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Synthesis, Properties, and Applications of 2-D

Materials: A Comprehensive Review
a b c a
Santanu Das , Moonkyung Kim , Jo-won Lee & Wonbong Choi
a
Department of Materials Science and Engineering, University of North Texas, Denton, TX
76207, USA
b
School of Electrical and Computer Engineering, Cornell University, Ithaca, NY 14853, USA
c
Department of Convergence Nanoscience, Hanyang University, Seoul 133-791, Korea
Published online: 15 Apr 2014.

To cite this article: Santanu Das, Moonkyung Kim, Jo-won Lee & Wonbong Choi (2014) Synthesis, Properties, and Applications
of 2-D Materials: A Comprehensive Review, Critical Reviews in Solid State and Materials Sciences, 39:4, 231-252, DOI:
10.1080/10408436.2013.836075

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 Critical Reviews in Solid State and Materials Sciences, 39:231–252, 2014
Copyright c Taylor and Francis Group, LLC
ISSN: 1040-8436 print / 1547-6561 online
DOI: 10.1080/10408436.2013.836075

Synthesis, Properties, and Applications of 2-D Materials:

A Comprehensive Review
Santanu Das,1 Moonkyung Kim,2 Jo-won Lee,3 and Wonbong Choi1,∗
1
Department of Materials Science and Engineering, University of North Texas, Denton, TX 76207, USA
2
School of Electrical and Computer Engineering, Cornell University, Ithaca, NY 14853, USA
3
Department of Convergence Nanoscience, Hanyang University, Seoul 133-791, Korea
Downloaded by [b-on: Biblioteca do conhecimento online UL] at 03:26 22 April 2014

Recent advances in atomically thin two-dimensional (2-D) materials have led to a variety
of promising future technologies for post-CMOS nanoelectronics and energy generation. This
review is an attempt to thoroughly illustrate the current status and future prospects for 2-D ma-
terials other than graphene (e.g., BN nanosheets, MoS2 , NbSe2 , WS2 , etc.), which have already
been contemplated for both low-end and high-end technological applications. An overview of
the different synthesis techniques for 2-D materials is presented here, with an exploration of the
potential for developing methods of controllable large scale synthesis. Furthermore, we sum-
marize the underlying theories which correlate the structural and physical properties of 2-D
materials with their state-of-the-art applications. Finally, we show that utilizing the unprece-
dented properties arising from these materials would lead to innovative devices. Such devices
would significantly reduce both device dimensions and power consumption, as necessary for
the creation of tomorrow’s sustainable technology.

Keywords two-dimensional (2D) materials, nanoelectronics, energy, synthesis, property

Table of Contents

1. INTRODUCTION ................................................................................................................................................ 232

2. CRYSTAL STRUCTURES AND PHYSICAL PROPERTIES ............................................................................... 233

2.1. Transition Metal di-chalcogenides materials (TMDC) ....................................................................................... 233
2.2. Boron Nitride Nano-sheet ............................................................................................................................... 233

3. SYNTHESIS PROCESSES FOR 2-D TMDC MATERIALS ................................................................................. 234

3.1. Exfoliation Processes ..................................................................................................................................... 235
3.1.1. Mechanical Exfoliation ........................................................................................................................ 235
3.1.2. Chemical/Solvent Exfoliations .............................................................................................................. 237
3.2. Chemical Synthesis ........................................................................................................................................ 239
3.3. Chemical Vapor Deposition/Vapor-Phase Growth Process .................................................................................. 241

4. PROPERTIES AND APPLICATIONS OF 2-D MATERIALS ............................................................................... 243

4.1. Electrical Properties ....................................................................................................................................... 243
4.2. Applications .................................................................................................................................................. 245

5. SUMMARY ......................................................................................................................................................... 247

6. FUTURE PERSPECTIVES .................................................................................................................................. 248

∗
E-mail: Wonbong.Choi@unt.edu
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/bsms.

231
 232 S. DAS ET AL.

ACKNOWLEDGMENTS .......................................................................................................................................... 248

FUNDING ................................................................................................................................................................. 248

REFERENCES ......................................................................................................................................................... 248

1. INTRODUCTION materials can be metallic, semi-metallic, or semiconducting. In

An atomically thin two-dimensional (2-D) material is defined
as a material whose free charges are immobile in one spatial di-
mension, but mobile in the other two. This property enables 2-D
materials to have new or superior functions, distinct from tra-
ditional bulk materials or thin films. Interest in 2-D films dates
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addition, much like graphene, these materials exhibit physical,
chemical, and mechanical properties which are well suited for
applications in electronics, photonics, composites, and energy
storage. In particular, some of the TMDC materials and their
heterostructures have shown remarkable electronic and opto-

back to the late 1970s and early 1980s, when the formation electronic properties. For example, monolayer MoS2 exhibits a
of a 2-D electron gas in III-V semiconductors was achieved by direct intrinsic bandgap (∼1.8 eV), acceptable mobility for tran-
molecular beam epitaxial (MBE) growth. This structure led to an sistor operation (∼200 cm2V−1s−1), and quantum confinement.
electron mobility higher than 106 cm2/Vs at 4åK, and resulted in In this context, the intrinsic semiconducting property of the 2-
the development of high electron mobility transistors (HEMT) D MoS2 structure is advantageous, since there is no need for
for the high-frequency analog ICs used in cell phones, satellite doping or making super-narrow ribbons, as would be required
television receivers, etc. However, a combination of relatively to create a comparable energy band gap in graphene. Therefore,
expensive fabrication processes and high power consumption, even at room temperature, 2-D MoS2 based field effect transis-
limits the extensive use of HEMTs. In 2004, the successful exfo- tors exhibit high current on/off ratios of 1 × 108 and ultra-low
liation of graphite into atomically thin 2-D graphene sparked a power dissipation, which will be highly advantageous for future
resurrection of interest in 2-D materials. Graphene is exception- low power electronics.17,18
ally strong, lightweight, flexible, has high optical transmittance, Research on 2-D materials has attracted huge attention from
and allows electrons to move much faster than other materials the scientific community, especially in the last few years19.
with higher thermal conductivity.1,2 These excellent electrical Figure 1 charts the recent exponential increase in the num-
properties could be exploited for transistors that are faster than ber of publications related to BN alone. Although research into
any in existence, as well as ultra wide-bandwidth optical mod- other 2-D materials is at a relatively early stage, it is expected to
ulators. Thus, this material is often referred to as a “wonder
material” of the 21st century. In spite of the excellent properties
of graphene, it is well known that graphene has some shortcom-
ings in electronics applications, including: zero energy bandgap,
intrinsic defects, and severe degradation of carrier mobility due
to scattering caused by defects and/or surface adatoms.
Transition metal dichalcogenides (TMDCs) are the group
of hexagonal structured, van der Waals bonded, layered ma-
terials with the molecular formula MX2 (where M = transi-
tion metals such as Mo, W, Nb, and X = chalcogens such as
S, Se, Te), and space group P63/mmc. The TMDC materials
exhibit strong in-plane bonding along with weak out-of-plane
bonding, enabling the exfoliation of the materials into single
crystal two-dimensional flakes with atomic level thickness. It
has emerged recently that there are over 150 exotic layered
materials which can be split into a single atom thick mate-
rial, including molybdenum disulfide (MoS2 ),3 molybdenum
disilicide (MoSe2 ),4 silicene,5,6 boron nitride (BN),7 tungsten
disulfide (WS2 ),8 WSe2, 8 germanene,9 etc., and their hybrid-
structures.10–16 Looking at these materials very closely, we ob- FIG. 1. The number of publications on different 2-D nanosheets
serve that the consequences of their extraordinary properties including MoS2 , h-BNNS, and others in the period of
are more dimension-dependent than size-dependent, hence cre- 2004–2013. (© American Chemical Society. Reproduced by
ating a new area for research. Depending on their chemical permission of American Chemical Society. Permission to reuse
composition and structural configurations, atomically thin 2-D must be obtained from the rightsholder.)
 SYNTHESIS, PROPERTIES, AND APPLICATIONS OF 2-D MATERIALS
experience a surge similar to graphene/hexigonal-BN research
in the near future.
2. CRYSTAL STRUCTURES AND PHYSICAL PROPERTIES
2.1. Transition Metal di-chalcogenides materials (TMDC)
Monolayer molybdenum disulfide (MoS2 ) is a rising star
among the other 2-D layered materials as a candidate for fu-
ture nano-electronics and optoelectronics,3,20 owing to its direct
intrinsic band gap, high mobility, and quantum confinement.
As discussed in Sec. 1, 2-D MoS2 based FETs will be highly
useful for low-power electronics in post-Si-based technologies.
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In addition to the transistor applications, MoS2 has also proven
to be useful in photocatalysts, solar cells, Li ion batteries.21
and catalysts for hydrogen evolution. In this context, MoS2 and
other TMDC isomorphs have been extensively studied for scal-
able applications in photooxidation, photocatalysis leading to
water/air purification, H2 evolution, and energy storage.22
MoS2 is a direct band gap material, with a non centro-
symmetric crystal structure with long-range periodic order. It
is an sp3 bonded solid, consisting of two Mo-S covalent bonds
(as shown in Fig. 2) in a layered structure, where single layers
are connected via interlayer van der Waals interactions.23 The
basic building block of MoS2 resembles a graphene-like hexag-
onal honeycomb arrangement of Mo and S atoms. One Mo and
two S atoms occupy two different sublattices of the hexagonal
MoS2 structure, in which a molybdenum layer is sandwiched
between two sulfur layers. Each Mo atom is arranged in a trian-
gular prismatic coordination (i.e., a hexagonally packed six-fold
coordination between two three-fold coordinated sulfur atoms).
This S-Mo-S structure constitutes a single layer of 2D-MoS2 ,
as shown in Fig. 2a. When two or three stacked single layers of
FIG. 2. (a) Schematic illustrating the crystal structure of MoS2
(© Macmillan Publishers, Ltd. Reproduced by permission of
Radisavljevic et al.3 Permission to reuse must be obtained from
the rightsholder); (b) and (c) showing the in-plane and out of
plane crystal structure of MoS2, respectively (© American
Physical Society. Reproduced by permission of Mak et al.27
Permission to reuse must be obtained from the rightsholder).
233
S-Mo-S are held together by weak van der Waals forces, bi- and
tri-layer structures of MoS2 are formed, respectively. If more
than 100 single layers of MoS2 are stacked together, 3-D bulk
MoS2 is formed.
Cao et al. calculated the optimized structure of MoS2 using
local density approximations in density functional theory. They
found that the MoS2 unit cell consists of a honeycomb lattice
structure with a lattice parameter “a” of 3.12 Å, and a vertical
separation between sulfur layers “c” of 3.11 Å (shown in Figs.
2a and b).24 MoS2 is classified as a d-orbital material,25,26 be-
cause Mo d-orbitals form both the highest valence bands and
the lowest conduction bands. Furthermore, the outer d-electron
interactions give rise to a band gap (∼1 eV) between the occu-
pied and unoccupied “d” states of 2-D MoS2 , which makes it
different from other sp bonded semiconductor nanostructures.
However, theoretical calculations and experimental techniques
show that the band gap of MoS2 varies from 0.8–1.8 eV based
on the number of layers. Similarly, other TMDC materials ex-
hibit characteristics identical to MoS2, owing to third-orbital
interactions as reported earlier.
Interestingly, the observed bandgap changes from an indirect
band gap into a direct band gap when the 3-D bulk structure is
transformed into a 2-D superstructure, as illustrated in Fig. 3c.27
In 3-D MoS2 , the indirect band gap lies below the direct band
gap. However, the direct band gap shifts upwards as the number
of layers decreases, resulting in a crossover to a direct-gap mate-
rial in single layer MoS2. 27 This band gap transition occurs due
to the extensive quantum confinement in the 2-D structure, in
comparison to the 3-D structure. The photoluminiscence prop-
erties also arise from direct-gap transitions between the split
valence band maxima (v1 and v2) (Fig. 2c), and the conduc-
tion band minima (c1) at the K point of the Brillouin zone, as
described in Mak et al.27 This is the primary reason that MoS2
shows photoluminescence in its 2-D forms, whereas photolu-
minescence properties are absent in its 3-D bulk structure.23,28
Likewise, atomic layer thick TMDC materials are uniquely dis-
tinguished by the quantum confinement they exhibit, which is
not seen in other sp3 bonded semiconductor materials.23 On the
other hand, dimension dependent band gap transitions along the
visible to near-infrared light regime are manifestations of carrier
generation, suggesting promise for these types of materials in
applications in sustainable solar-energy conversion systems.29
2.2. Boron Nitride Nano-sheet
2-D single-layered hexagonal boron nitride nanosheets (h-
BNNSs) are iso-structural to graphene; hence, they are also
known as white graphene, boron nitrene, and boronitrene.
BNNSs are insulator materials with a large band gap of
∼5.0–7.0 eV. Thus, they exhibit a high breakdown voltage,
typically ∼ 1 × 106 Vm−1, but the exact value somewhat de-
pendent upon the number of stacked layers in h-BN. As in
graphene, hexagonal boron nitride nano ribbons (h-BNNRs)
show anisotropic electronic and magnetic properties based on
 234 S. DAS ET AL.
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FIG. 3. (a) Illustration of the coordination structure of Mo (blue
sphere) in MoS2 . Mo and S are shown with blue and golden
spheres, respectively. (b) A top view of the monolayer MoS2
lattice, emphasizing the iso-structure of a honeycomb lattice.
The yellow shaded region bounded by dashed lines represents
one primitive cell as shown in Fig. 2a (© Macmillan Publishers,
Ltd. Reproduced by permission of Cao et al.24 Permission to
reuse must be obtained from the rightsholder). (c) Simplified
band structures of 3-D bulk MoS2 showing the indirect band gap
Eg / and direct band gap Eg for 2-D monolayer (© American
Physical Society. Reproduced by permission of Mak et al.27
Permission to reuse must be obtained from the rightsholder).
their edge shapes (zigzag or armchair), owing to their edge de-
pendent quantum confinement.30,31 Hence, the electronic trans-
port properties and band gap of h-BNNRs display variations
like graphene nano ribbons (GNRs) based on the edge structure,
width, and chemical functionalization.30–32 In this context, the
optical band gap of h-BNNSs are experimentally found to be
∼6.0 eV33; hence, low dimension h-BNNSs exhibit high trans-
parency through the visible region34,35. Furthermore, the band
gap of h-BNNSs is tunable by changing the number of layers,
by varying the width, or by applying an external field, which
is well known as the “Stark Effect.” Similarly, the band gap of
2-D h-BNNS nano structures can also be controlled by molecu-
lar functionalization,36–39 introducing defects,40 and the applica-
tion of longitudinal strain,41–43 just as in graphene. However, the
band gap of graphene increases with chemical functionalization,
whereas h-BNNSs show a decrease in band gap with function-
alization, a phenomenon known as the “reversal effect.” The
physical properties of 2-D h-BNNSs strongly depend on their
crystallinity, stacking order, and defects, which are correlated
with the electrical, optical, magnetic, and dielectric properties of
h-BNNSs.40,44 Up until now, 2-D h-BNNSs have been success-
fully integrated into several applications, such as substrates for
graphene electronics,13,16,34 catalysts,45 deep ultraviolet (DUV)
lasing,33,46 energy storage,47 piezoelectric devices,42 compos-
ites,48,49 and many more.50
The crystallographic parameters of h-BN and graphite re-
semble each other, therefore boron nitride is frequently referred
to as white graphite. Like graphite, hexagonal forms of BN ex-
hibit a planar honeycomb layered lattice with strong inter atomic
(B-N) covalent bonds, and interlayer van der Walls bonds. The
interatomic bond distance “a” and the interlayer distance “c” of
h-BN are ∼2.51Å and ∼ 3.35 Å, respectively, which is essen-
tially isostructural with graphite. Similarly to graphite, h-BN is
the softest allotrope of h-BN isomorphs with a wide range of
properties. A single atomic layer of h-BN, also known as boron
nitride nanosheet (h-BNNS), white graphene, boron nitrene, or
boronitrene, exhibits interesting properties when it is separated
from the bulk structure. The only difference between graphite
and h-BN is their super-imposed inter-layer stacking order, is
superposed. In the case of h-BN (as shown in Fig. 4a), all B
and N atoms are exactly located upon one another in between
the two layers. In graphite, however, the layers are shifted by a
half-hexagon relative to each other. However, there is no such
difference between a single graphene layer and h-BNNS, ex-
cept that half of the lattice consists of nitrogen atoms (Fig. 4a).
Boron nitride nano-sheets also exhibit a ribbon structure when
the width is scaled down from the submicron to nanometer scale
as shown in Figs. 4b, c, and d. Like graphene, h-BNNRs exhibit
the zigzag and armchair edge structures (Figs. 4c and d), which
subsequently have an effect on their properties. Since BNNS are
iso-structural to graphene, carbon can readily replace boron and
nitrogen, forming a new type of material called carbo-boron ni-
tride (CBN). The primary structural difference between BN and
graphene is their bonding characteristics. The in-plane bonds
between B and N atoms exhibit a mixture of covalent and ionic
bonding, owing to the difference in electronegativity between
boron and nitrogen atoms. However, graphene exhibits purely
covalent bonding between C-C atoms. Recent studies show that
the band structure and band gap of h-BN is solely correlated
to its interlayer stacking order, determining the direct and the
indirect nature of its band structures.51
3. SYNTHESIS PROCESSES FOR 2-D TMDC MATERIALS
Recently, several methods have been proposed for synthe-
sizing 2-D materials. The synthetic route of 2-D materials
can be divided into two basic categories: (1) top-down meth-
ods and (2) bottom-up methods.53 Top-down methods dictate
the synthesis of 2-D nanostructures by isolating one or few
atomic layers from the bulk under the application of external
energy (mechanical/ultra-sound energy). In contrast, the
bottom-up methods can be defined as processes by which atoms
 SYNTHESIS, PROPERTIES, AND APPLICATIONS OF 2-D MATERIALS 235
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FIG. 4. Structural models of boron nitride illustrating (a) 3-D BN interlayer stacking and (b) a single nano-sheet of hexagonal
honeycomb BN nanosheets consisting of armchair and zigzag edges; (c) and (d) shows zigzag and armchair boron nitride
nanoribbons resembling graphene nanostructures. (© RSC Publisher. Reproduced by permission of Lin and Connell.52 Permission
to reuse must be obtained from the rightsholder.)

are deposited through thermal and/or chemical reactions on a
substrate in order to synthesize 2-D nanostructures.
Among them, mechanical exfoliation (micromechanical
cleaving), chemical exfoliation (high energy exfoliations in so-
lution), chemical synthesis reactions, and thermal chemical va-
por deposition (CVD) are most commonly used for synthesizing
2-D nanostructures. Several other methods such as laser abla-
tion, laser thinning, carbothermal reduction, and high-energy
electron beam irradiation have been proposed for synthesizing
2-D nanostructures. In this section, a brief overview will be pre-
sented of the synthetic processes for 2-D nanostructures, includ-
ing their advantages and limitations. This discussion continues
with a concise overview of the top down and bottom up synthesis
processes in the development of novel 2-D nanostructures.
3.1. Exfoliation Processes
3.1.1. Mechanical Exfoliation
Invented by Novoselov and Geim in 2004 for graphene syn-
thesis, micro-mechanical exfoliation (MME) became highly
popular for synthesizing 2-D materials, due to its versatility and
low cost. Mechanical exfoliation is a straightforward method of
material synthesis which yields one to a few layers of 2-D crys-
talline flakes, while maintaining the crystal structure and prop-
erties. In this process, simple scotch tape is used to exfoliate an
atomic layer thick graphene from the bulk graphite mesas, fol-
lowed by the deposition of those exfoliated layers of graphene on
the substrate. Several other researchers have attempted micro-
mechanical exfoliation by applying a lateral force with atomic
force microscopy (AFM) tips. However, these attempts were
unable to yield single or few layers of graphene.54,55 Follow-
ing graphene, other non carbonaceous 2-D layered inorganic
materials, like the MX2 group of materials, have been success-
fully synthesized using micromechanical exfoliation. To date,
several reports illustrate the synthesis of materials in the MX2
group, including MoS2 , MoSe2 , WS2 , NbSe2 , and WSe2, using
the MME method.56–58 Similarly, a few other reports have suc-
cessfully demonstrated the mechanical exfoliation of BN.57,59
Among them, 2-D MoS2 is considered a potential transistor
material capable of replacing Si in upcoming CMOS based
technology. Toward this end, MoS2 nanosheets have been effec-
tively synthesized using micromechanical exfoliation, as found
in several recent report.3,20,23,60,61 Radisavljevic et al.3 first re-
ported the transistor performance of a single layer MoS2 flake
produced by mechanical exfoliation. The process involved rapid
slicing of 2-D monolayers from a commercially available MoS2
single crystal using scotch tape. The exfoliated MoS2 layers
were further transferred to a SiO2 -Si substrate as shown in the
optical micrograph in Fig. 5a. Figure 5b shows the device fab-
ricated using nano-patterning of the exfoliated MoS2 flake. As
in graphite, the interlayer bonds (van der Waal bonds) in MoS2
are almost ∼100 times weaker than in-plane primary bonds (co-
valent/ionic).62 Hence, a single layer can easily be peeled off
from the bulk, keeping in-plane bonds intact. The same applies
to other TMDC materials as well. The thickness of the MoS2
exfoliated layer was measured using AFM, to be 0.65–0.7 nm
(Figs. 5c and d).
The exfoliated MoS2 layers can also be characterized using
optical microscopy, where contrasting colors were observed in
areas with different layer thicknesses (Figs. 5a and 6a).
 236 S. DAS ET AL.
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FIG. 5. (a) and (b) Optical micrographs of a micro-mechanically exfoliated monolayer of MoS2 on a SiO2 /Si substrate, and a
transistor device made out of the monolayer MoS2 , respectively; (c) AFM image of a scotch tape exfoliated, large-scale single
MoS2 layer, 6.5 Å thick (© Macmillan Publishers, Ltd. Reproduced by permission of Radisavljevic et al.3 Permission to reuse
must be obtained from the rightsholder) and (d) Profile of a monolayer MoS2 fabricated using mechanical exfoliation with a similar
height of ∼7 Å, found in a separate report (© American Chemical Society. Reproduced by permission of Late et al.60 Permission
to reuse must be obtained from the rightsholder).

Splendiani et al. demonstrated a straightforward characteri-
zation technique for determining the number of layers in exfoli-
ated MoS2 by combining optical microscopy with AFM height
profiles (Figs. 6a–). However, optical contrast is only capable of
distinguishing up to four layers. Therefore, for 2-D nanostruc-
tures having more than four layers, high resolution transmission
electron microscopy and AFM are the only available options
for measuring the exact number of layers. Similarly, attempts
have been made to fabricate h-BNNSs by the mechanical ex-
foliation method. Paciléet et al.59 reported the exfoliation of
few layer BN membranes using the scotch tape method (Figs.
7a and b). The thickness of h-BNNS deposited on SiO2 /Si is
approximately 10 layers thick. This report delineated that it is
quite difficult to fabricate monolayer h-BNNS using mechanical
exfoliation, because the interlayer bonds of h-BN are stronger
than in graphite.59 A few other reports demonstrated a different
approach for synthesizing large scale mechanically exfoliated
BNNS and other 2-D materials, by low-energy ball milling, and
combining ball milling with sonication. The ball milling method
is effective in producing large scale 2-D BNNS; nevertheless,
the yield of mono- to few layer sheets by this process is ex-
tremely low. Furthermore, the ball milling process is unreliable
for controlling the nanosheet morphology and defects in the
structure.63,64 Recently, hydrogen-terminated germanane (GeH)
is synthesized using mechanical exfoliation. Bianco et al.65
demonstrated the chemical conversion of β-CaGe2 into GeH
followed by the extraction of single to few layer using the
scotch-tape mechanical exfoliation. Optical micrograph, and
corresponding height profile, shows that the formation of single
to few layer-thick germanane flakes on the substrate.65
Mechanical exfoliation is a low cost method of 2-D mate-
rials production, and is extremely convenient for fundamental
research. However, scalable production of 2-D flakes is highly
challenging at this time. Although mechanical exfoliation is
quite capable of fabricating single layer 2-D graphene and
TMDC materials, production of single layer BNNS is not easily
achievable. This difficulty is due to the strong interlayer bonding
energy of h-BN compared to the other layered materials hav-
ing interlayer van der Waals bonds.52,63,66 Additionally, several
other factors (stoichiometry and stacking orders) play a key role
in successful fabrication of monolayer MX2 nanostructures by
the mechanical exfoliation.
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FIG. 6. (a) & (b) Mechanically exfoliated MoS2 layers on a
Si/SiO2 substrate. (a) Optical microscope image of layered of
MoS2 , with differing colors corresponding to different layer
thicknesses. The areas are marked as “1L”, “2L,” and “4L”
are monolayer, bilayer, and quadri-layer, respectively; (b) AFM
image of the same sample; and (c) sample height profile (mea-
sured using AFM) along the red line in (b), which confirms
the corresponding thickness of areas as 1L, 2L, 4L, and 6L.
(© American Chemical Society. Reproduced by permission of
Splendiani et al.23 Permission to reuse must be obtained from the
rightsholder.)
3.1.2. Chemical/Solvent Exfoliations
Solvent exfoliation processe is another top-down approach,
where sonication is applied to bulk layered materials to exfoli-
ate 2-D nano-sheets, which are then dispersed in liquid solvents.
Low power sonication is used as a source of external energy,
which exfoliates the bulk crystals into atomically thin sheets. In
this liquid-state exfoliation process, different types of organic
237
FIG. 7. (a) Tapping mode atomic force micrograph of exfoliated
boron nitride nanosheets on SiO2 /Si; (b) AFM height profile
along the black dashed line in Fig. 7a, illustrating the thickness
of the thinnest region at 3.5 nm, which is 10 layers thick. (©
AIP Publishing. Reproduced by permission of Pacile et al.59
Permission to reuse must be obtained from the rightsholder.)
solvents (listed in Table 1) are used as a dispersing medium,
depending on the bulk crystal material. This process may also
involve the dispersion of powders in a solvent by sonication,
followed by the centrifugation. A variety of 2-D materials have
been synthesized using solvent exfoliation processes, as detailed
in a few recent reports (Table 1).67–69 These processes yield 5–20
layers of 2-D nanosheets homogeneously dispersed in a solvent.
Coleman et al.67 emphasized that the sonication time and cen-
trifugation rate are the primary parameters for controlling the
quality of the dispersion.67,68 Figures 8a, b, and c show transmis-
sion electron micrographs (TEM) of BN, MoS2 , and WS2 2-D
nanostructures, respectively. However, these nanostructures are
only ∼ 1μm in size, and the report does not directly comment
upon whether the process is capable of producing larger flakes.
In general, optimal dispersion takes place in solvents where
the specific surface tension is close to 40 mJ.m−2, the value
previously reported for dispersions of CNT and graphene.70,71
The syntheses of hybrid 2-D nanosheets- MoS2 /graphene,
WS2 /graphene, and BN/graphene have been effectively demon-
strated using the solvent exfoliation process. However, di-
rect chemical exfoliation is incapable of peeling off a single
 238 S. DAS ET AL.

TABLE 1
Solvents used for dispersion of BN, MoS2 and WS2 . (© AAAS. Reproduced by permission of Coleman et al.67 Permission to
reuse must be obtained from the rightsholder)

BN MoS2 WS2
Solvent A/l (AU) 300 nm Solvent A/l (AU) 670 nm Solvent A/l (AU) 630 nm

1 Cyclohexyl-pyrrolidinone (CHP) 100 NVP 100 DMSO 100

2 N-dodecyl-pyrrolidone (N12P) 61 N8P 98 NVP 92
3 Benzyl Benzoate 44 N12P 97 NMF 90
4 Isopropanol 44 CHP 88 N12P 84
5 N-Octyl-pyrrolidone (N8P) 44 NMP 80 DMEU 75
6 N-vinyl-Pyrrolidinone (NVP) 41 DMEU 73 DMF 73
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7 Benzyl Ether 40 DMSO 61 Benzyl benzoate 71

8 dimethyl-imidazolidinone (DMEU) 36 DMF 54 CHP 69
9 Cyclohexanone 29 DMA 54 Cyclohexanone 63
10 Chlorobenzene 28 Benzaldehyde 51 Benzonitrile 59
11 Dimethylsulphoxide (DMSO) 27 Benzonitrile 47 N8P 59
12 Benzonitrile 26 Benzyl benzoate 46 Isopropanol 59
13 Chlorobenzene 25 NMF 41 DMA 57
14 Chloroform 23 Cyclohexanone 38 Benzylether 55
15 Bromobenzene 23 Isopropanol 32 Chlorobenzene 45
16 N-methyl-pyrrolidinone (NMP) 23 Qunioline 26 Methanol 45
17 N-Methyl Formamide (NMF) 21 Acetone 24 Formamide 40
18 dimethylformamide (DMF) 18 Benzylether 23 Bromobenzene 29
19 dimethylacetamide (DMA) 16 Cyclohexane 22 Quinoline 26
20 Formamide 9 Methanol 21 Acetone 17

layer of a 2-D nanostructure, which is a primary need for elec-
tronic applications. To address this issue, a Lithium (Li) inter-
calation process for synthesizing a single sheet of MoS2 was
introduced. The process involves the intercalation of Li ions
between the MoS2 layers, which can be exfoliated into mono-
layers via forced hydration, yielding a stable MoS2 colloidal
suspension. Eda et al. reported that the Li intercalation can be
performed by immersing bulk MoS2 crystals in a butyllithium-
hexane solution for a few days in an inert gas filled flask.69
This reaction formed Lix MoS2, which was fully recovered by
filtration, followed by washing with hexane to remove excess
lithium and organic residues. In this report, the intercalation-
induced phase transformation was fully reversed by performing
a thermal annealing process, which restored the semiconductor
properties of the pristine MoS2 as confirmed by the occurrence
of the band gap in photoluminescence spectra.69 In a separate

FIG. 8. (A), (B), and (C) TEM of BN, MoS2 , and WS2 , respectively. (© AAAS. Reproduced by permission of Coleman et al.67
Permission to reuse must be obtained from the rightsholder.)
 SYNTHESIS, PROPERTIES, AND APPLICATIONS OF 2-D MATERIALS
report, Li intercalation was applied to a WS2 film using LiBH4 ,
according to the reaction shown in Eq. (1):72
LiBH4 + WS2 → LiWS2 + 1/2B2 H6 + 1/2H2 . [1]
Similarly, other Fe/Co based intercalation exfoliation processes
have also been used to synthesize monolayers of MoS2, for use
as a substrate for magnetic materials.73 Chemical exfoliation is
a highly desirable, versatile process that is relevant for gram
scale production of 2-D nanomaterials.72 However, achieving a
homogeneous dispersion of 2-D materials is a challenging task,
as an effective dispersion is dependent on the specific surface
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tension of the solvent. Similarly, a Li+ ion-based intercalation
process unfortunately incorporates physisorbed Li+ ions at the
surface, which deteriorates the electrical and thermal properties
of the end products.
3.2. Chemical Synthesis
Chemical synthesis is a low-cost room temperature process,
which can effectively synthesize several types of carbonaceous
and non-carbonaceous 2-D nanosheets. The chemical synthesis
process is a bottom up approach, where atoms/molecules are
deposited on a substrate, forming a 2-D layered structure by a
step-by-step deposition process. Whereas solvent exfoliation is
already well optimized and commonly used to synthesize 2-D
nanostructures, chemical synthesis methods are still being ac-
tively investigated to achieve further optimizations. Basically,
these are wet chemical methods, which yield 2-D nanostruc-
tures via chemical reactions and deposition onto the substrates.
Chemical synthesis is a low-cost scalable synthesis technique for
2-D TMDC materials. However, when a TMDC is synthesized
chemically, it is comparatively difficult to obtain the optimum
stoichiometry in the final product. A few recent reports have
demonstrated the synthesis of 2-D MoS2 , WS2 , NbSe2 , BN,
etc. using chemical synthesis processes. The starting materi-
als/precursors and synthesis approaches vary with each type of
material. In general, these processes have several strengths and
weaknesses, which are discussed in the following sections.
Sekar et al.74 reported the synthesis of 2-D NbSe2 nanostruc-
tures using a solution reaction process, followed by the ther-
mal decomposition of the precursor materials niobium chloride
(NbCl5 ) and elemental selenium (Se). The process consists of
the reaction of 20 mL of degassed oleylamine (dodecylamine)
with a mixture of NbCl5 (1 mM) and Se (2 mM) under an
inert atmosphere, followed by the heating at 250–280◦ C for
4 h. During this process, the precursors dissolved and formed a
black suspension. This black suspension was collected, washed
and heated at 450◦ C for 3 h under the inert atmosphere, yield-
ing the nanoscale 2-D lamellar structure of NbSe2 shown in
Fig. 9. The authors also proposed controlling the shape and size
of the 2-D NbSe2 nanostructures by changing the ratio of the
Nb and Se precursors.74 The authors claimed that this method
239
FIG. 9. Scanning electron micrographs (SEM) of 2-D nanoscale
NbSe2 plates produced by a chemical synthesis process. Top
inset Figure: NbSe2 nanoplates synthesized in dodecylamine.
Bottom inset: HRTEM of individual nanoplates viewed on-
edge, showing their multi-layered structure. The short axis of
the nanoplates is parallel to the c-axis and perpendicular to the
(002) planes. (© American Chemical Society. Reproduced by
permission of Sekar et al.74 Permission to reuse must be obtained
from the rightsholder.)
can be readily extended for the synthesis of other 2-D mate-
rials, such as TaS2 , TaSe2 , and NaTaO3 , etc. Similarly, a few
interesting chemical synthesis methods have been proposed to
synthesize 2-D MoS2 75 and WS2 75,76 nanostructures. Altavilla
et al.75 demonstrated the synthesis of MoS2 and WS2 by decom-
posing a single source precursor of metal and sulfur in oley-
lamine, which produced a high-quality 2-D free standing single
nanosheet.
Another interesting approach illustrates the formation of
a 2-D WS2 layer through a rolling-out shape-transformation
process (A step-by-step schematic of the mechanism of the
process is shown in Fig. 10a) of a 1D W18 O49 nanorod
precursor, as shown in Figure 10b. In this process, tungsten
oxide nanorods were used as a starting material/precursor, and
were transformed into laterally confined (less than 100 nm)
2-D WS2 nanosheets (as shown in Fig. 10c) after several
steps of surfactant-assisted sulfurization reactions. First,
sulfurization occurs by a reaction between carbon disulfide
and hexadecylamine, which generates hydrogen disulfide and
hexadecylisothiocyanate via an N-hexa-decyldithiocarbamate
intermediate, as shown in Eq. (2). Next, the sulfurization
reaction continues, followed by the unrolling of the W18 O49
nanorods into a sheet structure. In fact, the transformation from
nanorods to nanosheets occurred with a simultaneous reduction
 240 S. DAS ET AL.
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FIG. 10. (a) Mechanism of 2-D WS2 nanosheet crystal formation, through a rolling-out shape-transformation processes of 1D
W18 O49 nanorod precursors. (b) TEM image of W18 O49 nanorod precursors. (c) TEM image of the formation of 2-D WS2 . (©
Wiley. Reproduced by permission of Seo et al.76 Permission to reuse must be obtained from the rightsholder.)

from oxide to sulfide. Hence, this report also highlighted the
development of massive strain in the final product, due to the
continuous heterogeneous transformation from a 1-D to a 2-D
nanostructure. Furthermore, the assembling of nanosheets in
a multilayered structure because of van der Walls attraction
was also observed in this process.76 The process is capable of
producing high quality 2-D nanosheets with dimensions of ∼
100 nm, with a large surface area. Furthermore, the open-edge
morphology of the 2-D nanosheet could play an important role
in retaining a high intercalation capacity, which enables this
type of restructured material to make an excellent electrode.
Preparation of 2-D boron nitride nano sheets (h-BNNS) via
chemical synthesis processes have been demonstrated in another
report, by reacting boric acid with urea. Hwang et al. demon-
strated a series of chemical reactions using different molar ratios
(1:6, 1:12, 1:24, 1:48, and 1:72) of boric acid and urea, dissolved
in 40 mL of water and heated to 65◦ C until the mixture dried.
The dried mixture was further heated to 900◦ C in an inert at-
mosphere for a prolonged period of time. The reactions occur
in a three-step process, as shown in Eqs. (3), (4), and (5). The
reactions subsequently yield a white powder containing BN as
the final product:77
2B(OH)3 → B2 O3 + 3H2 O [3]
NH2 CONH2 → NH3 + HNCO [4]
B2 O3 + 2NH3 → 2BN + 3H2 O. [5]
The authors of this article also discussed the effect of the molar
ratios of Boric acid and urea, finding that an increase in urea
content in the reaction mixture reduced the number of layers in
the final product. Therefore, it was claimed that this process is
well capable of controlling the number of BN layers produced.77
The production of other non carbonaceous 2-D TMDC ma-
terials via wet chemical synthesis needs further rigorous in-
vesigation. The chemical synthesis processes themselves are
highly useful, as they may be able to produce gram-scale 2-D
nanomaterials with fewer defects and less crystalline disorder
than other methods. Additionally, chemical synthesis exhibits
other advantages, such as low-temperature processes, low-cost
starting materials, easy functionalization, and high reliability.
 SYNTHESIS, PROPERTIES, AND APPLICATIONS OF 2-D MATERIALS 241

However, due to their non stoichiometic structure and wide

range of physical properties, many optimizations will be re-
quired to apply those materials in commercial products.

3.3. Chemical Vapor Deposition/Vapor-Phase Growth

Process
Chemical Vapor Deposition (CVD) is a high-temperature
chemical synthesis process by which a desired material is de-
posited on substrates. CVD processes have been extensively
studied for synthesizing thin film coatings of a wide range of ma-
terials, including metals, semiconductors, and insulators. How-
ever, the process was not recognized as a method for 2-D nanos-
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tructure synthesis until Li et al.78 demonstrated the synthesis

of a large-scale monolayer graphene on Cu foil by CVD under
conditions of flowing methane at 1000◦ C. Similarly, graphene
synthesis on other transition metals using CVD of hydrocarbons
has been discussed in several recent reports.79 In this context,
Hwang et al. and Fanton et al. reported on the van der Waals
epitaxial growth of graphene over large areas on c-plane (0001)
sapphire without using a metal catalyst.80,81
The CVD process has also been applied to the synthesis of
large scale homogeneous 2-D transition metal dichalcogenides
(TMDC) and boron nitride nanosheets. CVD is a very straight-
forward method of synthesizing metal sulfides, by reacting sul-
fur vapor with metal thin films at high temperatures under an
inert atmosphere. Using a metal thin film and sulfur powder as
starting materials, the following reaction occurs during the CVD
process (Eq. (6)):
M(s) + 2S(g) → MS2 (s), [6]
where “M” signifies any transition metal thin film, such as Mo,
Nb, W, etc. The reaction temperature is kept at 750◦ C under a
constant flow of N2 .Among the MX2 group of TMDCs, large
area synthesis of 2-D MoS2 has been demonstrated by CVD
methods.82–84 In this process, a molybdenum (Mo) thin film
is exposed to a flow of sulfur (S) vapor at high temperature
under an inert atmosphere, which transforms the Mo thin film
into a 2-D MoS2 thin layer. Zhan et al.82 demonstrated this
MoS2 synthesis on SiO2 /Si by depositing the Mo thin film on
the substrate, followed by the CVD process. The Mo-coated
substrate and sulfur powder were placed inside a CVD furnace,
and the reaction environment was kept inert under a constant
flow of ∼200 sccm N2 . The temperature was increased to 750◦ C
for 90 min, allowing the Mo to react with evaporated sulfur,
resulting in the synthesized MoS2 film on SiO2 /Si shown in Fig.
11a. HRTEM images confirmed the formation of a MoS2 thin
film, with a thickness ranging from single to a few layers (Figs.
11b, c, and d.). This is one of the first reports of direct synthesis
of single- and few-layered MoS2 on SiO2 /Si substrates by any
CVD method. The authors emphasized that the size and thick-
ness of the 2-D MoS2 layer varies predictably with the substrate
size and the Mo thickness, as demonstrated in Figs.11c and d.
FIG. 11. (a) Scanning electron micrograph (SEM) of 2-D MoS2
on SiO2 /Si, (b) TEM image of CVD grown MoS2 film, and
(c) TEM image illustrating the number of layers of 2-D MoS2
formed by a CVD process. (© Wiley. Reproduced by permis-
sion of Zhan et al.82 Permission to reuse must be obtained from
the rightsholder.)
In a similar approach, a metal oxide thin film may be exposed
to sulfur vapor to reduce the oxide to a 2-D MoS2 layer. This
reaction process, also known as sulfurization, is carried out at
elevated temperatures under a constant flow of inert gas (N2 ). In
the overall process, the starting material molybdenum trioxide
(MoO3 ) is reduced to the metal disulfide according to the re-
actions (Eqs. (7) and (8)). Upon exposure to a stream of sulfur
vapor at elevated temperatures, MoO3 is initially converted into
a sub oxide MoO3-x , which reacts further to form a 2-D layered
MoS2 nanostructure (as shown in Fig. 12a):
MoO3 (S) + S(g) → MoO3−x (S) + SOx (g) [7]
MoO3−x (S) + S(g) → MoS2 (S). [8]
The reduction reaction (sulfurization) of MoO3 occurs at
650◦ C, which is comparatively a lower temperature syn-
thesis process than the direct reaction method.82 The pro-
cess schematic is shown in Fig. 12a, where the substrate is
mounted top down inside the CVD chamber for more effi-
cient deposition.83 This simple process is capable of produc-
ing large-scale MoS2 multilayers; however, synthesizing a sin-
gle layer of MoS2 by this method is extremely difficult. The
report cites inhibition of the growth of MoS2 by the inter-
facial oxide layer as a significant obstacle to synthesis of a
single layer of MoS2 on SiO2 /Si. To address this issue, Lee
et al.83 introduced a highly sensitive process for pre-treatment
of the substrate prior to synthesis of the thin layer of MoS2 .
 242 S. DAS ET AL.
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FIG. 12. (a) Schematic illustrating the experimental set-up for the large scale CVD synthesis of MoS2 . (b) The optical micrographs
of the MoS2 layers grown by CVD on the substrate treated with RGO solution. The inset shows the magnified OM of the MoS2
films, where the seed is observed at the center of each star-shaped sheet. (c) AFM of a monolayer MoS2 film on a SiO2 /Si substrate
(pre-treated with RGO). (d) The height profile of the MoS2 layer, measured by AFM to be 0.72 nm. (© Wiley. Reproduced by
permission of Lee et al.83 Permission to reuse must be obtained from the rightsholder.)

The SiO2 /Si substrate was pretreated with reduced graphene
oxide (rGO), parylene-3,4,9,10-tetracarboxylic acid tetra-
potassium salt (PTAS) and parylene-3,4,9,10-tetracarboxylic di-
anhydride (PTCDA), which promote the successful formation
of large area 2-D single layer MoS2 . The authors suggest that
the rGO pre-treatment of the substrate creates nucleation sites
for the synthesis of MoS2 as shown in the optical micrograph
in Fig. 12b. The thickness of the 2-D nanosheet was measured
using AFM and found to be ∼0.7 nm, which confirms the depo-
sition of single layer MoS2 on SiO2 /Si as illustrated in Figs. 12c
and d. In a recent approach, Wang et al.84 demonstrated con-
trol over the deposition of a specific number of layers of highly
crystalline MoS2 using a CVD process. Microcrystalline MoO2
templates were used as starting materials for the synthesis of
highly crystalline 2-D MoS2 flakes with a controllable number
of layers.
As an alternative to transition metal dichalcogenides, large-
scale 2-D h-BNNS has received much interest from the scien-
tific community for integration with graphene in the scalable
fabrication of graphene based FET devices.11,85 More specif-
ically, h-BN exhibits a large band gap (5.97 eV), hexago-
nal lattice structure, and very small lattice mismatch (only
1.7%) with graphene.86 Thus, h-BN is proposed as an ideal
substrates for graphene electronics.86–88 The synthesis of 2-
D h-BNNS is technologically significant because it exhibits
a high breakdown voltage (1 × 106 V.m−1), good thermal con-
ductivity (300–2000 Wm−1K−1), high transparency, and useful
mechanical properties. One recent review systematically ex-
amined all the h-BNNS synthesis methods which use high-
temperature chemical vapor deposition.52 In fact, the depo-
sition of BN thin films by CVD with diborane (B2 H6 ) and
ammonia (NH3 ) at ∼ 600–1000◦ C was demonstrated in the
early 1960’s.89 Recently, 2-D h-BNNS was synthesized using
CVD with ammonia borane/ borazane (BH3 NH3 ) and borazine
(B3 N3 H6 ) as precursors, while maintaining a 1:1 ratio of boron
(B) and nitrogen (N). Deposition of 2–5 layers of h-BNNS on
a centimeter-scale was first demonstrated by ambient pressure
CVD at 1000◦ C on a Cu substrate using an ammonia borane
precursor under a reducing atmosphere.34 Song et al.34 reported
that the film contained a few layers of h-BNNS with high trans-
parency and a large band gap (5.56 eV). Nevertheless, the crys-
tallinity, electrical and thermal properties depend strongly on
 SYNTHESIS, PROPERTIES, AND APPLICATIONS OF 2-D MATERIALS
several other factors such as: (1) precursor materials, (2) sub-
strate morphologies, (3) synthesis temperature, and (4) other
growth conditions. In this context, several variations on the 2-D
h-BNNS CVD process have been reported, using different pre-
cursors, substrates, and substrate morphologies, which led to
improvements in h-BNNSs’ crystallinity and electrical conduc-
tance.90–92 To date, several reports have described the synthesis
of few-layer h-BNNS on a variety of metal substrates, such as
Cu,35,91 Ni (111),93,94 Ru (0001),95 Rd (111),96 Pd (111),97 Pd
(110),98 Pt (111),97 Cr (110),99 Fe (110),100 and single crystal
Cu.101 Similarly, monolayer deposition of h-BNNS on transi-
tion metals has been reported extensively using an ultra-high
vacuum (UHV) process at >700◦ C.94,96–98 Although monolayer
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h-BNNS exhibits excellent properties as discussed above, the
expensive UHV set-up required for this CVD process limits its
usefulness for h-BNNS synthesis from an industrial point of
view.
A few recent articles have also reported the in-situ synthesis
of hybrid 2-D nanostructures of graphene-BNNS and graphene-
MoS2 by thermal CVD processes.11,13,16,102,103 Furthermore, Ci
et al.14 reported the in situ growth of a graphene-h-BNNS hybrid
structure using a thermal CVD process at 900–1000◦ C. These
hybrids between graphene and BN were achieved by simultane-
ously flowing methane (CH4 ) and ammonia borane (NH3 -BH3 )
in the CVD reaction chamber under a reducing atmosphere.
Here, CH4 was used as the source of carbon for graphene growth
whereas NH3 -BH3 used as the source of boron (B) and nitrogen
(N) for BN deposition. Cu foil, which was annealed at 600◦ C
for 20 min before the growth process, was used as a substrate.
The process pressure was kept under ∼200 mT at 1000◦ C, with
a constant flow of CH4 . The ratios of B, C, and N in the final
hybrid structures may be controlled by changing the ratios of
the flow rates of the process gases.14 Liu et al. (2011)13 also
report the synthesis of large scale graphene/h-BN stacked hy-
brid layers grown on a Cu foil using a two-step thermal CVD
process. This process consists of two steps: graphene growth
by using CVD of n-hexane (C6 H14 ) at 950◦ C, followed by the
h-BNNS growth using CVD of ammonia borane (NH3 -BH3 ) at
1000◦ C. The process is highly efficient for the scalable synthesis
of stacked graphene and h-BNNS layers. The uniformity of the
stacked layers and the interlayer hybridizations is further con-
firmed by Raman spectroscopy and x-ray photoelectron spec-
troscopy. Levendorf et al.11 reported a similar two-step CVD
process of graphene/h-BNNS growth on Cu foil which incor-
porated a templated synthesis process. After the graphene was
deposited, it was patterned with photolithography, followed by
h-BN growth using the method described in Mattheiss.25 Hence,
the two-step process for graphene- h-BNNS synthesis is versa-
tile and easily adaptable for synthesizing other hybrid materials.
Shi et al.104 use the same two-step approach for the CVD synthe-
sis of graphene-MoS2 . In this article, graphene is grown on Cu,
followed by the growth of 2-D MoS2 layers. First, Cu foil is used
to grow graphene by the CVD of methane at 1000◦ C, and then
an ammonium thiomolybdate precursor is deposited at 400◦ C.
243
This process also demonstrates that graphene can be used as
an epitaxial substrate for the synthesis of other hexagonal ma-
terials in future. Similarly, a low-temperature synthesis of 2-D
silicene has been reported by direct deposition of evaporated
Si on to Ag (110) substrates at 220–260◦ C.5 Angular-resolved
photoelectron spectroscopy (ARPES) and low-energy electron
diffraction (LEED) confirm the formation of silicone, i.e., the
formation of silicone.5
The main advantage of the CVD synthesis process is to
obtain high quality, high purity 2-D nanomaterials with con-
trolled properties. Additionally, the CVD process allows one
to control the morphology, crystallinity, and defects of the 2-
D nanostructures by controlling different process parameters.
Moreover, by combining a variety of solid, liquid, and gaseous
precursor materials, synthesizing a wide variety of new types of
2-D nanosheets and their hybrids becomes possible. Similarly,
nanosheets can easily be doped and functionalized by introduc-
ing one additional precursor source in the mixture. In contrast,
tailoring atomic level properties, and controlling stoichiometry
and defects in 2-D materials will require further optimizations,
and remain significant challenges in the development of CVD
processes.
4. PROPERTIES AND APPLICATIONS OF 2-D
MATERIALS
4.1. Electrical Properties
The digital revolution has been accomplished mainly by the
dramatic miniaturization of silicon transistors. However, sci-
entists in transistor R&D generally believe that further minia-
turization of silicon transistors cannot continue much longer,
due to physical and technological limits. Nevertheless, new
computer systems such as an Exaflop supercomputer will be
necessary to deal with the explosive increase in data and infor-
mation expected to occur by 2019.105 In general, faster chips
are required to improve the processing power of computer
electronic devices. If the mobility is fixed, the best way to
achieve a higher speed transistor is by scaling-down devices
to narrow the channel size. The 2-D materials exhibit very high
surface-to-volume ratio which is a natural advantage for the re-
duction in power consumption of future nanoelectronics where
the atomic-scale thin materials enable highly efficient modula-
tion of charge transport via surface gates with minimum number
of charges. The new nanoelectronics based on the 2-D materials
could lead to the ultimate size scaling envisioned by Moore’s
Law and beyond. Among 2-D materials, graphene has a theoret-
ical mobility of 1,000,000 cm2/Vsec,106 and has experimentally
shown the fastest mobility, approaching ∼200,000 cm2/Vsec in
a suspended structure.107,108 Although Reddy et al.109 achieved
a mobility of 8,000 cm2/Vsec in a graphene-FET, this value is
still much inferior to that of suspended graphene. This degra-
dation is mainly due to defects induced by the direct deposi-
tion of an insulator layer on graphene109. To prevent mobility
degradation in graphene applications, surface treatments using
 244 S. DAS ET AL.

polyvinyl alcohol (PVA) or other polymers have been suggested,
as a method to suppress random potential fluctuations at the
graphene interface.110 MoS2 turns out to be a direct band gap
semiconductor having extraordinary electronic properties when
made into a 2-D nanosheet. Monolayer MoS2 has many advan-
tages over graphene for more feasible electronic applications,
especially its semiconductor behavior with high on/off current
ratios. Like graphene, 2-D MoS2 has electrical properties that
are much better than those found in the 3-D form of the ma-
terial. The band gap of single layer MoS2 is greater than that
of bulk MoS2 (1.2 eV) by ∼0.6 eV. Likewise, the band gaps of
other 2-D materials such as WS2 , MoSe2 , and WSe2 are larger
than those of the corresponding bulk materials, as shown in
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metal-semiconductor contact. Its room temperature mobility is
∼50 cm2/Vsec, and its on/off ratio at Vd = 1V is larger than
106. The direct band gap of MoSe2 is smaller than that of MoS2
by 0.3 eV in the 2-D material.
Bulk WSe2 , which has an indirect band gap of ∼1.2 eV,
is a layered inorganic semiconductor weakly bonded by van
der Waals forces.113,114 The field-induced hole mobility in bulk
WSe2 based devices has been reported as up to ∼500 cm2/Vsec
at room temperature,115 which is very comparable to that of n-
MOSFETs. The device shows an ambipolar operation and a low
threshold voltage due to an intrinsically low density of surface
traps. However, the reported current on/off ratio of ∼10 at room
temperature is not good enough for digital logic devices. 2-D

Table 2. The dimensional transition from bulk (3-D) to 2-D
MoS2 structure causes a transformation from an indirect band
gap to a direct band gap, which gives the material promise for
many other applications. The direct band gap in 2-D MoS2 leads
to electron-hole pair excitation, which could find applications in
LEDs, photo-detectors and other photonic devices.111 The mo-
bility of an unmodified MoS2 based transistor has been reported
as 200 cm2/Vsec, which has been increased up to 800 cm2/Vsec
with the use of a hafnium oxide gate dielectric. This results in
on/off ratios of as high as 1 × 108 with 25fA/um of off-current
and 2 pA/μm of gate leakage current.3 (Fig. 13)
MoSe2 has also been investigated in a back-gated FET struc-
ture.112 As in MoS2 , its band gap changes from an indirect band
gap in the bulk to a direct band gap in the 2-D sheet, mak-
ing it applicable for energy conversion and photo-electronics.
Figure 14 exhibits the electrical characteristics of a MoSe2 -FET,
where Ni is used as the source/drain contacts to the highly doped
Si back-gate. The asymmetry of drain currents when swapping
the source and drain contacts reveals the Schottky barrier at the
WSe2 based devices (Fig. 15) having high-k dielectric top-gates
show a comparable hole mobility of ∼250 cm2/Vsec, a sub-
threshold swing of ∼60 mV/sec, and very high current on/off
ratios of >106.56
Other group-IV elements, such as silicene and germanene,
also exhibit a stable honeycomb 2-D structure, which shows
superior properties to those of bulk material. Silicine (i.e., a
monolayer of Si) is constructed with a mixed hybridization
of sp2 and sp3 bonding, due to the larger ionic radius of Si
atoms. In this context, single layer silicene exhibits a buckled
structure (i.e., not planar like graphene and h-BN) (Fig. 16),
and the low-buckled structure is more energetically stable than
the high-buckled structure.116–118 Figure 16 depicts the vertical
displacement of two sub-lattices of the honeycomb lattice. Sil-
icene and germanene have shown very similar electronic band
structures to that of graphene. Both silicene and germanene
are zero-gap semi-metallic, and because their π and π ∗ bands
touch at the Fermi level (Ef ), their charge carriers are massless
fermions.119 However, a perpendicular electrical field can break

TABLE 2
The electrical properties of various 2-D materials

Band gap Band gap Mobility

Type (Mono Layer) (bulk) (cm2/Vsec)

Graphene semi metallic N/A N/A ∼2×105

Silicene semi metallic N/A N/A ∼1×105 (Theory)
Germanene semi metallic N/A N/A ∼1×105 (Theory)
BN insulating 5.2eV 5.2eV N/A
MoS2 semi conducting 1.8eV 1.2eV ∼200 (Mono Layer)
WS2 semi conducting 1.9–2.1eV 1.4eV 100-200 (bulk)
TaS2 metallic super conducting N/A N/A –
NbS2 metallic super conducting N/A N/A –
MoSe2 semi conducting 1.5eV 1.1eV ∼50 (exfoliated)
WSe2 semi conducting 1.7eV 1.2eV 100∼500 (bulk)
TaSe2 metallic super conducting N/A N/A –
NbSe2 metallic super conducting N/A N/A –
MoTe2 semi conducting 1.1eV 1.0eV ∼50 (bulk)
WTe2 semi conducting 1.1eV N/A ∼20 (bulk)
 SYNTHESIS, PROPERTIES, AND APPLICATIONS OF 2-D MATERIALS 245
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FIG. 13. Characterization of MoS2 monolayer transistors. (a) Cross-sectional view of the structure of a monolayer MoS2 FET
having 30 nm of ALD-grown HfO2 . A single layer of MoS2 (thickness, 6.5Å) is deposited on a degenerately doped silicon
substrate with 270 nm thick SiO2 . The substrate acts a back gate. The top gate width for the device is 4 mm and the top gate
length, source–gate, and gate–drain spacing are each 500 nm. (b) Room-temperature transfer characteristic for the FET with 10 mV
applied bias voltage Vds. Back-gate voltage Vbg is applied to the substrate and the top gate is disconnected. Inset: Ids –Vds curve
acquired for Vbg values of 0, 1 and 5 V. (© RSC Publisher. Reproduced by permission of Ma et al.15 Permission to reuse must be
obtained from the rightsholder.)

the equivalence of atoms in the buckled structure, resulting in
the opening of a band gap near the K point. The theoretical
mobility in suspended silicene and germanene under 0.4 V/Å
of vertical electrical field has been simulated to be ∼ 1×105
cm2/Vsec, assuming a similar scattering time between graphene
and silicene/germanene.9
As described in the previous section, some 2-D materials
show superior electrical properties compared with those in Si or
Si-based devices. Even though various 2-D materials have been
discovered and developed, most of their electrical properties
still remain unexplored. Henceforth, the ongoing challenge for
upgrading current technologies will be to introduce 2-D materi-
als into prototype devices, to achieve characteristics comparable
with Si-based technologies.

FIG. 14. Two sets of output characteristics obtained by swap-
ping drain and source contacts on the same device. The asym-
metry of the ID values when swapping the S and D contacts is
characteristic of FETs with Schottky contacts. (© AIP Publish-
ing. Reproduced by permission of Larentis et al.112 Permission
to reuse must be obtained from the rightsholder.)
4.2. Applications
Among the 2-D family of materials, graphene is the first
and foremost to prove useful for a wide range of applications
including electronics, photonics, energy, and several other ar-
eas, due to its exceptional properties.2,121,122 However, due to
several shortcomings such as zero band gap, difficulty control-
ling the number of layers, and the presence of intrinsic defects,
the application of graphene for future semiconductor devices
presents real challenges. Thus, there has been a high demand
for the development of other 2-D materials which have built-in
semiconductor properties. For example, the direct band gap in
2-D MoS2 leads to an electron-hole pair excitation, which could
be utilized for the application of LEDs, photo-detectors and
other photonic devices.111 The high on/off ratio of 2-D MoS2
transistors gives them the potential to be applied in various
low-standby-power digital circuits. Appropriate 2-D semicon-
ducting materials such as MoS2 , MoSe2 , WS2 , and WSe2 , etc.
 246 S. DAS ET AL.
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FIG. 15. Top-gated 2-D WSe2 based FETs with electrical characteristics. (a) Schematic of a top-gated WSe2 ML-FET with S/D
contacts chemically p-doped by NO2 exposure. (b) Transfer characteristics of a device with a length of ∼9.4 μm before and after
NO2 patterned doping of the S/D contacts. (c) Extracted effective hole mobility as a function of gate overdrive of the device shown
in panel b at VDS = −0.05 V. (d) Output characteristics of the same device shown in panel b. (© American Chemical Society.
Reproduced by permission of Fang et al.56 Permission to reuse must be obtained from the rightsholder.)

can be used as a floating gate in Flash memory applications,
by matching the retention/endurance characteristics and lower
power programming/erasing operations required of nonvolatile
memories. The reduction of the thickness of the gate stack leads
to lower voltage operations, and opens up many potential so-
lutions for miniaturization of devices and ultra-high density
applications.123–125
Silicene, a single layer of silicon, is highly advantageous
because it is compatible with current Si technology, and can
be easily applied into existing circuits and devices without
adding additional steps to current Si device fabrication pro-
cesses. Single-atom-thick silicene/germanene could be an ideal
fit into this stacking structure, and due to their higher mobility
could possibly improve operational speed in a broad range of
systems.
Regardless of its transistor applications, MoS2 has also been
devised as a photocatalyst, anode material for Li ion batteries21
and catalyst for hydrogen evolution. Monolayer MoS2 could be
an efficient photocatalyst material, as reported by Li. et al.126,127
Most importantly, the photo-catalyzing ability of a 2-D mono-
layer MoS2 can be effectively modulated by the applied me-
chanical strain as well as by doping. In this context, p-type
doping could improve the catalyzing ability more efficiently, as
p-type doping would be effective for promoting the direct tran-
sition of an electron from the valence band to the conduction
band, and it could separate the water splitting reaction sites into
reduction at the Mo sites and oxidation at the p- dopant sites,
respectively.126 Similarly, other transition metal dichalcogenide
isomorphs like WS2 , WSe2 , MoSe2 have been extensively stud-
ied for scalable applications in photooxidation and photocatal-
ysis leading to water/air purification, H2 evolution, and energy
storage.22 A recent report shows the application of 2-D WS2
as anode material for Li-ion batteries, with an electrochemical
capacity of 118 mAh/g after 50 cycles; however, WS2 is a heavy
 SYNTHESIS, PROPERTIES, AND APPLICATIONS OF 2-D MATERIALS
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FIG. 16. Atomic structure of silicene, together with a sketch
of the charge density for the highest occupied valence band
in the vicinity of the K point. (© American Physical Society.
Reproduced by permission of Drummond et al.120 Permission
to reuse must be obtained from the rightsholder.)
material which is unsuitable to replace conventional lightweight
materials.22
h-BNNS is a quite new material, which is proposed for use as
a substrate for graphene electronics owing to its excellent me-
chanical and thermal properties, as well as chemical inertness.
To date, graphene on h-BNNS has shown the best reported per-
formance for low-power electronics of which we are aware.87
Noble metal nanoparticles decorated h-BNNS are used as effec-
tive catalysts for CO removal through oxidation reactions.45 On
the other hand, a recent report reveals that h-BNNS edges are
very useful sites for electron emission, and hence could have
a potential application in UV light emission devices. Yu et. al
reported broad band light emission ranging from 200–400 nm
from vertically oriented h-BNNS on Si substrates.50 However,
this structure is not very useful for application in field emission
devices (FED), owing to the insulating nature of h-BNNS. Fur-
thermore, the the wide band gap and limited charge transport
of h-BNNS materials are likely to limit their applications in
energy-related devices.
Although energy applications of single 2-D atomic layer
thick materials are limited, combinations of 2-D nanostruc-
tures open a vast number of possibilities for the applicability
of these materials as energy devices. The benefits of combining
2-D nanostructures could be found from the easily achievable
combined properties of both of materials, which are far more
advantageous than single materials. However, synthesizing the
hybrid 2-D nanostructures and comprehensively characterizing
their properties is highly challenging. A few recent reports have
demonstrated energy devices based on 2-D hybrid materials, in-
cluding graphene-MoS2 , graphene/h-BNNS and graphene/WS2 .
Chang et al. demonstrated the L-Cysteine-assisted synthesis of a
layered graphene/MoS2 composite with superior electrochem-
ical performance, which is attributed to the robust composite
247
structure and synergistic effects between layered MoS2 and
graphene. Furthermore, this composite was applied as an anode
material in a Li-ion battery, and displayed a specific capacity of
∼1100 mAh.g−1 at a current of 100 mA.g−1, as well as excellent
cycling stability and high-rate capability.128 Another similar re-
port presents the MoS2 /graphene versatile composite as the an-
ode material for Li-ion batteries. In this report, the synergistic
MoS2 /graphene anode illustrates the excellent electrochemical
reversibility of Li+ storage with good cycle stability.129 Zhou
et al.130 demonstrated a 2-D MoS2 nanosheet- reduced graphene
oxide (rGO) hybrid material as the Li ion battery anode. This
electrode has a 915 mAh.g−1 capacity, superior rate capabil-
ity, and long-term stability. It speculated that the improvement
in electrode capacity is mainly due to the synergistic effect of
MoS2 and rGO, which forms a gel like polymeric layer which
facilitates the interfacial Li+ storage.130 On the other hand, the
MoS2 /graphene composite could be an excellent catalyst ma-
terial for H2 evolution reaction as reported elsewhere.12 The
2-D MoS2 and TiO2 nano-belt heterostructures show enhanced
photocatalytic activities, while exhibiting the highest reported
hydrogen production rate of 1.6 mM h−1g−1.131
MoS2 exhibits strong photoluminescence properties, which
could be further applied in the field of nanophotonics and pho-
totransistors.23,69,132 It is reported that 2-D MoS2 devices can
effectively detect/emit visible light, and electroluminescence
by hot carrier processes and photoluminescence occurred at the
same excited state of 1.8eV.133
Phototransistors based on mechanically exfoliated 2-D MoS2
perform better than graphene based devices. Photoresponsivity
in MoS2 based devices, defined as generated photocurrent over
total incident optical power, reaches ∼7.5 mA/W at 50 V of
gate voltage in 2-D MoS2, compared with ∼1 mA/W at 60 V
of gate bias in graphene based devices.134 The switching behav-
ior of photocurrent generation and annihilation in 2-D MoS2
was repeatedly within 50 ms. Recently, Tongay et al. demon-
strated the diamagnetic and ferromagnetic responses from 2-D
single crystal MoS2 . Although MoS2 itself is nonmagnetic, fer-
romagnetic impurities and magnetization from sulfur vacancies
contributed to diamagnetic and ferromagnetic responses, which
will allow the further extention of 2-D semiconductor chalco-
genides materials into the field of magnetic and magneto-
resistive applications.134 2-D h-BNNSs also have numerous
applications in the field of composite structural materials. h-
BNNSs play the role of fillers in h-BNNS-polymer composites,
significantly improving the thermal properties and enhancing
the mechanical properties of composite films.135,136 In one of the
most interesting applications, Ag/dispersed h-BNNS is used as
high thermal oxidation-resistant substrate for surface enhanced
Raman spectroscopy (SERS).137
5. SUMMARY
In summary, 2-D nanostructures promise the development of
a new field of fundamental research which will contribute to next
generation devices with outstanding performance. Starting with
 248 S. DAS ET AL.
graphene and h-BNNS, other non carbonaceous 2-D transition
metal dichalcogenides and their hybrid structures are anticipated
as key materials for applications in ultra-fast, low-energy elec-
tronics devices. The advantage of MX2 materials (M: Metals;
X: Chalcogens), such as MoS2 , WS2 , MoSe2 , MoTe2 NbSe2 ,
etc., is having their controllable intrinsic band gap with satis-
factory mobility which could be utilized in high-speed device
fabrication beyond Si-CMOS technology. Additionally, as the
thickness of MX2 materials decrease, they are transformed from
indirect band gap into direct band gap, which holds promise for
optoelectronic applications as well. In contrast, h-BNNSs ex-
hibit a large band gap of ∼6 eV, and therefore are highly likely
to be a good substrate with rapid heat dissipation and good me-
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chanical strength. Synthesis of 2-D nanostructures and their hy-
brids are demonstrated using several methods, such as mechan-
ical exfoliation (ME), chemical synthesis, and CVD processes.
ME is widely used for the synthesis of any 2-D nanostructure
materials, including graphene and beyond. On the other hand,
recent achievements in chemical synthesis and CVD process-
ing show excellent future potential for the scalable synthesis of
those 2-D nanostructures, although further optimizations must
be explored. Since the MX2 group of 2-D nanostructures ex-
hibit exceptional electrical properties, basing nanoelectronics
devices upon these new 2-D materials could, in the near future,
lead technology to the ultimate limits of size scaling envisioned
by Moore’s Law. Several other generic approaches demonstrate
the different methodologies of synthesis, and tuning of the prop-
erties of, the 2-D and hybrid nanostructures, which would allow
these materials to be used in several other applications, such
as catalysis, energy storage, photocatalysis, memory devices,
optospintronics, and many more.
6. FUTURE PERSPECTIVES
At present, high-quality 2-D materials are very difficult to
grow, but much technological progress has been made, thanks
to multi-disciplinary efforts worldwide. It is thus expected, that
utilizing these results could lead to new functional materials,
devices, and systems which represent significant advances over
existing ones. For these innovative applications, we need various
component technologies associated with atomically thin films,
particularly synthesis technologies; crystal growth technologies;
manufacturing technologies; measurement; and analysis. As of
now, several other potentially very important 2-D materials have
yet to be discovered. Hopefully, these newly discovered TMDC
materials could solve several technological issues not addressed
by graphene. Finally, if we can create unprecedented properties
at low cost utilizing these abundant 2-D materials, huge changes
will be expected in various sectors of many industries, as they are
freed from the inconveniences of scarcity and the localization
of natural resources.
Present silicon technology has followed the famous Moore’s
law for miniaturization, higher integration, higher performance,
lower power dissipation, and lower cost. In the coming decade
(according to international technology roadmap for semicon-
ductors (ITRS), silicon technology will face unprecedented
technological challenges regarding the scaling-down of the tran-
sistor, the device integration process, and power consumption
issues. Although many attempts have been made to cope with
these types of challenges, the status of present technologies for
the future of below -10 nm silicon technology is still uncertain.
Specifically, power consumption and heat dissipation issues are
still a dilemma concurrent with the scaling-down of the tran-
sistor. To decrease power dissipation, new state variables like
Q-bits, spin, molecules, and so-on, have been investigated as
switching mechanisms to replace the electrons used in CMOS.
To date, no alternative variables can compete with the electron.
The 2-D materials exhibit a very high surface-to-volume ra-
tio, which is a natural advantage for the reduction of power
consumption in future nanoelectronics, in that the atomically
thin materials enable the highly efficient modulation of charge
transport via surface gates. In this regard, new nanoelctronics
based on novel 2-D materials could lead to the ultimate size
scaling envisioned by Moore’s Law and beyond.
ACKNOWLEDGMENTS
The authors wish to thank Dr. Lori Lepak (University of
Wisconsin – Stevens Point) for helpful scientific discussions.
FUNDING
This work was, in part, supported by the World Class Univer-
sity (WCU) program funded by the Ministry of Education, Sci-
ence, and Technology (R31-2008-000-10092) and the Air Force
Office of Scientific Research project (FA9550-09-1-0544).
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