, Y.; Takenobu, T.; Matsuda, K. Enhanced Photovoltaic Ultrathin Nanosheets by Nitrogen Doping of 3D Graphene Hydrogel
Performances of Graphene/Si Solar Cells by Insertion of a MoS2 Thin for Improved Electrocatalytic Hydrogen Evolution. Carbon 2017, 116,
Film. Nanoscale 2015, 7, 14476−14482. 223−231.
(1014) Hao, L.; Liu, Y.; Gao, W.; Liu, Y.; Han, Z.; Xue, Q.; Zhu, J. (1031) Chatti, M.; Gengenbach, T.; King, R.; Spiccia, L.; Simonov,
Enhanced Photovoltaic Characteristics of MoS2/Si Hybrid Solar Cells A. N. Vertically Aligned Interlayer Expanded MoS2 Nanosheets on a
by Metal Pd Chemical Doping. RSC Adv. 2016, 6, 88443−88443. Carbon Support for Hydrogen Evolution Electrocatalysis. Chem.
(1015) Niu, L.; Li, K.; Zhen, H.; Chui, Y.-S.; Zhang, W.; Yan, F.; Mater. 2017, 29, 3092−3099.
Zheng, Z. Salt-Assisted High-Throughput Synthesis of Single- and (1032) Pramoda, K.; Servottam, S.; Kaur, M.; Rao, C. N. R. Layered
Few-Layer Transition Metal Dichalcogenides and Their Application Nanocomposites of Polymer-Functionalized Reduced Graphene
in Organic Solar Cells. Small 2014, 10, 4651−4657. Oxide and Borocarbonitride with MoS2 and MoSe2 and Their
(1016) Singh, R.; Giri, A.; Pal, M.; Thiyagarajan, K.; Kwak, J.; Lee, Hydrogen Evolution Reaction Activity. ACS Appl. Nano Mater. 2020,
J.-J.; Jeong, U.; Cho, K. Perovskite Solar Cell with MoS2 Electron 3, 1792−1799.
Transport Layer. J. Mater. Chem. A 2019, 7, 7151. (1033) Ko, D.; Jin, X.; Seong, K.-d.; Yan, B.; Chai, H.; Kim, J. M.;
(1017) Wi, S.; Kim, H.; Chen, M.; Nam, H.; Guo, L. J.; Meyhofer, Hwang, M.; Choi, J.; Zhang, W.; Piao, Y. Few-Layered MoS2
E.; Liang, X. Enhancement of Photovoltaic Response in Multilayer Vertically Aligned on 3D Interconnected Porous Carbon Nanosheets
MoS2 Induced by Plasma Doping. ACS Nano 2014, 8, 5270−5281. for Hydrogen Evolution. Appl. Catal., B 2019, 248, 357−365.
Chem. Rev. 2023, 123, 3329−3442
(1034) Ganesan, V.; Lim, S.; Kim, J. Hierarchical Nanoboxes (1051) Deng, J.; Li, H.; Xiao, J.; Tu, Y.; Deng, D.; Yang, H.; Tian,
Composed of Co9S8−MoS2 Nanosheets as Efficient Electrocatalysts H.; Li, J.; Ren, P.; Bao, X. Triggering the Electrocatalytic Hydrogen
for the Hydrogen Evolution Reaction. Chem. Asian J. 2018, 13, 413− Evolution Activity of the Inert Two-Dimensional MoS2 Surface via
420. Single-Atom Metal Doping. Energy Environ. Sci. 2015, 8, 1594−1601.
(1035) Guo, Y.; Tang, J.; Qian, H.; Wang, Z.; Yamauchi, Y. One-Pot (1052) Du, C.; Huang, H.; Jian, J.; Wu, Y.; Shang, M.; Song, W.
Synthesis of Zeolitic Imidazolate Framework 67-Derived Hollow Enhanced Electrocatalytic Hydrogen Evolution Performance of MoS2
Co3S4@MoS2 Heterostructures as Efficient Bifunctional Catalysts. Ultrathin Nanosheets via Sn Doping. Appl. Catal., A 2017, 538, 1−8.
Chem. Mater. 2017, 29, 5566−5573. (1053) Dai, X.; Du, K.; Li, Z.; Liu, M.; Ma, Y.; Sun, H.; Zhang, X.;
(1036) Paquin, F.; Rivnay, J.; Salleo, A.; Stingelin, N.; Silva-Acuña, Yang, Y. Co-Doped MoS2 Nanosheets with the Dominant CoMoS
C. Multi-Phase Microstructures Drive Exciton Dissociation in Neat Phase Coated on Carbon as an Excellent Electrocatalyst for Hydrogen
Semicrystalline Polymeric Semiconductors. J. Mater. Chem. C 2015, 3, Evolution. ACS Appl. Mater. Interfaces 2015, 7, 27242−27253.
10715−10722. (1054) Wu, Z.; Guo, J.; Wang, J.; Liu, R.; Xiao, W.; Xuan, C.; Xia,
(1037) Vikraman, D.; Hussain, S.; Truong, L.; Karuppasamy, K.; K.; Wang, D. Hierarchically Porous Electrocatalyst with Vertically
Kim, H.-J.; Maiyalagan, T.; Chun, S.-H.; Jung, J.; Kim, H.-S. Aligned Defect-Rich CoMoS Nanosheets for the Hydrogen Evolution
Fabrication of MoS2/WSe2 Heterostructures as Electrocatalyst for Reaction in an Alkaline Medium. ACS Appl. Mater. Interfaces 2017, 9,
Enhanced Hydrogen Evolution Reaction. Appl. Surf. Sci. 2019, 480, 5288−5294.
611−620. (1055) Shifa, T. A.; Wang, F.; Liu, K.; Xu, K.; Wang, Z.; Zhan, X.;
(1038) Wu, L.; Zhang, K.; Wang, T.; Xu, X.; Zhao, Y.; Sun, Y.; Jiang, C.; He, J. Engineering the Electronic Structure of 2D WS2
Zhong, W.; Du, Y. Cobalt Sulfide Nanotubes (Co9S8) Decorated with Nanosheets Using Co Incorporation as CoxW(1‑x)S2 for Conspicuously
Amorphous MoSx as Highly Efficient Hydrogen Evolution Electro- Enhanced Hydrogen Generation. Small 2016, 12, 3802−3809.
catalyst. ACS Appl. Nano Mater. 2018, 1, 1083−1093. (1056) Jian, J.; Li, H.; Sun, X.; Kong, D.; Zhang, X.; Zhang, L.; Yuan,
(1039) Zhou, X.; Yang, X.; Li, H.; Hedhili, M. N.; Huang, K.-W.; Li, H.; Feng, S. 1T-2H Crx-MoS2 Ultrathin Nanosheets for Durable and
L.-J.; Zhang, W. Symmetric Synergy of Hybrid CoS2−WS2 Electro- Enhanced Hydrogen Evolution Reaction. ACS Sustainable Chem. Eng.
catalysts for the Hydrogen Evolution Reaction. J. Mater. Chem. A 2019, 7, 7227−7232.
2017, 5, 15552−15558. (1057) Vasu, K.; Meiron, O. E.; Enyashin, A. N.; Bar-Ziv, R.; Bar-
(1040) Sun, L.; Wang, T.; Zhang, L.; Sun, Y.; Xu, K.; Dai, Z.; Ma, F. Sadan, M. Effect of Ru Doping on the Properties of MoSe2
Mace-Like Hierarchical MoS2/NiCo2S4 Composites Supported by Nanoflowers. J. Phys. Chem. C 2019, 123, 1987−1994.
Carbon Fiber Paper: An Efficient Electrocatalyst for the Hydrogen (1058) Zhao, G.; Wang, X.; Wang, S.; Rui, K.; Chen, Y.; Yu, H.; Ma,
Evolution Reaction. J. Power Sources 2018, 377, 142−150. J.; Dou, S. X.; Sun, W. Heteroatom-Doped MoSe2 Nanosheets with
(1041) Tang, B.; Yu, Z. G.; Zhang, Y.; Tang, C.; Seng, H. L.; Seh, Z.
Enhanced Hydrogen Evolution Kinetics for Alkaline Water Splitting.
W.; Zhang, Y.-W.; Pennycook, S. J.; Gong, H.; Yang, W. Metal−
Chem.-Asian J. 2019, 14, 301−306.
Organic Framework-Derived Hierarchical MoS2/CoS2 Nanotube
(1059) Maiti, A.; Srivastava, S. K. Sulphur Edge and Vacancy
Arrays as Ph-Universal Electrocatalysts for Efficient Hydrogen
Assisted Nitrogen−Phosphorus Co-Doped Exfoliated Tungsten
Evolution. J. Mater. Chem. A 2019, 7, 13339−13346.
Disulfide: A Superior Electrocatalyst for Hydrogen Evolution
(1042) Liu, J.; Zheng, Y.; Zhu, D.; Vasileff, A.; Ling, T.; Qiao, S. Z.
Reaction. J. Mater. Chem. A 2018, 6, 19712−19726.
Identification of Ph-Dependent Synergy on Ru/MoS2 Interface: A
(1060) Xiao, W.; Liu, P.; Zhang, J.; Song, W.; Feng, Y. P.; Gao, D.;
Comparison of Alkaline and Acidic Hydrogen Evolution. Nanoscale
Ding, J. Dual-Functional N Dopants in Edges and Basal Plane of
2017, 9, 16616−16621.
(1043) Li, F.; Zhang, L.; Li, J.; Lin, X.; Li, X.; Fang, Y.; Huang, J.; Li, MoS2 Nanosheets toward Efficient and Durable Hydrogen Evolution.
W.; Tian, M.; Jin, J.; Li, R. Synthesis of Cu−MoS2/RGO Hybrid as Adv. Energy Mater. 2017, 7, 1602086.
Non-Noble Metal Electrocatalysts for the Hydrogen Evolution (1061) Liu, Q.; Liu, Q.; Kong, X. Anion Engineering on Free-
Reaction. J. Power Sources 2015, 292, 15−22. Standing Two-Dimensional MoS2 Nanosheets toward Hydrogen
(1044) Shi, Y.; Wang, J.; Wang, C.; Zhai, T. T.; Bao, W. J.; Xu, J. J.; Evolution. Inorg. Chem. 2017, 56, 11462−11465.
Xia, X. H.; Chen, H. Y. Hot Electron of Au Nanorods Activates the (1062) Liu, P.; Zhu, J.; Zhang, J.; Xi, P.; Tao, K.; Gao, D.; Xue, D. P
Electrocatalysis of Hydrogen Evolution on MoS2 Nanosheets. J. Am. Dopants Triggered New Basal Plane Active Sites and Enlarged
Chem. Soc. 2015, 137, 7365−70. Interlayer Spacing in MoS2 Nanosheets toward Electrocatalytic
(1045) Zhao, Y.; Mao, G.; Huang, C.; Cai, P.; Cheng, G.; Luo, W. Hydrogen Evolution. ACS Energy Lett. 2017, 2, 745−752.
Decorating WSe2 Nanosheets with Ultrafine Ru Nanoparticles for (1063) Zhu, T.; Ding, J.; Shao, Q.; Qian, Y.; Huang, X. P,Se-
Boosting Electrocatalytic Hydrogen Evolution in Alkaline Electrolytes. Codoped MoS2 Nanosheets as Accelerated Electrocatalysts for
Inorg. Chem. Front. 2019, 6, 1382−1387. Hydrogen Evolution. ChemCatChem. 2019, 11, 689−692.
(1046) Cheng, Y.; Lu, S.; Liao, F.; Liu, L.; Li, Y.; Shao, M. Rh-MoS2 (1064) Shifa, T. A.; Wang, F.; Liu, K.; Cheng, Z.; Xu, K.; Wang, Z.;
Nanocomposite Catalysts with Pt-Like Activity for Hydrogen Zhan, X.; Jiang, C.; He, J. Efficient Catalysis of Hydrogen Evolution
Evolution Reaction. Adv. Funct. Mater. 2017, 27, 1700359. Reaction from WS2(1‑x)P2x Nanoribbons. Small 2017, 13, 1603706.
(1047) Liu, P.; Zhu, J.; Zhang, J.; Tao, K.; Gao, D.; Xi, P. Active (1065) Liang, K.; Yan, Y.; Guo, L.; Marcus, K.; Li, Z.; Zhou, L.; Li,
Basal Plane Catalytic Activity and Conductivity in Zn Doped MoS2 Y.; Ye, R.; Orlovskaya, N.; Sohn, Y.-H.; Yang, Y. Strained W(SexS1−x)2
Nanosheets for Efficient Hydrogen Evolution. Electrochim. Acta 2018, Nanoporous Films for Highly Efficient Hydrogen Evolution. ACS
260, 24−30. Energy Lett. 2017, 2, 1315−1320.
(1048) Qian, J.; Wang, T.; Xia, B.; Xi, P.; Gao, D. Zn-Doped MoSe2 (1066) Yang, J.; Liu, Y.; Shi, C.; Zhu, J.; Yang, X.; Liu, S.; Li, L.; Xu,
Nanosheets as High-Performance Electrocatalysts for Hydrogen Z.; Zhang, C.; Liu, T. Carbon Nanotube with Vertical 2D
Evolution Reaction in Acid Media. Electrochim. Acta 2019, 296, Molybdenum Sulphoselenide Nanosheet Arrays for Boosting Electro-
701−708. catalytic Hydrogen Evolution. ACS Appl. Energy Mater. 2018, 1,
(1049) Shi, Y.; Zhou, Y.; Yang, D. R.; Xu, W. X.; Wang, C.; Wang, F. 7035−7045.
B.; Xu, J. J.; Xia, X. H.; Chen, H. Y. Energy Level Engineering of MoS2 (1067) Gao, D.; Xia, B.; Zhu, C.; Du, Y.; Xi, P.; Xue, D.; Ding, J.;
by Transition-Metal Doping for Accelerating Hydrogen Evolution Wang, J. Activation of the MoSe2 Basal Plane and Se-Edge by B
Reaction. J. Am. Chem. Soc. 2017, 139, 15479−15485. Doping for Enhanced Hydrogen Evolution. J. Mater. Chem. A 2018, 6,
(1050) Jiang, A.; Zhang, B.; Li, Z.; Jin, G.; Hao, J. Vanadium-Doped 510−515.
WS2 Nanosheets Grown on Carbon Cloth as a Highly Efficient (1068) Vikraman, D.; Hussain, S.; Akbar, K.; Karuppasamy, K.;
Electrocatalyst for the Hydrogen Evolution Reaction. Chem.-Asian J. Chun, S.-H.; Jung, J.; Kim, H.-S. Design of Basal Plane Edges in
2018, 13, 1438−1446. Metal-Doped Nanostripes-Structured MoSe2 Atomic Layers to
Chem. Rev. 2023, 123, 3329−3442
Enhance Hydrogen Evolution Reaction Activity. ACS Sustainable (1088) Wang, C.; Han, Q.; Xie, R.; Wang, B.; He, T.; Xie, W.; Tang,
Chem. Eng. 2019, 7, 458−469. Q.; Li, Y.; Xu, J.; Yu, B. Fabrication of Petal-Like Ni3S2 Nanosheets on
(1069) Nishi, Y. Lithium Ion Secondary Batteries; Past 10 Years and 3D Carbon Nanotube Foams as High-Performance Anode Materials
the Future. J. Power Sources 2001, 100, 101−106. for Li-Ion Batteries. Electrochim. Acta 2020, 331, 135383.
(1070) Landi, B. J.; Ganter, M. J.; Cress, C. D.; DiLeo, R. A.; (1089) Xiao, X.; Ni, L.; Chen, G.; Ai, G.; Li, J.; Qiu, T.; Liu, X. Two-
Raffaelle, R. P. Carbon Nanotubes for Lithium Ion Batteries. Energy Dimensional NiSe2 Nanosheets on Carbon Fiber Cloth for High-
Environ. Sci. 2009, 2, 638−654. Performance Lithium-Ion Batteries. J. Alloys Compd. 2020, 821,
(1071) Pumera, M. Graphene-Based Nanomaterials for Energy 153218.
Storage. Energy Environ. Sci. 2011, 4, 668−674. (1090) Xu, X.; Mai, B.; Liu, Z.; Ji, S.; Hu, R.; Ouyang, L.; Liu, J.;
(1072) Wu, H.; Cui, Y. Designing Nanostructured Si Anodes for Zhu, M. Self-Sacrificial Template-Directed ZnSe@C as High
High Energy Lithium Ion Batteries. Nano Today 2012, 7, 414−429. Performance Anode for Potassium-Ion Batteries. Chem. Eng. J.
(1073) Reddy, M. V.; Subba Rao, G. V.; Chowdari, B. V. Metal 2020, 387, 124061.
Oxides and Oxysalts as Anode Materials for Li Ion Batteries. Chem. (1091) Wang, M.; Guo, H.; An, C.; Zhang, Y.; Li, W.; Zhang, Z.;
Rev. 2013, 113, 5364−457. Liu, G.; Liu, Y.; Wang, Y. In-Situ Carbon Coated CoSe Microrods as a
(1074) Wu, F.; Yuan, Y.-X.; Cheng, X.-B.; Bai, Y.; Li, Y.; Wu, C.; High-Capacity Anode for Sodium Ion Batteries. J. Alloys Compd.
Zhang, Q. Perspectives for Restraining Harsh Lithium Dendrite 2020, 820, 153090.
Growth: Towards Robust Lithium Metal Anodes. Energy Storage (1092) Wang, J.; Wang, H.; Cao, D.; Lu, X.; Han, X.; Niu, C.
Mater. 2018, 15, 148−170. Epitaxial Growth of Urchin-Like CoSe2 Nanorods from Electrospun
(1075) Yuan, Y.; Wu, F.; Bai, Y.; Li, Y.; Chen, G.; Wang, Z.; Wu, C. Co-Embedded Porous Carbon Nanofibers and Their Superior
Regulating Li Deposition by Constructing Lif-Rich Host for Dendrite- Lithium Storage Properties. Part. Part. Syst. Charact. 2017, 34,
Free Lithium Metal Anode. Energy Storage Mater. 2019, 16, 411−418. 1700185.
(1076) Fan, H.; Yu, H.; Wu, X.; Zhang, Y.; Luo, Z.; Wang, H.; Guo, (1093) Li, L.; Zhang, W.; Wang, X.; Zhang, S.; Liu, Y.; Li, M.; Zhu,
Y.; Madhavi, S.; Yan, Q. Controllable Preparation of Square Nickel G.; Zheng, Y.; Zhang, Q.; Zhou, T.; et al. Hollow-Carbon-Templated
Chalcogenide (NiS and NiSe2) Nanoplates for Superior Li/Na Ion Few-Layered V5S8 Nanosheets Enabling Ultrafast Potassium Storage
Storage Properties. ACS Appl. Mater. Interfaces 2016, 8, 25261− and Long-Term Cycling. ACS Nano 2019, 13, 7939−7948.
25267. (1094) Yang, G.; Wang, H.; Zhang, B.; Foo, S.; Ma, M.; Cao, X.; Liu,
(1077) Zhou, J.; Wang, Y.; Zhang, J.; Chen, T.; Song, H.; Yang, H. J.; Ni, S.; Srinivasan, M.; Huang, Y. Superior Li-Ion Storage of VS4
Y. Two Dimensional Layered Co0.85Se Nanosheets as a High-Capacity Nanowires Anchored on Reduced Graphene. Nanoscale 2019, 11,
Anode for Lithium-Ion Batteries. Nanoscale 2016, 8, 14992−5000. 9556−9562.
(1078) Chen, T.; Li, S.; Wen, J.; Gui, P.; Fang, G. Metal-Organic (1095) Teng, Y.; Zhao, H.; Zhang, Z.; Li, Z.; Xia, Q.; Zhang, Y.;
Framework Template Derived Porous CoSe2 Nanosheet Arrays for Zhao, L.; Du, X.; Du, Z.; Lv, P.; et al. MoS2 Nanosheets Vertically
Energy Conversion and Storage. ACS Appl. Mater. Interfaces 2017, 9, Grown on Graphene Sheets for Lithium-Ion Battery Anodes. ACS
35927−35935. Nano 2016, 10, 8526−8535.
(1079) Li, H.; Jiang, J.; Wang, F.; Huang, J.; Wang, Y.; Zhang, Y.; (1096) Liu, H.; Guo, H.; Liu, B.; Liang, M.; Lv, Z.; Adair, K. R.; Sun,
Zhao, J. Facile Synthesis of Rod-Like Cu2−xSe and Insight into Its X. Few-Layer MoSe2 Nanosheets with Expanded (002) Planes
Improved Lithium-Storage Property. ChemSusChem 2017, 10, 2235− Confined in Hollow Carbon Nanospheres for Ultrahigh-Performance
2241. Na-Ion Batteries. Adv. Funct. Mater. 2018, 28, 1707480.
(1080) Li, H.; Jiang, J.; Huang, J.; Wang, Y.; Peng, Y.; Zhang, Y.; (1097) Liu, Y.; Wang, N.; Zhao, X.; Fang, Z.; Zhang, X.; Liu, Y.; Bai,
Hwang, B. J.; Zhao, J. Investigation of the Na Storage Property of Z.; Dou, S.; Yu, G. Hierarchical Nanoarchitectured Hybrid Electrodes
One-Dimensional Cu2‑xSe Nanorods. ACS Appl. Mater. Interfaces Based on Ultrathin MoSe2 Nanosheets on 3D Ordered Macroporous
2018, 10, 13491−13498. Carbon Frameworks for High-Performance Sodium-Ion Batteries. J.
(1081) Tian, W.; Ma, W.; Feng, Z.; Tian, F.; Li, H.; Liu, J.; Xiong, S. Mater. Chem. A 2020, 8, 2843−2850.
Formation of Hierarchical Fe7Se8 Nanorod Bundles with Enhanced (1098) Wang, J.; Li, F.; Chen, C.; Liu, X.; Yao, T.; Liu, T.; Zhu, L.;
Sodium Storage Properties. J. Energy Chem. 2020, 44, 97−105. Ji, X.; Wang, H. Atomic Layer Deposition of TiO2 Shells on CoSe2
(1082) Fan, C. Y.; Zhang, X. H.; Shi, Y. H.; Xu, H. Y.; Zhang, J. P.; Nanorods Towards Enhanced Lithium Storage Performance. J. Alloys
Wu, X. L. Three-Dimensional Hierarchical Ni3Se2 Nanorod Array as Compd. 2020, 829, 154537.
Binder/Carbon-Free Electrode for High-Areal-Capacity Na Storage. (1099) Pham-Cong, D.; Choi, J. H.; Yun, J.; Bandarenka, A. S.; Kim,
Nanoscale 2018, 10, 18942−18948. J.; Braun, P. V.; Jeong, S. Y.; Cho, C. R. Synergistically Enhanced
(1083) Zhang, J.; Wu, M.; Liu, T.; Kang, W.; Xu, J. Hierarchical Electrochemical Performance of Hierarchical MoS2/TiNb2O7 Hetero-
Nanotubes Constructed from Interlayer-Expanded MoSe2 Nanosheets Nanostructures as Anode Materials for Li-Ion Batteries. ACS Nano
as a Highly Durable Electrode for Sodium Storage. J. Mater. Chem. A 2017, 11, 1026−1033.
2017, 5, 24859−24866. (1100) Xing, L.; Yu, Q.; Jiang, B.; Chu, J.; Lao, C.-Y.; Wang, M.;
(1084) Ma, Y.; Ma, Y.; Kim, G.-T.; Diemant, T.; Behm, R. J.; Geiger, Han, K.; Liu, Z.; Bao, Y.; Wang, W. Carbon-Encapsulated Ultrathin
D.; Kaiser, U.; Varzi, A.; Passerini, S. Superior Lithium Storage MoS2 Nanosheets Epitaxially Grown on Porous Metallic TiNb2O6
Capacity of α-MnS Nanoparticles Embedded in S-Doped Carbona- Microspheres with Unsaturated Oxygen Atoms for Superior
ceous Mesoporous Frameworks. Adv. Energy Mater. 2019, 9, 1902077. Potassium Storage. J. Mater. Chem. A 2019, 7, 5760−5768.
(1085) Lin, X.; Cui, X.; Yan, H.; Lei, J.; Xu, P.; Fan, J.; Yuan, R.; (1101) Cui, L.; Tan, C.; Yang, G.; Li, Y.; Pan, Q.; Zhang, M.; Chen,
Zheng, M.; Dong, Q. A Sodium Storage Material Based on Chamber- Z.; Zheng, F.; Wang, H.; Li, Q. Constructing an Interface Synergistic
Confined Conversion of Co9S8 Nanorod Encapsulated by N-Doped Effect from a SnS/MoS2 Heterojunction Decorating N, S Co-Doped
Carbon Shell. ACS Sustainable Chem. Eng. 2019, 7, 15729−15738. Carbon Nanosheets with Enhanced Sodium Ion Storage Performance.
(1086) Xu, L.; Xiong, P.; Zeng, L.; Fang, Y.; Liu, R.; Liu, J.; Luo, F.; J. Mater. Chem. A 2020, 8, 22593−22600.
Chen, Q.; Wei, M.; Qian, Q. Electrospun VSe1.5/CNF Composite (1102) Chen, F.; Shi, D.; Yang, M.; Jiang, H.; Shao, Y.; Wang, S.;
with Excellent Performance for Alkali Metal Ion Batteries. Nanoscale Zhang, B.; Shen, J.; Wu, Y.; Hao, X. Novel Designed MnS-MoS2
2019, 11, 16308−16316. Heterostructure for Fast and Stable Li/Na Storage:Insights into the
(1087) Guo, X.; Wang, S.; Yang, B.; Xu, Y.; Liu, Y.; Pang, H. Porous Advanced Mechanism Attributed to Phase Engineering. Adv. Funct.
Pyrrhotite Fe7s8 Nanowire/SiOx/Nitrogen-Doped Carbon Matrix for Mater. 2021, 31, 2007132.
High-Performance Li-Ion-Battery Anodes. J. Colloid Interface Sci. (1103) Hong, Y. J.; Kim, J. H.; Chan Kang, Y. Sodium-Ion Storage
2020, 561, 801−807. Performance of Hierarchically Structured (Co1/3Fe2/3)Se2 Nanofibers
Chem. Rev. 2023, 123, 3329−3442
with Fiber-in-Tube Nanostructures. J. Mater. Chem. A 2016, 4, Assemblies: A Universal Host Material for the Reversible Storage of
15471−15477. Alkali Metal Ions. Adv. Mater. 2017, 29, 1702061.
(1104) Zhao, Y.; Bi, M.; Qian, F.; Zeng, P.; Chen, M.; Wang, R.; Liu, (1121) He, P.; Yan, M.; Zhang, G.; Sun, R.; Chen, L.; An, Q.; Mai,
Y.; Ding, Y.; Fang, Z. Heterostructure CoS/NC@MoS2 Hollow L. Layered VS2 Nanosheet-Based Aqueous Zn Ion Battery Cathode.
Spheres for High-Performance Hydrogen Evolution Reactions and Adv. Energy Mater. 2017, 7, 1601920.
Lithium-Ion Batteries. ChemElectroChem. 2018, 5, 3953−3960. (1122) Rout, C. S.; Kim, B.-H.; Xu, X.; Yang, J.; Jeong, H. Y.;
(1105) Park, S.-K.; Kim, J. K.; Chan Kang, Y. Metal−Organic Odkhuu, D.; Park, N.; Cho, J.; Shin, H. S. Synthesis and
Framework-Derived CoSe2/(NiCo)Se2 Box-in-Box Hollow Nano- Characterization of Patronite Form of Vanadium Sulfide on Graphitic
cubes with Enhanced Electrochemical Properties for Sodium-Ion Layer. J. Am. Chem. Soc. 2013, 135, 8720−8725.
Storage and Hydrogen Evolution. J. Mater. Chem. A 2017, 5, 18823− (1123) Yang, W.; Luo, N.; Zheng, C.; Huang, S.; Wei, M.
18830. Hierarchical Composite of Rose-Like VS2@S/N-Doped Carbon
(1106) Lu, J.; Xia, G.; Gong, S.; Wang, C.; Jiang, P.; Lin, Z.; Wang, with Expanded (001) Planes for Superior Li-Ion Storage. Small
D.; Yang, Y.; Chen, Q. Metallic 1T Phase MoS2 Nanosheets 2019, 15, 1903904.
Decorated Hollow Cobalt Sulfide Polyhedra for High-Performance (1124) Kumar, N. A.; Dar, M. A.; Gul, R.; Baek, J.-B. Graphene and
Lithium Storage. J. Mater. Chem. A 2018, 6, 12613−12622. Molybdenum Disulfide Hybrids: Synthesis and Applications. Mater.
(1107) Guan, S.; Wang, T.; Fu, X.; Fan, L.-Z.; Peng, Z. Coherent Today 2015, 18, 286−298.
SnS2/NiS2 Hetero-Nanosheet Arrays with Fast Charge Transfer for (1125) Daraghmeh, A.; Hussain, S.; Servera, L.; Xuriguera, E.;
Enhanced Sodium-Ion Storage. Appl. Surf. Sci. 2020, 508, 145241. Cornet, A.; Cirera, A. Impact of Binder Concentration and Pressure
(1108) Zhang, C.; Han, F.; Wang, F.; Liu, Q.; Zhou, D.; Zhang, F.; on Performance of Symmetric CNFs Based Supercapacitors. Electro-
Xu, S.; Fan, C.; Li, X.; Liu, J. Improving Compactness and Reaction chim. Acta 2017, 245, 531−538.
Kinetics of MoS2@C Anodes by Introducing Fe9S10 Core for Superior (1126) Zhang, L.; Hu, X.; Wang, Z.; Sun, F.; Dorrell, D. G. A Review
Volumetric Sodium/Potassium Storage. Energy Storage Mater. 2020, of Supercapacitor Modeling, Estimation, and Applications: A
24, 208−219. Control/Management Perspective. Renewable Sustainable Energy Rev.
(1109) Zhang, Z.; Zhao, J.; Xu, M.; Wang, H.; Gong, Y.; Xu, J. Facile 2018, 81, 1868−1878.
Synthesis of Sb2S3/MoS2 Heterostructure as Anode Material for (1127) Yu, X.; Yun, S.; Yeon, J. S.; Bhattacharya, P.; Wang, L.; Lee,
Sodium-Ion Batteries. Nanotechnology 2018, 29, 335401. S. W.; Hu, X.; Park, H. S. Emergent Pseudocapacitance of 2D
(1110) Yang, S.; He, M.; Deng, X.; Feng, Y.; Huang, X.; Wu, K.; Bai, Nanomaterials. Adv. Energy Mater. 2018, 8, 1702930.
C.; Ke, J.; Xiong, D. Wafer-Like FeSe2-NiSe2/C Nanosheets as (1128) Lin, L.; Lei, W.; Zhang, S.; Liu, Y.; Wallace, G. G.; Chen, J.
Efficient Anode for High-Performances Lithium Batteries. Chem. Phys. Two-Dimensional Transition Metal Dichalcogenides in Super-
Lett. 2020, 746, 137274. capacitors and Secondary Batteries. Energy Storage Mater. 2019, 19,
(1111) Qin, Y.; Zhang, Y.; Wang, J.; Zhang, J.; Zhai, Y.; Wang, H.;
408−423.
Li, D. Heterogeneous Structured Bi2S3/MoS2@NC Nanoclusters: (1129) Lei, Z.; Sun, X.; Wang, H.; Liu, Z.; Zhao, X. S. Platelet CMK-
Exploring the Superior Rate Performance in Sodium/Potassium Ion
5 as an Excellent Mesoporous Carbon to Enhance the Pseudocapa-
Batteries. ACS Appl. Mater. Interfaces 2020, 12, 42902−42910.
citance of Polyaniline. ACS Appl. Mater. Interfaces 2013, 5, 7501−
(1112) Wang, Y.; Xie, W.; Li, D.; Han, P.; Shi, L.; Luo, Y.; Cong, G.;
7508.
Li, C.; Yu, J.; Zhu, C.; et al. One-Pot Synthesis of Hierarchical
(1130) Wang, G.; Zhang, L.; Zhang, J. A Review of Electrode
Co1−xS/NC@MoS2/C Hollow Nanofibers Based on One-Dimen-
Materials for Electrochemical Supercapacitors. Chem. Soc. Rev. 2012,
sional Metal Coordination Polymers for Enhanced Lithium and
41, 797−828.
Sodium-Ion Storage. Sci. Bull. 2020, 65, 1460−1469.
(1131) Gu, Y.; Fan, L. Q.; Huang, J. L.; Geng, C. L.; Lin, J. M.;
(1113) Ou, X.; Cao, L.; Liang, X.; Zheng, F.; Zheng, H.-S.; Yang, X.;
Wang, J.-H.; Yang, C.; Liu, M. Fabrication of SnS2/Mn2SnS4/Carbon Huang, M. L.; Huang, Y. F.; Wu, J. H. Hydrothermal Synthesis of Co-
Heterostructures for Sodium-Ion Batteries with High Initial Doped NiSe2 Nanowire for High-Performance Asymmetric Super-
Coulombic Efficiency and Cycling Stability. ACS Nano 2019, 13, capacitors. Materials 2018, 11, 1468.
3666−3676. (1132) Guo, K.; Cui, S.; Hou, H.; Chen, W.; Mi, L. Hierarchical
(1114) Li, Y.; Liang, Y.; Robles Hernandez, F. C.; Deog Yoo, H.; An, Ternary Ni-Co-Se Nanowires for High-Performance Supercapacitor
Q.; Yao, Y. Enhancing Sodium-Ion Battery Performance with Device Design. Dalton. Trans. 2016, 45, 19458−19465.
Interlayer-Expanded MoS2−PEO Nanocomposites. Nano Energy (1133) Zhou, J.; Fang, G.; Pan, A.; Liang, S. Oxygen-Incorporated
2015, 15, 453−461. MoS2 Nanosheets with Expanded Interlayers for Hydrogen Evolution
(1115) Xu, J.; Zhang, J.; Zhang, W.; Lee, C.-S. Interlayer Reaction and Pseudocapacitor Applications. ACS Appl. Mater.
Nanoarchitectonics of Two-Dimensional Transition-Metal Dichalco- Interfaces 2016, 8, 33681−33689.
genides Nanosheets for Energy Storage and Conversion Applications. (1134) Lee, S.; Hwang, J.; Kim, D.; Ahn, H. Oxygen Incorporated in
Adv. Energy Mater. 2017, 7, 1700571. 1T/2H Hybrid MoS2 Nanoflowers Prepared from Molybdenum Blue
(1116) Cai, Y.; Yang, H.; Zhou, J.; Luo, Z.; Fang, G.; Liu, S.; Pan, A.; Solution for Asymmetric Supercapacitor Applications. Chem. Eng. J.
Liang, S. Nitrogen Doped Hollow MoS2/C Nanospheres as Anode for 2021, 419, 129701.
Long-Life Sodium-Ion Batteries. Chem. Eng. J. 2017, 327, 522−529. (1135) Wang, D.; Xiao, Y.; Luo, X.; Wu, Z.; Wang, Y.-J.; Fang, B.
(1117) Meng, Y.; Zhao, Y.; Wang, D.; Yang, D.; Gao, Y.; Lian, R.; Swollen Ammoniated MoS2 with 1T/2H Hybrid Phases for High-
Chen, G.; Wei, Y. Fast Li+ Diffusion in Interlayer-Expanded Rate Electrochemical Energy Storage. ACS Sustainable Chem. Eng.
Vanadium Disulfide Nanosheets for Li+/Mg2+ Hybrid-Ion Batteries. 2017, 5, 2509−2515.
J. Mater. Chem. A 2018, 6, 5782−5788. (1136) Thiyagarajan, K.; Song, W. J.; Park, H.; Selvaraj, V.; Moon,
(1118) Ding, Z.; Zhang, Q.; Chen, Y.; Liu, G.; Xin, X.; He, H.; Cai, S.; Oh, J.; Kwak, M. J.; Park, G.; Kong, M.; Pal, M.; et al. Electroactive
B.; Wu, J.; Yao, X. PEDOT-PSS Coated VS2 Nanosheet Anodes for 1T-MoS2 Fluoroelastomer Ink for Intrinsically Stretchable Solid-State
High Rate and Ultrastable Lithium-Ion Batteries. New J. Chem. 2019, in-Plane Supercapacitors. ACS Appl. Mater. Interfaces 2021, 13,
43, 1681−1687. 26870−26878.
(1119) Sun, R.; Wei, Q.; Sheng, J.; Shi, C.; An, Q.; Liu, S.; Mai, L. (1137) Wang, X.; Shi, B.; Fang, Y.; Rong, F.; Huang, F.; Que, R.;
Novel Layer-by-Layer Stacked VS2 Nanosheets with Intercalation Shao, M. High Capacitance and Rate Capability of a Ni3S2@CdS
Pseudocapacitance for High-Rate Sodium Ion Charge Storage. Nano Core−Shell Nanostructure Supercapacitor. J. Mater. Chem. A 2017, 5,
Energy 2017, 35, 396−404. 7165−7172.
(1120) Zhou, J.; Wang, L.; Yang, M.; Wu, J.; Chen, F.; Huang, W.; (1138) Ye, B.; Gong, C.; Huang, M.; Ge, J.; Fan, L.; Lin, J.; Wu, J. A
Han, N.; Ye, H.; Zhao, F.; Li, Y.; et al. Hierarchical VS2 Nanosheet High-Performance Asymmetric Supercapacitor Based on Ni3S2-
Chem. Rev. 2023, 123, 3329−3442
Coated NiSe Arrays as Positive Electrode. New J. Chem. 2019, 43, (1155) Wang, L.; Ma, Y.; Yang, M.; Qi, Y. One-Pot Synthesis of 3D
2389−2399. Flower-Like Heterostructured SnS2/MoS2 for Enhanced Super-
(1139) Yang, X.; Chen, X.; Cao, H.; Li, C.; Wang, L.; Wu, Y.; Wang, capacitor Behavior. RSC Adv. 2015, 5, 89069−89075.
C.; Li, Y. Rational Synthesis of Cu7Se4-CuxCo1‑xSe2 Double-Shell (1156) Wang, Q.; Liu, J.; Ran, X.; Zhang, D.; Shen, G.; Miao, M.
Hollow Nanospheres for High Performance Supercapacitors. J. Power High-Performance Flexible Self-Powered Strain Sensor Based on
Sources 2020, 480, 228741. Carbon Nanotube/ZnSe/CoSe2 Nanocomposite Film Electrodes.
(1140) He, Y.; Zhang, X.; Wang, S.; Meng, J.; Sui, Y.; Wei, F.; Qi, J.; Nano Res. 2022, 15, 170−178.
Meng, Q.; Ren, Y.; Zhuang, D. Rubik’s Cube-Like Ni3S4/CuS2 (1157) Zhao, Y.; He, X.; Chen, R.; Liu, Q.; Liu, J.; Song, D.; Zhang,
Nanocomposite for High-Performance Supercapacitors. J. Alloys H.; Dong, H.; Li, R.; Zhang, M.; et al. Hierarchical NiCo2S4@
Compd. 2020, 847, 156312. CoMoO4 Core-Shell Heterostructures Nanowire Arrays as Advanced
(1141) Han, X.; Chen, Q.; Zhang, H.; Ni, Y.; Zhang, L. Template Electrodes for Flexible All-Solid-State Asymmetric Supercapacitors.
Synthesis of NiCo2S4/Co9S8 Hollow Spheres for High-Performance Appl. Surf. Sci. 2018, 453, 73−82.
Asymmetric Supercapacitors. Chem. Eng. J. 2019, 368, 513−524. (1158) Adhikari, A. D.; Oraon, R.; Tiwari, S. K.; Saren, P.; Lee, J. H.;
(1142) Kumar, R.; Agrawal, A.; Nagarale, R. K.; Sharma, A. High Kim, N. H.; Nayak, G. C. CdS-CoFe2O4@Reduced Graphene Oxide
Performance Supercapacitors from Novel Metal-Doped Ceria- Nanohybrid: An Excellent Electrode Material for Supercapacitor
Decorated Aminated Graphene. J. Phys. Chem. C 2016, 120, 3107− Applications. Ind. Eng. Chem. Res. 2018, 57, 1350−1360.
(1159) Zardkhoshoui, A. M.; Hosseiny Davarani, S. S. An Efficient
3116.
Hybrid Supercapacitor Based on Zn−Mn−Ni−S@NiSe Core−Shell
(1143) Xia, H.; Hong, C.; Shi, X.; Li, B.; Yuan, G.; Yao, Q.; Xie, J.
Architectures. Sustainable Energy Fuels 2021, 5, 900−913.
Hierarchical Heterostructures of Ag Nanoparticles Decorated MnO2
(1160) Aslam, M.; Chaudhary, V. A.; Mulla, I. S.; Sainkar, S. R.;
Nanowires as Promising Electrodes for Supercapacitors. J. Mater.
Mandale, A. B.; Belhekar, A. A.; Vijayamohanan, K. A Highly Selective
Chem. A 2015, 3, 1216−1221. Ammonia Gas Sensor Using Surface-Ruthenated Zinc Oxide. Sens.
(1144) Lv, Q.; Wang, S.; Sun, H.; Luo, J.; Xiao, J.; Xiao, J.; Xiao, F.; Actuators, A 1999, 75, 162−167.
Wang, S. Solid-State Thin-Film Supercapacitors with Ultrafast (1161) Kong, J.; Franklin, R.; Zhou, C.; Chapline, G.; Peng, S.; Cho,
Charge/Discharge Based on N-Doped-Carbon-Tubes/Au-Nanopar- K.; Dai, H. Nanotube Molecular Wires as Chemical Sensors. Science
ticles-Doped-MnO2 Nanocomposites. Nano Lett. 2016, 16, 40−47. 2000, 287, 622−625.
(1145) Zhang, J.; Xu, Y.; Liu, Z.; Yang, W.; Liu, J. A Highly (1162) Farahani, H.; Wagiran, R.; Hamidon, M. N. Humidity
Conductive Porous Graphene Electrode Prepared via in Situ Sensors Principle, Mechanism, and Fabrication Technologies: A
Reduction of Graphene Oxide Using Cu Nanoparticles for the Comprehensive Review. Sensors 2014, 14, 7881−7939.
Fabrication of High Performance Supercapacitors. RSC Adv. 2015, 5, (1163) Yang, Z.; Dou, X.; Zhang, S.; Guo, L.; Zu, B.; Wu, Z.; Zeng,
54275−54282. H. A High-Performance Nitro-Explosives Schottky Sensor Boosted by
(1146) Dai, Y.; Tang, S.; Vongehr, S.; Meng, X. Silver Nanoparticle- Interface Modulation. Adv. Funct. Mater. 2015, 25, 4039−4048.
Induced Growth of Nanowire-Covered Porous Mno2 Spheres with (1164) Wetchakun, K.; Samerjai, T.; Tamaekong, N.; Liewhiran, C.;
Superior Supercapacitance. ACS Sustainable Chem. Eng. 2014, 2, 692− Siriwong, C.; Kruefu, V.; Wisitsoraat, A.; Tuantranont, A.;
698. Phanichphant, S. Semiconducting Metal Oxides as Sensors for
(1147) Kang, J.; Hirata, A.; Kang, L.; Zhang, X.; Hou, Y.; Chen, L.; Environmentally Hazardous Gases. Sens. Actuators, B 2011, 160,
Li, C.; Fujita, T.; Akagi, K.; Chen, M. Enhanced Supercapacitor 580−591.
Performance of MnO2 by Atomic Doping. Angew. Chem., Int. Ed. (1165) Vanalakar, S. A.; Patil, V. L.; Patil, P. S.; Kim, J. H. Rapid
2013, 52, 1664−1667. Synthesis of CdS Nanowire Mesh via a Simplistic Wet Chemical
(1148) Su, X.; Yu, L.; Cheng, G.; Zhang, H.; Sun, M.; Zhang, L.; Route and Its NO2 Gas Sensing Properties. New J. Chem. 2018, 42,
Zhang, J. Controllable Hydrothermal Synthesis of Cu-Doped δ-MnO2 4232−4239.
Films with Different Morphologies for Energy Storage and (1166) Wang, X.; Xie, Z.; Huang, H.; Liu, Z.; Chen, D.; Shen, G.
Conversion Using Supercapacitors. Appl. Energy 2014, 134, 439−445. Gas Sensors, Thermistor and Photodetector Based on ZnS Nano-
(1149) Xu, Q.; Jiang, D.; Wang, T.; Meng, S.; Chen, M. Ag wires. J. Mater. Chem. 2012, 22, 6845−6850.
Nanoparticle-Decorated CoS Nanosheet Nanocomposites: A High- (1167) Wu, B.; Lin, Z.; Sheng, M.; Hou, S.; Xu, J. Visible-Light
Performance Material for Multifunctional Applications in Photo- Activated ZnO/CdSe Heterostructure-Based Gas Sensors with Low
catalysis and Supercapacitors. RSC Adv. 2016, 6, 55039−55045. Operating Temperature. Appl. Surf. Sci. 2016, 360, 652−657.
(1150) Jayababu, N.; Jo, S.; Kim, Y.; Kim, D. Novel Conductive Ag- (1168) Kumar, R.; Zheng, W.; Liu, X.; Zhang, J.; Kumar, M. MoS2-
Decorated NiFe Mixed Metal Telluride Hierarchical Nanorods for Based Nanomaterials for Room-Temperature Gas Sensors. Adv.
High-Performance Hybrid Supercapacitors. ACS Appl. Mater. Mater. Technologies 2020, 5, 1901062.
(1169) Guo, R.; Han, Y.; Su, C.; Chen, X.; Zeng, M.; Hu, N.; Su, Y.;
Interfaces 2021, 13, 19938−19949.
Zhou, Z.; Wei, H.; Yang, Z. Ultrasensitive Room Temperature NO2
(1151) Huang, Y.; Cui, F.; Bao, J.; Zhao, Y.; Lian, J.; Liu, T.; Li, H.
Sensors Based on Liquid Phase Exfoliated WSe2 Nanosheets. Sens.
MnCo2S4/FeCo2S4 “Lollipop” Arrays on a Hollow N-Doped Carbon
Actuators, B 2019, 300, 127013.
Skeleton as Flexible Electrodes for Hybrid Supercapacitors. J. Mater. (1170) Jarvinen, T.; Lorite, G. S.; Perantie, J.; Toth, G.; Saarakkala,
Chem. A 2019, 7, 20778−20789. S.; Virtanen, V. K.; Kordas, K. WS2 and MoS2 Thin Film Gas Sensors
(1152) Chen, S.; Lu, C.; Liu, L.; Xu, M.; Wang, J.; Deng, Q.; Zeng, with High Response to NH3 in Air at Low Temperature.
Z.; Deng, S. A Hierarchical Glucose-Intercalated Nimn-G-LDH@ Nanotechnology 2019, 30, 405501.
NiCo2S4 Core-Shell Structure as a Binder-Free Electrode for Flexible (1171) Wu, E.; Xie, Y.; Yuan, B.; Zhang, H.; Hu, X.; Liu, J.; Zhang,
All-Solid-State Asymmetric Supercapacitors. Nanoscale 2020, 12, D. Ultrasensitive and Fully Reversible No2 Gas Sensing Based on P-
1852−1863. Type MoTe2 under Ultraviolet Illumination. ACS Sens. 2018, 3,
(1153) Xiang, G.; Yin, J.; Qu, G.; Sun, P.; Hou, P.; Huang, J.; Xu, X. 1719−1726.
Construction of ZnCo2S4@Ni(OH)2 Core−Shell Nanostructures for (1172) Zeng, J.; Niu, Y.; Gong, Y.; Wang, Q.; Li, H.; Umar, A.; de
Asymmetric Supercapacitors with High Energy Densities. Inorg. Chem. Rooij, N. F.; Zhou, G.; Wang, Y. All-Dry Transferred ReS 2
Front. 2019, 6, 2135−2141. Nanosheets for Ultrasensitive Room-Temperature NO2 Sensing
(1154) Yang, X.; Zhao, L.; Lian, J. Arrays of Hierarchical Nickel under Visible Light Illumination. ACS Sens. 2020, 5, 3172−3181.
Sulfides/MoS2 Nanosheets Supported on Carbon Nanotubes Back- (1173) Aftab, S.; Samiya, M.; Hussain, M. S.; Elahi, E.; Yousuf, S.;
bone as Advanced Anode Materials for Asymmetric Supercapacitor. J. Ajmal, H. M. S.; Iqbal, M. W.; Iqbal, M. Z. ReSe2/Metal Interface for
Power Sources 2017, 343, 373−382. Hydrogen Gas Sensing. J. Colloid Interface Sci. 2021, 603, 511−517.
Chem. Rev. 2023, 123, 3329−3442
(1174) Sun, J.; Xiong, W.; Zhang, J.; Zhang, Y.; Xie, B. Sns2 Properties of Their Nanocomposites. Adv. Mater. 2013, 25, 1425−
Nanoparticle-Based Gas Sensor with Highly Sensitive NO2 Detection 1429.
at Room Temperature. Mater. Lett. 2022, 308, 131214. (1192) Rongione, N. A.; Li, M.; Wu, H.; Nguyen, H. D.; Kang, J. S.;
(1175) Niu, Y.; Zeng, J.; Liu, X.; Li, J.; Wang, Q.; Li, H.; Rooij, N. F. Ouyang, B.; Xia, H.; Hu, Y. High-Performance Solution-Processable
d.; Wang, Y.; Zhou, G. A Photovoltaic Self-Powered Gas Sensor Based Flexible SnSe Nanosheet Films for Lower Grade Waste Heat
on All-Dry Transferred MoS2/GaSe Heterojunction for ppb-Level Recovery. Adv. Electron. Mater. 2019, 5, 1800774.
NO2 Sensing at Room Temperature. Adv. Sci. 2021, 8, 2100472. (1193) Finefrock, S. W.; Zhang, G.; Bahk, J. H.; Fang, H.; Yang, H.;
(1176) Lee, E.; Yoon, Y. S.; Kim, D.-J. Two-Dimensional Transition Shakouri, A.; Wu, Y. Structure and Thermoelectric Properties of
Metal Dichalcogenides and Metal Oxide Hybrids for Gas Sensing. Spark Plasma Sintered Ultrathin PbTe Nanowires. Nano Lett. 2014,
ACS Sens. 2018, 3, 2045−2060. 14, 3466−73.
(1177) Yang, D.; Cho, I.; Kim, D.; Lim, M. A.; Li, Z.; Ok, J. G.; Lee, (1194) Zhang, G.; Kirk, B.; Jauregui, L. A.; Yang, H.; Xu, X.; Chen,
M.; Park, I. Gas Sensor by Direct Growth and Functionalization of Y. P.; Wu, Y. Rational Synthesis of Ultrathin N-Type Bi2Te3
Metal Oxide/Metal Sulfide Core-Shell Nanowires on Flexible Nanowires with Enhanced Thermoelectric Properties. Nano Lett.
Substrates. ACS Appl. Mater. Interfaces 2019, 11, 24298−24307. 2012, 12, 56−60.
(1178) Cho, B.; Kim, A. R.; Kim, D. J.; Chung, H. S.; Choi, S. Y.; (1195) Mulla, R.; Jones, D. R.; Dunnill, C. W. Economical and
Kwon, J. D.; Park, S. W.; Kim, Y.; Lee, B. H.; Lee, K. H.; Kim, D. H.; Facile Route to Produce Gram-Scale and Phase-Selective Copper
Nam, J.; Hahm, M. G. Two-Dimensional Atomic-Layered Alloy Sulfides for Thermoelectric Applications. ACS Sustainable Chem. Eng.
Junctions for High-Performance Wearable Chemical Sensor. ACS 2020, 8, 14234−14242.
Appl. Mater. Interfaces 2016, 8, 19635−19642. (1196) Piao, M.; Li, C.; Joo, M.-K.; Chu, J.; Wang, X.; Chi, Y.;
(1179) Moumen, A.; Konar, R.; Zappa, D.; Teblum, E.; Perelshtein, Zhang, H.; Shi, H. Hydrothermal Synthesis of Stable 1T-WS2 and
I.; Lavi, R.; Ruthstein, S.; Nessim, G. D.; Comini, E. Robust Room- Single-Walled Carbon Nanotube Hybrid Flexible Thin Films with
Temperature NO2 Sensors from Exfoliated 2D Few-Layered CVD- Enhanced Thermoelectric Performance. Energy Technol. 2018, 6,
Grown Bulk Tungsten Di-Selenide (2H-WSe2). ACS Appl. Mater. 1921−1928.
Interfaces 2021, 13, 4316−4329. (1197) Huang, H.; Cui, Y.; Li, Q.; Dun, C.; Zhou, W.; Huang, W.;
(1180) Zhang, S.; Zhang, W.; Nguyen, T. H.; Jian, J.; Yang, W. Chen, L.; Hewitt, C. A.; Carroll, D. L. Metallic 1T Phase MoS2
Synthesis of Molybdenum Diselenide Nanosheets and Its Ethanol- Nanosheets for High-Performance Thermoelectric Energy Harvesting.
Sensing Mechanism. Mater. Chem. Phys. 2019, 222, 139−146. Nano Energy 2016, 26, 172−179.
(1181) Late, D. J.; Huang, Y.-K.; Liu, B.; Acharya, J.; Shirodkar, S. (1198) Hong, M.; Chen, Z.-G.; Yang, L.; Chasapis, T. C.; Kang, S.
N.; Luo, J.; Yan, A.; Charles, D.; Waghmare, U. V.; Dravid, V. P.; et al. D.; Zou, Y.; Auchterlonie, G. J.; Kanatzidis, M. G.; Snyder, G. J.; Zou,
Sensing Behavior of Atomically Thin-Layered MoS2 Transistors. ACS J. Enhancing the Thermoelectric Performance of SnSe 1−XTe x
Nano 2013, 7, 4879−4891. Nanoplates through Band Engineering. J. Mater. Chem. A 2017, 5,
(1182) Qin, Z.; Zeng, D.; Zhang, J.; Wu, C.; Wen, Y.; Shan, B.; Xie, 10713−10721.
C. Effect of Layer Number on Recovery Rate of WS2 Nanosheets for (1199) Liu, S.; Peng, N.; Bai, Y.; Ma, D.; Ma, F.; Xu, K. Fabrication
Ammonia Detection at Room Temperature. Appl. Surf. Sci. 2017, 414, of Cu-Doped Bi2Te3 Nanoplates and Their Thermoelectric Proper-
244−250. ties. J. Electron. Mater. 2017, 46, 2697−2704.
(1183) Li, Y.; Song, Z.; Li, Y.; Chen, S.; Li, S.; Li, Y.; Wang, H.; (1200) Gong, Y.; Chang, C.; Wei, W.; Liu, J.; Xiong, W.; Chai, S.; Li,
Wang, Z. Hierarchical Hollow MoS2 Microspheres as Materials for D.; Zhang, J.; Tang, G. Extremely Low Thermal Conductivity and
Conductometric NO2 Gas Sensors. Sens. Actuators, B 2019, 282, 259− Enhanced Thermoelectric Performance of Polycrystalline SnSe by Cu
267. Doping. Scr. Mater. 2018, 147, 74−78.
(1184) Shim, Y. S.; Kwon, K. C.; Suh, J. M.; Choi, K. S.; Song, Y. G.; (1201) Wu, F.; Shi, W.; Hu, X. Preparation and Thermoelectric
Sohn, W.; Choi, S.; Hong, K.; Jeon, J. M.; Hong, S. P.; et al. Synthesis Properties of Flower-Like Nanoparticles of Ce-Doped Bi2Te3.
of Numerous Edge Sites in MoS2 via SiO2 Nanorods Platform for Electron. Mater. Lett. 2015, 11, 127−132.
Highly Sensitive Gas Sensor. ACS Appl. Mater. Interfaces 2018, 10, (1202) Han, G.; Popuri, S. R.; Greer, H. F.; Bos, J. W.; Zhou, W.;
31594−31602. Knox, A. R.; Montecucco, A.; Siviter, J.; Man, E. A.; Macauley, M.;
(1185) Cho, S. Y.; Kim, S. J.; Lee, Y.; Kim, J. S.; Jung, W. B.; Yoo, H. et al. Facile Surfactant-Free Synthesis of P-Type SnSe Nanoplates
W.; Kim, J.; Jung, H. T. Highly Enhanced Gas Adsorption Properties with Exceptional Thermoelectric Power Factors. Angew. Chem., Int.
in Vertically Aligned MoS2 Layers. ACS Nano 2015, 9, 9314−9321. Ed. Engl. 2016, 55, 6433−6437.
(1186) Yang, Z.; Guo, L.; Zu, B.; Guo, Y.; Xu, T.; Dou, X. CdS/ZnO (1203) Saha, S.; Banik, A.; Biswas, K. Few-Layer Nanosheets of N-
Core/Shell Nanowire-Built Films for Enhanced Photodetecting and Type SnSe2. Chemistry 2016, 22, 15634−15638.
Optoelectronic Gas-Sensing Applications. Adv. Opt. Mater. 2014, 2, (1204) Ivanov, O.; Yaprintsev, M.; Lyubushkin, R.; Soklakova, O.
738−745. Enhancement of Thermoelectric Efficiency in Bi2Te3 via Rare Earth
(1187) Wu, C.-M.; Shrisha; Motora, K. G.; Chen, G.-Y.; Kuo, D.-H.; Element Doping. Scr. Mater. 2018, 146, 91−94.
Gultom, N. S. Highly Efficient MoS2/CsxWO3 Nanocomposite (1205) Li, X.; Chen, C.; Xue, W.; Li, S.; Cao, F.; Chen, Y.; He, J.;
Hydrogen Gas Sensors. Front. Mater. 2022, 9, 831725. Sui, J.; Liu, X.; Wang, Y.; Zhang, Q. N-Type Bi-Doped SnSe
(1188) Hicks, L. D.; Dresselhaus, M. S. Effect of Quantum-Well Thermoelectric Nanomaterials Synthesized by a Facile Solution
Structures on the Thermoelectric Figure of Merit. Phys. Rev. B 1993, Method. Inorg. Chem. 2018, 57, 13800−13808.
47, 12727−12731. (1206) Ju, H.; Kim, M.; Park, D.; Kim, J. A Strategy for Low
(1189) Qiu, G.; Huang, S.; Segovia, M.; Venuthurumilli, P. K.; Thermal Conductivity and Enhanced Thermoelectric Performance in
Wang, Y.; Wu, W.; Xu, X.; Ye, P. D. Thermoelectric Performance of SnSe: Porous SnSe1−xSx Nanosheets. Chem. Mater. 2017, 29, 3228−
2D Tellurium with Accumulation Contacts. Nano Lett. 2019, 19, 3236.
1955−1962. (1207) Hong, M.; Chasapis, T. C.; Chen, Z. G.; Yang, L.; Kanatzidis,
(1190) Wang, Y.; Qiu, G.; Wang, R.; Huang, S.; Wang, Q.; Liu, Y.; M. G.; Snyder, G. J.; Zou, J. N-Type Bi2Te3‑XSex Nanoplates with
Du, Y.; Goddard, W. A.; Kim, M. J.; Xu, X.; et al. Field-Effect Enhanced Thermoelectric Efficiency Driven by Wide-Frequency
Transistors Made from Solution-Grown Two-Dimensional Tellurene. Phonon Scatterings and Synergistic Carrier Scatterings. ACS Nano
Nat. Electron. 2018, 1, 228−236. 2016, 10, 4719−4727.
(1191) Min, Y.; Roh, J. W.; Yang, H.; Park, M.; Kim, S. I.; Hwang, (1208) An, J.; Han, M.-K.; Kim, S.-J. Synthesis of Heavily Cu-Doped
S.; Lee, S. M.; Lee, K. H.; Jeong, U. Surfactant-Free Scalable Synthesis Bi2Te3 Nanoparticles and Their Thermoelectric Properties. J. Solid
of Bi2Te3 and Bi2Se3 Nanoflakes and Enhanced Thermoelectric State Chem. 2019, 270, 407−412.
Chem. Rev. 2023, 123, 3329−3442
(1209) Joseph, D.; Navaneethan, M.; Abinaya, R.; Harish, S.; Graphene Hybrid Film for Thermoelectric Device Utilizing Low-
Archana, J.; Ponnusamy, S.; Hara, K.; Hayakawa, Y. Thermoelectric Grade Heat. ACS Appl. Mater. Interfaces 2021, 13, 51245−51254.
Performance of Cu-Doped MoS2 Layered Nanosheets for Low Grade (1227) Nandihalli, N.; Liu, C.-J.; Mori, T. Polymer Based
Waste Heat Recovery. Appl. Surf. Sci. 2020, 505, 144066. Thermoelectric Nanocomposite Materials and Devices: Fabrication
(1210) Wu, F.; Wang, W.; Hu, X.; Tang, M. Thermoelectric and Characteristics. Nano Energy 2020, 78, 105186.
Properties of I-Doped N-Type Bi2Te3-Based Material Prepared by (1228) Min, Y.; Park, G.; Kim, B.; Giri, A.; Zeng, J.; Roh, J. W.; Kim,
Hydrothermal and Subsequent Hot Pressing. Prog. Nat. Sci.: Mater. S. I.; Lee, K. H.; Jeong, U. Synthesis of Multishell Nanoplates by
Int. 2017, 27, 203−207. Consecutive Epitaxial Growth of Bi2Se3 and Bi2Te3 Nanoplates and
(1211) Shi, X.; Zheng, K.; Hong, M.; Liu, W.; Moshwan, R.; Wang, Enhanced Thermoelectric Properties. ACS Nano 2015, 9, 6843−
Y.; Qu, X.; Chen, Z. G.; Zou, J. Boosting the Thermoelectric 6853.
Performance of P-Type Heavily Cu-Doped Polycrystalline SnSe via (1229) Yang, H.; Valenzuela, S. O.; Chshiev, M.; Couet, S.; Dieny,
Inducing Intensive Crystal Imperfections and Defect Phonon B.; Dlubak, B.; Fert, A.; Garello, K.; Jamet, M.; Jeong, D.-E.; et al.
Scattering. Chem. Sci. 2018, 9, 7376−7389. Two-Dimensional Materials Prospects for Non-Volatile Spintronic
(1212) Zhang, Y.; Liu, Y.; Lim, K. H.; Xing, C.; Li, M.; Zhang, T.; Memories. Nature 2022, 606, 663−673.
Tang, P.; Arbiol, J.; Llorca, J.; Ng, K. M.; et al. Tin Diselenide (1230) Popov, I.; Gemming, S.; Okano, S.; Ranjan, N.; Seifert, G.
Molecular Precursor for Solution-Processable Thermoelectric Materi- Electromechanical Switch Based on Mo6S6 Nanowires. Nano Lett.
als. Angew. Chem., Int. Ed. Engl. 2018, 57, 17063−17068. 2008, 8, 4093−4097.
(1213) Guo, Y.; Dun, C.; Xu, J.; Li, P.; Huang, W.; Mu, J.; Hou, C.; (1231) Petrović, A. P.; Ansermet, D.; Chernyshov, D.; Hoesch, M.;
Hewitt, C. A.; Zhang, Q.; Li, Y.; et al. Wearable Thermoelectric Salloum, D.; Gougeon, P.; Potel, M.; Boeri, L.; Panagopoulos, C. A
Devices Based on Au-Decorated Two-Dimensional MoS2. ACS Appl. Disorder-Enhanced Quasi-One-Dimensional Superconductor. Nat.
Mater. Interfaces 2018, 10, 33316−33321. Commun. 2016, 7, 12262.
(1214) Li, X.; Wang, T.; Jiang, F.; Liu, J.; Liu, P.; Liu, G.; Xu, J.; Liu, (1232) Liu, Y.; Wu, H.; Cheng, H.-C.; Yang, S.; Zhu, E.; He, Q.;
C.; Jiang, Q. Optimizing Thermoelectric Performance of MoS2 Films Ding, M.; Li, D.; Guo, J.; Weiss, N. O.; et al. Toward Barrier Free
by Spontaneous Noble Metal Nanoparticles Decoration. J. Alloys Contact to Molybdenum Disulfide Using Graphene Electrodes. Nano
Compd. 2019, 781, 744−750. Lett. 2015, 15, 3030−3034.
(1215) Zhao, W.; Jin, K.; Fu, L.; Shi, Z.; Xu, B. Mass Production of (1233) Wang, C.; He, Q.; Halim, U.; Liu, Y.; Zhu, E.; Lin, Z.; Xiao,
Pt Single-Atom-Decorated Bismuth Sulfide for N-Type Environ- H.; Duan, X.; Feng, Z.; Cheng, R.; et al. Monolayer Atomic Crystal
mentally Friendly Thermoelectrics. Nano Lett. 2022, 22, 4750−4757. Molecular Superlattices. Nature 2018, 555, 231−236.
(1216) Yang, H.; Bahk, J. H.; Day, T.; Mohammed, A. M.; Snyder, (1234) Neumaier, D.; Pindl, S.; Lemme, M. C. Integrating Graphene
G. J.; Shakouri, A.; Wu, Y. Enhanced Thermoelectric Properties in into Semiconductor Fabrication Lines. Nat. Mater. 2019, 18, 525−
Bulk Nanowire Heterostructure-Based Nanocomposites through 529.
Minority Carrier Blocking. Nano Lett. 2015, 15, 1349−1355. (1235) Henckel, D. A.; Lenz, O.; Cossairt, B. M. Effect of Ligand
(1217) Ju, Z.; Crawford, C.; Adamczyk, J.; Toberer, E. S.; Coverage on Hydrogen Evolution Catalyzed by Colloidal WSe2. ACS
Kauzlarich, S. M. Study of the Thermoelectric Properties of Bi2Te3/ Catal. 2017, 7, 2815−2820.
Sb2Te3 Core−Shell Heterojunction Nanostructures. ACS Appl. Mater. (1236) Wang, Y.; Ma, Z.; Chen, Y.; Zou, M.; Yousaf, M.; Yang, Y.;
Interfaces 2022, 14, 24886−24896. Yang, L.; Cao, A.; Han, R. P. Controlled Synthesis of Core-Shell
(1218) Rani, R.; Tusseau-Nenez, S.; Coulon, P.-E.; Wade, T. L.; Carbon@MoS2 Nanotube Sponges as High-Performance Battery
Konczykowski, M. Synthesis and Characterization of a Sb2Te3/Bi2Te3 Electrodes. Adv. Mater. 2016, 28, 10175−10181.
P-N Junction Heterostructure via Electrodeposition in Nanoporous (1237) Wang, X.; Wang, Z.; Zhang, J.; Wang, X.; Zhang, Z.; Wang,
Membranes. iScience 2021, 24, 102694. J.; Zhu, Z.; Li, Z.; Liu, Y.; Hu, X.; et al. Realization of Vertical Metal
(1219) Chen, X.; Cai, F.; Liu, C.; Dong, R.; Qiu, L.; Jiang, L.; Yuan, Semiconductor Heterostructures via Solution Phase Epitaxy. Nat.
G.; Zhang, Q. Enhanced Thermoelectric Performance of Commun. 2018, 9, 3611.
Bi2Te2.7Se0.3/Bi2S3 Synthesized by Anion Exchange Method. Phys. (1238) Lin, L.; Sherrell, P.; Liu, Y.; Lei, W.; Zhang, S.; Zhang, H.;
Status Solidi RRL 2020, 14, 1900679. Wallace, G. G.; Chen, J. Engineered 2D Transition Metal
(1220) Gautam, A. K.; Faraz, M.; Khare, N. Enhanced Thermo- Dichalcogenides�a Vision of viable Hydrogen Evolution Reaction
electric Properties of MoS2 with the Incorporation of Reduced Catalysis. Adv. Energy Mater. 2020, 10, 1903870.
Graphene Oxide (RGO). J. Alloys Compd. 2020, 838, 155673.
(1221) Huang, L.; Lu, J.; Ma, D.; Ma, C.; Zhang, B.; Wang, H.;
Wang, G.; Gregory, D. H.; Zhou, X.; Han, G. Facile in Situ Solution
Synthesis of SnSe/RGO Nanocomposites with Enhanced Thermo-
electric Performance. J. Mater. Chem. A 2020, 8, 1394−1402.
(1222) Buks, K.; Andzane, J.; Bugovecka, L.; Katkov, M. V.; Smits,
̅ s,̌ A.; Brauna, L.; Voikiva, V.;
K.; Starkova, O.; Katkevics, J.; Berziņ
et al. Highly Efficient Flexible n-Type Thermoelectric Films Formed
by Encapsulation of Bi2Se3-MWCNT Hybrid Networks in Polyvinyl
Alcohol. Adv. Mater. Interfaces 2022, 9, 2200318.
(1223) Buks, K.; Andzane, J.; Smits, K.; Zicans, J.; Bitenieks, J.;
Zarins, A.; Erts, D. Growth Mechanisms and Related Thermoelectric
Properties of Innovative Hybrid Networks Fabricated by Direct
Deposition of Bi2Se3 and Sb2Te3 on Multiwalled Carbon Nanotubes.
Mater. Today Energy 2020, 18, 100526.
(1224) Liao, Y.; Liu, W.; Jia, W.; Wang, B.; Chen, L.; Huang, K.;
Montgomery, M. J.; Qian, J.; Lv, S.; Pfefferle, L. D. Bismuth Sulfide
Strongly Coupled to Functionalized Mwnts Hybrids with Improved
Thermoelectric Properties. Adv. Electron. Mater. 2021, 7, 2100468.
(1225) Chen, R.; Lee, J.; Lee, W.; Li, D. Thermoelectrics of
Nanowires. Chem. Rev. 2019, 119, 9260−9302.
(1226) Wang, Y.; Pang, H.; Guo, Q.; Tsujii, N.; Baba, T.; Baba, T.;
Mori, T. Flexible n-Type Abundant Chalcopyrite/PEDOT:PSS/
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4.4. Deposition Methods 3363 7.6.4. Heterostructure Control 3404

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