Zhao 2018

Received: 6 April 2018 Revised: 19 June 2018 Accepted: 20 June 2018
DOI: 10.1002/wcms.1387
OVERVIEW
Theoretical studies on tunable electronic structures and potential

applications of two-dimensional arsenene-based materials
Jun Zhao1,2 | Zheng-Hang Qi1 | Yong Xu3,4,5* | Jun Dai6 | Xiao Cheng Zeng6* | Wanlin Guo7* |
Jing Ma1
1
School of Chemistry and Chemical Engineering,
Key Laboratory of Mesoscopic Chemistry of Research efforts in the area of two-dimensional (2D) arsenene-based materials have
MOE, Nanjing University, Nanjing, China been fueled up recently due to similarities in honeycomb atomic structures and dif-
2
School of Science, Nanjing University of Posts ferences in physical and chemical properties between arsenene and graphene. The
and Telecommunications, Nanjing, China
pioneering prediction of monolayered arsenene in 2015 and successful synthesis of
3
State Key Laboratory of Low Dimensional
multilayered arsenene nanoribbons in 2016 have promoted intensive subsequent
Quantum Physics, Department of Physics,
Tsinghua University, Beijing, P. R. China studies, especially in the theoretical aspect. Density functional theory computations
4
Collaborative Innovation Center of Quantum not only revealed desirable fundamental band gap, structural stability, and high car-
Matter, Beijing, P. R. China rier mobility of various arsenene-based materials but also suggested promising
5
RIKEN Center for Emergent Matter Science applications in future optoelectronic and thermoelectric devices, as well as in the
(CEMS), Saitama, Japan quantum spin Hall devices via surface functionalization and modulation of inter-
6
Department of Chemistry, University of layer interactions. With an aim to present a comprehensive review on the tunable
Nebraska-Lincoln, Lincoln, Nebraska
7
electronic structures of 2D arsenene-based materials, our focus is placed on the tai-
State Key Laboratory of Mechanics and Control
for Mechanical Structures and Key Laboratory for
loring routes through surface functionalization to modify the electronic and opto-
Intelligent Nano Materials and Devices (MOE), electronic properties of the arsenenes. An emphasis is also given to recent progress
Nanjing University of Aeronautics and in designing topological states in arsenene monolayers. The challenges and out-
Astronautics, Nanjing, China
looks are also laid out in aspects of experimental fabrication, device performance,
Correspondence
Jing Ma, School of Chemistry and Chemical
and arsenene-based chemical reactions.
Engineering, Key Laboratory of Mesoscopic
This article is categorized under:
Chemistry of MOE, Nanjing University, Nanjing,
China. • Structure and Mechanism > Computational Materials Science
Email: majing@nju.edu.cn • Electronic Structure Theory > Density Functional Theory
Funding information
UNL Holland Computing Center; National Natural
Science Foundation of China, Grant/Award
KEYWORDS
Numbers: 51535005, 11404037, 21673111;
National Key R&D Program of China, Grant/ arsenene, density functional theory, band structure, electric field modulation,
Award Numbers: 2017YFB0702601, strain engineering, topological insulator
2017YFB0702600, 2018YFA0305603; Tsinghua
University Initiative Scientific Research Program and
the National Thousand-Young-Talents Program
1 | INTRODUCTION
The successful fabrication of single-atom-thick graphene sheet in 20041 has rekindled researchers' enthusiasm to study 2D
nanomaterials. Although graphene possesses extraordinary properties and great potentials in a variety of applications, the
absence of an electronic band gap restricts its application in the semiconductor industry.2,3 During the following past few
years, many other 2D atomic-layered materials, including h-BN, transition-metal dichalcogenides, black phosphorene, layered
*Yong Xu (yongxu@mail.tsinghua.edu.cn), Xiao Cheng Zeng (xzeng1@unl.edu), and Wanlin Guo (wlguo@nuaa.edu.cn) contributed equally to this study.
WIREs Comput Mol Sci. 2018;e1387. wires.wiley.com/compmolsci © 2018 Wiley Periodicals, Inc. 1 of 23
https://doi.org/10.1002/wcms.1387
2 of 23 ZHAO ET AL.
borides, and MAXenes (mixed metal carbides or carbonitrides) have become active areas of research.4–18 Studies on these 2D
nanomaterials have contributed improved understanding of the physical connotation of these novel materials and hence pre-
dicted potential applications ranging from electronics to future nanodevices.19 Very recently, the arsenic (As) monolayer
(named as arsenene20–22), a group-V cousin of phosphorene and a newly predicted atomic-layered semiconductor, has aroused
growing interests due to not only its own novel properties, such as wide fundamental bandgap and remarkable carrier mobility,
but also intriguing responses to strain, electric field, magnetic field, light stimuli, and interaction with various substrates
(Figure 1). For example, through exerting small in-plane biaxial strains, the band-gap of arsenene monolayers could undergo
indirect-gap to direct-gap transitions.21
The most stable form of bulk As allotrope is the rhombohedral phase23 with a buckled structure (called gray As). Experi-
mental observation indicates that when the gray As is heated to a temperature of about 370 K, an orthorhombic phase24
appears with a puckered or washboard structure, which is analogous to black phosphorene. Zhang20 and Kamal21
et al. theoretically predicted the stable structures of the buckled monolayer honeycomb (b-As) and the symmetrically puckered
or washboard monolayer (w-As) of arsenene almost at the same time in 2015, both structures exhibiting semiconducting fea-
tures. First principles calculations predicted that b-As and w-As possess indirect band gaps within 1.5–2.1 eV. This intrinsic
indirect-gap property may limit their applications in photovoltaic devices, since additional phonons are needed to assist the
optical transition, leading to a much lower energy conversion efficiency than direct-gap semiconductors.25,26 By applying
biaxial tensile strains or external electric fields, arsenene monolayer was predicted to undergo a transition from indirect-gap to
direct-gap semiconductor.20,21 However, the need of stretching 2D nanomaterials may significantly increase the complexity of
the devices.27 Therefore, over the past 2 years, surface functionalization and modulation of interlayer interactions have been
demonstrated to be more feasible approaches to tune electronic structures of arsenene-based materials. Much theoretical effort
has been devoted to investigating structural configurations, optoelectronic performance, topological electronic characteristics
as well as potential applications of the functionalized arsenenes.
The fundamental basis for understanding various materials and related phenomena rests upon getting a comprehensive
knowledge of their structure–property relationship, particularly the electronic properties. Density functional theory (DFT) has
achieved great successes in providing reliable ground-state geometries, vibrational frequencies, and reasonable electronic
structures of molecules, crystals, and surface systems while it also satisfactorily balances the computational cost and accu-
racy.28 However, the most commonly used generalized gradient approximation in the form of Perdew-Burke-Eruzerhof
(GGA/PBE)29 in standard DFT method tends to underestimate the band gaps of semiconductors. Many-body perturbation the-
ory utilized in the GW approach can yield more accurate electronic structures, but this approach is extremely time-consuming.
Tunable band structures

e
ε=4%
as
Int
ph
erl
al
ay
gic
er
olo
int
top
e rac
al
tio
ivi
ntr
n
No
b-As w-As
Photoisomerization-Induced Exfoliation
es
Ex
rti
fol
e
i
op
ati
pr
n o
Near-Infrared Visible region

c
s
eti
tra
gn
teg
Ma
UV-Vis optional absorption
FIGURE 1 Schematic illustration of 2D arsenene-based nanomaterials and their electronic structure properties
ZHAO ET AL. 3 of 23
At present, the screened exchange hybrid density functional, namely Heyd-Scuseria-Ernzerhof (HSE06),30 has been regarded
as the most effective method to predict improved bandgap values comparable with experimental data. However, it should be
pointed out that the HSE06 functional is just an improved method in reproducing band gap, compared with GGA/PBE
method, but not a method that is always reliable.31
Herein, we present a comprehensive review on the tunable electronic structures of 2D arsenene-based materials, starting
from the geometric and electronic properties of the monolayer arsenene, followed by a review of the tailoring routes through
surface functionalization and variations of interlayer interactions to modulate the electronic and optoelectronic properties of
the arsenene. The progress in the design of topological states in monolayer arsenene and 2D chemically functionalized As-
based nanostructures is also highlighted. An outlook on the future research in the area of 2D arsenenes is also presented. We
hope this review will promote more experimental and theoretical efforts to achieve advancement in monolayer arsenene syn-
thesis, revealing new fundamental physical and chemical properties, as well as in designing new arsenene-based functional
devices with remarkable performance.
2 | AR SEN EN E NA NOST RU CT UR ES
2.1 | Free-standing monolayer arsenene

The goal of finding competitive candidates in replacing graphene has stimulated extensive exploration of various 2D group-V
elemental materials with similar honeycomb structures, in view of that bulk phosphorus (P), arsenic (As), and antimony
(Sb) also possess layered structures. Among the three bulk allotropes (gray, yellow, and black) of As, the gray As with a space
group of R3m is the most stable and its layered structure is also stable under ambient conditions.20 Even though all having
similar honeycomb structures, puckered (w-As), buckled (b-As), and planar arsenenes, shown in Figure 2a-c, were predicted
to have different stabilities based on DFT calculations. In contrast with graphene which features sp2 hybridization, planar
arsenene (with As–As bond length of 2.52 Å) was predicted to be unstable, and instead, the puckered arsenene (with sp3-like
hybridization and shorter As–As lengths of 2.49 and 2.50 Å) was the global minimum structure.21 The Brillouin zone of puck-
ered arsenene is rectangular, while those of planar and buckled arsenenes are hexagonal. The semiconductor properties of
puckered and buckled arsenenes were predicted with indirect band gaps of 0.83 and 1.64 eV, respectively, by DFT using the
PBE type exchange-correlation functional, while the planar arsenene was predicted to be a metal.21 It is well known that the
extraordinarily high carrier mobility (~15,000 cm2 V−1 s−1 at room temperature) of graphene is benefited from Dirac-like
electrons of the pz orbitals. Surprisingly, monolayer arsenene with a much wider band gap (1.64 eV at DFT-PBE level) was
(a) Buckled (b) Puckered
(c) Planar (d) Tricycle-shaped (e) Square and octagon rings
FIGURE 2 Illustrations of geometric structures of (a) buckled, (b) puckered, (c) planar, (d) tricycle-shaped, and (e) s/o-As arsenenes in the top and side
views. The unit cells are denoted by blue dashed lines
4 of 23 ZHAO ET AL.
also predicted to possess a high carrier mobility of several thousand cm2 V−1 s−1, implying potential applications in fabricat-
ing efficient optoelectronic transistors with favorable on/off ratios.32
In addition to the predicted stabilities of monolayer w-As and b-As, theoretical calculations also suggest two other types of
2D arsenene structures (Figure 2d and e), that is, T-As33 (tricycle-shaped arsenene) and s/o-As34 (containing the fused buckled
square/octagon rings). The above As-based monolayers are both semiconductors, whose band gaps are 1.38 and 2.47 eV,
respectively, as predicted by the HSE06 hybrid functional. The calculated band gap of s/o-As gets slightly smaller by switch-
ing on the spin-orbit coupling (SOC). The tricycle T-As structure was demonstrated to be mechanically unstable based on the
phonon calculations.35 In addition to the layered honeycomb structures listed above, it is likely that there exist other novel
arsenene geometries with distinct properties under different conditions.
2.2 | Exfoliation strategy

In 2016, the synthesis of multilayered 14-nm arsenene nanoribbons on the InAs substrate by using plasma-assisted process has been
reported (Figure 3a).36 To date, however, the exfoliation of gray arsenic into few layered arsenene still faces huge obstacles. Taking
advantage of the evident conformational change of alkyl-substituted azobenzenes (AB) during the trans–cis photochemical isomeri-
zation, the efficiency of liquid-phase exfoliation of graphite was shown to be improved.38 Stimulated by this success in liquid-phase
(a) (b)
hv
~14 nm 312 nm
SiO2 trans 4-(decyloxy)azobenzene cis 4-(decyloxy)azobenzene
452 nm
Multilayer
Arsenene
Multilayered arsenene
InN
~13.8 nm
InAs d
d
0.43 mm
20 nm 5 nm InAs
AB@two arsenene bilayers (0.15/nm2 and 0.30/nm2)
(c) (d) (e)

240 28 240 32
6.5 ps 0 ps 0.15/nm2
200 24 200 0.30/nm2
28.3 ps 24
160 20 11.3 Å 160
 (deg)
 (deg)
0.15/nm2 8.6 Å
d (Å)
d (Å)
120 120 16
16
80 16.3 Å 80
12
8
40 40
8 15.1 Å 0.30/nm 2
0 0 21.3 ps 0
0
0 5 10 15 20 25 30 0 5 10 15 20 25 30 0 5 10 15 20 25 30
Time (ps) Time (ps) Time (ps)
AB-OC10H21@two arsenene bilayers (0.15/nm2 and 0.30/nm2)
(f) 240 (g) 28 (h) 240 32
240 24 27 ps 200
0 ps
24
240 20 160
4 ps
 (deg)
 (deg)
d (Å)
d (Å)
240 120 16
16 6.4 Å 19.1 ps 8.3Å
11.3 Å
240 80
12
7.3 Å 8
240 40
8
0 0 0
4
0 5 10 15 20 25 30 0 5 10 15 20 25 30 0 5 10 15 20 25 30
Time (ps) Time (ps) Time (ps)
FIGURE 3 (a) Transmission electron microscope (TEM) images of the multilayer arsenene/InN/InAs. (Reprinted with permission from Reference 36.
Copyright 2016 American Chemical Society) (b) the schematically predicted light-assisted exfoliation of multilayered arsenene. (c)–(h) the dihedral angle,
interlayer distance and the corresponding average results of time evolutions in 20 independent RMD simulations for the arsenene-AB/AB-OC10H21-arsenene
hybrids. (Reprinted with permission from Reference 37. Copyright 2017 Royal Society of Chemistry)
ZHAO ET AL. 5 of 23
exfoliation of graphite, a theoretical prediction has recently been presented referred to the light-assisted exfoliation of multilayered
into few-layered or even monolayered arsenene by using AB derivatives.37 With exposure to light, the cis-to-trans conformational
change of AB or AB-OC10H21 (Figure 3b) could induce the changes of dihedral angle (Figure 3c) and interlayer spacing
(Figure 3d). The average distributions of interlayer distance, as shown in Figure 3e, also demonstrated that the interlayer distance of
multilayered arsenene is significantly affected by the isomerization process of the AB derivatives.
Long alkoxy chain substituted AB-OC10H21 in the system is anticipated to flip or bend less freely (Figure 3f–g) than the
unsubstituted AB. In Figure 3h, the calculated average interlayer distance changes in arsenene-AB-OC10H21-arsenene com-
posite, indicating the possibility of exfoliation of arsensenes.
More recently, the As nanosheets have been fabricated by using aqueous shear exfoliation method.39 The size of each as-
synthesized As nanosheet is demonstrated to be tenth of nanometers. The exfoliated materials are verified to be in nanoscale thickness
via Raman spectra. Combined with the plasma-assisted synthesis process and the predicted light-assisted exfoliation, it is expected
that more controlled few layered- and even monolayered-2D arsenene materials can be successfully fabricated in the near future.
3 | S UR F A CE F UN CT IO N AL IA Z T I O N
3.1 | Doping, defect, and adsorption

Surface functionalization is widely regarded as a flexible and effective route for modulating electronic and magnetic properties
of 2D semiconductors, contributing to the design of diverse functional devices. It was conceived that 2D arsenene nanosheets
with large magnetic moments could be used as components for spintronic devices. Electronic structures including energy
bands and magnetism of 2D arsenenes have been extensively explored, covering a broad range of substitutional doping,40–51
intrinsic defects,52–55 as well as adsorption of atoms and molecules.45,56–64
First-principles calculations indicated that substitutional doping and adsorption of various atoms could lead to magnetism
in some cases for monolayer b-As and w-As, as shown in Table 1. For monolayer b-As, the presence of transition metal
(TM) atoms (Ti, Cr, V, Mn et al.) could give rise to various kinds of magnetisms, including paramagnetic (PM), ferromagnetic
(FM), and antiferromagnetic (AFM) states. Magnetic moments were demonstrated to be increased from 0 to 4 μB (e.g., for the
Mn-doped monolayer) with the increment in the d electron number of TM atom. Fractional magnetic moments (in units of μB)
were predicted in the arsenenes doped with TM elements of Zn (0.78), Ni (0.99), Fe (3.26), and Cu (1.96), respectively.40 In
particular, the ferromagnetic moments of Ni-doped arsenene are mainly originated from the p–d orbital hybridization between
Ni and its neighboring As atoms.46 Most of the TM-doped arsenenes were demonstrated to be energetically favorable, and the
Ni-doped arsenene was the most stable system among them.40,41,46
In the case of non-TM-doped systems, including Ga, Ge, P, Sb, C, Si, Sn, O, S, Se, Bi, Te, B, N, and F dopant in b-As
structures,43–45,48 and B, C, N, O, F, Al, and Si dopant in w-As structures,47 magnetic properties are effectively modulated as well. In
the case of substitutional doping, group-IV elements, including C, Si, Ge, and Sn,43–45 could induce 1.0 μB total magnetic moment
for b-As monolayer. The replacement of one As atom by a single C or O atom in w-As monolayer led to ferromagnetism.47
The adsorption of atoms (e.g., H, Cl, B, P, As, and Sb)40,46 could result in magnetism for both b-As and w-As monolayers.
With the adsorption of group IV C or Ge atom at the valley or top site, 2.0 μB total magnetic moment per atom could be
achieved in b-As monolayer.58 Moreover, the adsorption of NO and NO2 can lead to a total 1.0 μB magnetic moment.51 How-
ever, the mechanism underlying those calculated magnetic parameters in the substitution- or adsorption-modified arsenene
monolayer has not been fully understood yet.
The dangling bonds, which are caused by removing or adding atoms, in the single vacancy (SV) and adatom defects could also
lead to magnetic moments.52,53 For example, both SV-55 and SV-59 configurations were reported to have magnetic moments of
1.0 μB (per vacancy).53 Thus, SV defect-containing 2D arsenene are anticipated to be used in the future quantum spintronic field.
As shown in Figure 4a, the hybridization of TM-3d and the neighboring As-4p orbitals induce impurity states for the
arsenene monolayer.40 In the case of Ga-doped arsenene monolayer, the transition from indirect-gap to direct-gap semiconduc-
tor may be ascribed to the hybridization of 4p–4p orbitals between Ga dopant and the As atoms nearby.44 However, for the
metallic O-doped arsenene, O dopant plays a negligible role in the occupied gap states.45
As mentioned above, the substitutional doping could lift the Fermi level, modulate the electronic properties and usually
introduce electrons or holes to the arsenene. Hybridization characteristics of As atoms near the dopants are largely changed. In
contrast, the effects of vacancy defect are much more complex. The vacancy defects could induce atomic reconstruction,
charge redistribution, bandgap reduction, and active sites for adsorbing other functional groups, atoms, and molecules. Vari-
ous structural defects are actually unavoidable during the synthesis of 2D nanomaterials, and they can dramatically affect the
electronic structures of the nanomaterials. For the monolayer b-As, atomic structures and electronic properties of point defects,
including adatoms, Stone Wales defects, SVs, and double vacancies (DVs), were studied through scanning tunneling
6 of 23 ZHAO ET AL.
TABLE 1 Substitution (s) or adsorption (a) site, bond length between dopant and As atoms (Å), calculated total magnetic moment (μB) and magnetic ground
state — = Not available; NM = Non-magnetic; FM = Ferromagnetic; AFM = Antiferromagnetic, PM = Paramagnetic) of various substitutional doping or
adatom of b-As and w-As monolayers. Adsorption sites are denoted as T (top), Br (bridge), H (hollow) and V (valley), respectively
Dopant Substitution/adsorption site Bond length Magnetic moment Ground state References
b-As
B s 1.97 0.0 — 45
C s 1.987, 1.99 1.0 — 44,45
N s 2.01 0.0 — 45
44,45
O s 2.09, 2.02 1.0 NM
Si s 2.41 1.0 — 44
P s 2.39 0.0 — 43
44
S s 2.44 0.0 NM
40
Sc s 2.66 0.0 NM
40
Ti s 2.53 1.0 FM
40
V s 2.47 2.0 FM
40
Cr s 2.46 3.0 AFM
40
Mn s 2.47 4.0 FM
40
Fe s 2.31 3.26 FM
40
Co s 2.27 0.0 NM
40
Ni s 2.31 0.99 PM
40
Cu s 2.36 1.96 PM
40
Zn s 2.46 0.78 PM
Ga s 2.423, 2.43 0.0 — 43,45
43–45
Ge s 2.482, 2.49 1.0 FM
Sb s 2.67 0.0 — 43
Sn s 2.65 1.0 — 44
44,45
Se s 2.558, 2.52 0.0 NM
44
Te s 2.72 0.0 NM
H a-TH 1.57 1.0 — 58
56,58
Li a-V 2.626, 2.680 0.0 NM
B a-V 1.99 1.0 — 58
C a-V 1.94 2.0 — 58
58
N a-BH 1.83 0.0 NM
O a-B 1.82 0.0 — 58
56
Na a 2.80 0.0 NM
56
Mg a 2.89 0.0 NM
56,58
Al a-V 2.809, 2.728 0.0 FM
Si a-VH 2.40 0.0 — 58
P a-BH 2.30 1.0 — 58
Cl a-T 2.39 1.0 — 58
Ti a-B 2.34 0.0 — 58
56,58
Ga a-V 2.865, 2.815 0.0 FM
Ge a-T 2.45 2.0 — 58
As a-BV 2.43 1.0 — 58
Se a-T 2.24 0.0 — 58
Sb a-T 2.53 1.0 — 58
w-As
B s 2.09/2.01 — — 47
C s 1.96/1.94 — FM 47
N s 1.96/1.94 — 47
O s 3.34/1.84 — FM 47
F s 3.33/1.83 — 47
Al s 2.46/2.46 — — 47
(Continues)
ZHAO ET AL. 7 of 23
TABLE 1 (Continued)
Dopant Substitution/adsorption site Bond length Magnetic moment Ground state References
Si s 2.43/2.42 — 47
P s 2.40/2.37 — — 47
S s 2.54/2.36 — 47
Cl s 3.26/2.25 — — 47
Ga s 2.47/2.47 — 47
Ge s 2.52/2.53 — — 47
Se s 2.51/2.76 — 47
H a-T 1.57 1.0 — 58
Li a-TH 2.59 0.0 — 58
B a-TH 2.02 1.0 — 58
C a-TH 1.86 0.0 — 58
N a-BrH 1.79 1.0 — 58
O a-TH 1.70 0.0 — 58
Al a-TH 1.73 0.0 — 58
Si a-BrH 2.60 0.0 — 58
P a-TH 2.34 1.0 — 58
Cl a-T 2.37 1.0 — 58
Ti a-TH 2.49 2.0 — 58
Ga a-TH 2.67 0.0 — 58
Ge a-V 2.48 0.0 — 58
As a-V 2.41 1.0 — 58
Se a-TH 2.27 0.0 — 58
Sb a-V 2.57 1.0 — 58
57
Au a-H 2.43 1.0
57
Ag a-H 2.46 1.0
57
Pb a-V 1.87 0.0
57
Pt a-H 1.90 0.0
microscopy (STM) simulations.52 Most of the studied defective b-As monolayers were still semiconductors with relatively
smaller indirect bandgaps, comparing to the pristine arsenene monolayer, as illustrated in Figure 4b.
In general, modification effects induced by adatoms are not very significant on the electronic properties of 2D material,
especially when the adatoms escape from 2D surfaces. Ersan et al.58 presented a systematical investigation on the chemisorp-
tion and physisorption of various nonmetal and metal adatoms and some inorganic molecules of b-As and w-As arsenene
monolayers. As shown in Table 1, some nonmetal adatoms like H, B, P, Cl et al. could induce total magnetic moments for
both 2D arsenenes. The physisorption of H2, O2, and H2O molecules brought weak impacts on the electronic structures of
arsenene monolayers. The attachment of other inorganic molecules, such as NO, and NO2, were demonstrated to induce sig-
nificant modulations of the density of states in the vicinity of the Fermi level by Liu et al.59 For the adsorptions of organic
molecules, like electron withdrawing tetracyanoquinodimethane (TCNQ) and electron-donating tetrathiafulvalene (TTF),
impurity states of the adsorbates reduced the band gap of the complexes. Through adsorbing TCNQ and introducing shallow
acceptor states, p-type-doped arsenene was obtained. While for TTF attachment, the donor state went far away from the
conduction band minimum (CBM) of arsenene monolayer, leading to a n-doped arsenene. For the functionalized AsF
monolayer,65 when a H2O molecule was adsorbed, the band gap of the AsF monolayer experienced a significant decrease from
0.15 eV to 0.09 eV, indicating that the adsorption interaction between H2O molecule and functionalized AsF monolayer was
different from that of pristine b-As monolayer.
3.2 | Covalent chemical decoration

It is well known that the covalent chemical decoration holds promise for realization of 2D-layered materials with increased
stability, highly tunable electronic structures, and enhanced topological electronic properties. For monolayer arsenene, chemi-
cal decoration makes the intrinsic buckled structure more planar, as shown in Figure 5. Such planarization could induce
unique electronic properties. The functionalized arsenene AsR nanosheets, which are terminally decorated with R=H, F, Cl,
Br, I, O, OH, CH3, etc, have aroused particular interests.65–77
8 of 23 ZHAO ET AL.
(a)
Ti-doped V-doped Cr-doped Mn-doped
Fe-doped Ni-doped Cu-doped Zn-doped
4.42 3.1 4.25

(b)
4.4
2.9 4.15
4.38
2.7 4.05
4.36
2.5 3.95
4.34
4.32 2.3 3.85

Perfect Stone-wales (55-77) Single vacancy
3.4 4.8 3.8
3 3 3.4
2.6 4.4 3
2.2 4.2 2.6
1.8 4 2.2
1.4 3.8 1.8

Double vacancy (5-8-5) Double vacancy (555-777) Adatom (hollow)
FIGURE 4 (a) Spin densities of various TM-doped arsenene. The majority and minority spin densities are depicted by purple and yellow isosurfaces.
(Reprinted with permission from Reference 40. Copyright 2016 Springer Nature) (b) Optimized configurations along with the simulated STM images of
various defect systems. The relative heights are represented by the color bars. (Reprinted with permission from Reference 52. Copyright 2017 Royal Society
of Chemistry)
The electronic structures of halogenated arsenenes were predicted to be stable via formation energy calculations, except
AsI monolayer. The Dirac cone was found to appear in the halogenated arsenenes,68,69 probably due to flattening of the struc-
tures of monolayer arsenenes upon fluorination.70 In fact, for a broad scope of the chemically functionalized systems, AsR
family (R=F, OH and CH3, etc.) were reported to be quasi planar structures.65 All the functionalized arsenene structures
exhibit gapless features when excluding the SOC. Since the enthalpy decreased linearly with the concentration of O atom, the
controllable fabrication of partially oxidized arsenene can be probably achieved through oxidation at low temperature in the
experiment.74 Fully oxidized arsenene, AsO,75 was predicted to possess remarkable stability and tunable SOC bandgaps.
Planarization induced unique

electronic properties Functionalized
Arsenene arsenene (AsR)
Chemical decoration
R= H, F/Cl/Br/I, OH, CH3, etc
Buckled structure Quasi planar structure
FIGURE 5 The schematic illustration of functionalized arsenene (AsR) with chemical decoration of R= H, F/Cl/Br/I, O, OH, CH3, etc
ZHAO ET AL. 9 of 23
It will be highlighted later in this review that planarization induced by the covalent chemical decoration with various func-
tional groups can also result in nontrivial topological electronic states for monolayer arsenene.
3.3 | Boundary modulation

In addition to the aforementioned decorated 2D nanosheets, the arsenene nanoribbons (N-AsNRs) were anticipated to gain sig-
nificant modifications in electronic structures owing to the boundary modulation and quantum size effect.78–86 The configura-
tions of armchair (a) and zigzag (z) nanoribbons are illustrated in Figure 6, where Na or Nz reflects the width of an armchair
or a zigzag nanoribbon. To eliminate the dangling bonds and enhance structural stabilities, the edge atoms in nanoribbons are
passivated by H atoms. Taking 10-aAsNR and 6-zAsNR, for example, the 10-aAsNR is a semiconductor possessing an indi-
rect band gap of 2.66 eV, while for 6-zAsNRs, it has a direct 2.48 eV band gap.78
For the a-AsNRs and z-AsNRs with different widths, the calculated results demonstrated that the band gap in larger
AsNRs was reduced due to the nanoscale size effects.79 Nanostructuring w-As monolayer into nanoribbons could induce direct
bandgaps when the armchair stripe is narrow or when the zigzag ribbon is wide, judged by the in-plane and out-of-plane bond-
ing competition.82
Under the different tensile strains, the band gap of aAsNRs and zAsNRs was predicted to exhibit a nonmonotonic
change.84 A direct gap to indirect-gap transition of the band structure of a-AsNRs was induced at the tensile strain of approxi-
mately 8%. For z-AsNRs, when the compressive strain was applied, the band gap decreased linearly with increasing strain.
Straining the AsNRs could also effectively modulate their transport properties.82 The effective mass of holes in zAsNRs were
found to increase with the external tensile strain applied.
Both external and internal electric fields were able to shift and split the energy levels of band structures in AsNRs configu-
rations, thereby tuning the electronic properties and inducing charge transfer in polarizable systems. For aAsNRs and zAsNRs
with different widths, the increasing external electric field caused a decrease of the band gap and made it to be zero
ultimately.79
Clearly, the electronic properties of the arsenene nanosheets can be also tuned via a variety of surface functionalization
routes. Considering that the presence of various molecules or ligands is practically inevitable during experimental fabrications,
we may sometimes take advantage of these dopants or ligands to tune the properties of arsenene by controlled surface functio-
nalization. The computational results shown above not only give rise to some suggestions to the effective modulation of the
properties of arsenene-based nanostructures, but also provide some indications to verify these adsorptions or defects in experi-
mental characterizations.
4 | M O DU L AT IO N O F I N T E R LA YE R I NT ER AC TION
4.1 | Arsenene bilayers and multilayers

The variation of physical properties induced by changing the number of layers is prominent in bilayered and multilayered
arsenene nanomaterials.87–91 With the number of arsenene layers (n) increasing from one to two, few-layered arsenenes were
demonstrated to undergo a transition from indirect-gap to direct-gap semiconductors.89 The energy shift of the band gap
induced by the quantum-confinement effect was found to change with the variation of thickness. With n further increasing to
infinity, the stacking of puckered layers turned to form the orthorhombic arsenic crystal in accompany with the bandgap varia-
tion in the range of 1.4–0.4 eV. The spin-polarized DFT calculations were also performed to study monolayer, bilayer, and tri-
layer structures of arsenene with an aim to unveil the nanoscale size effects.87 Important effects from the selection of hybrid
Armchair Zigzag
1 2 ⋯ ⋯ Na 1 2 ⋯ ⋯ Nz
10-aAsNRs 6-zAsNRs
FIGURE 6 The structures of armchair and zigzag As nanoribbons. The Na (Nz) denotes the number of the repeated units across the nanoribbon width
10 of 23 ZHAO ET AL.
functional, self-interaction corrections, and SOC were demonstrated (Figure 7). AA stacked b-As bilayer were energetically
more stable by 51 meV than the AB stacked one. Both direct and indirect band gaps were reduced (but more significantly for
the indirect one) as the thickness is increased from monolayer to b-As bilayer.
Four kinds of stacking arsenene bilayers (called AA, AB, AB', and AC) were constructed to investigate their electronic
structures.90 Semimetal properties were found to appear in the AB and AC bilayers. Moreover, the energy dispersion near the
Γ point was greatly changed due to the layer-stacking effect. The anisotropic energy dispersion around Γ-point was found to
be governed by the level repulsion from the additional arsenene layer. Interestingly, the few-layered arsenenes with n = 1–6
were predicted (at PBE functional with revPEB-vdW correction) to possess high carrier mobilities of several thousand
cm2 V−1 s−1,91 while exhibiting a high anisotropy.
4.2 | Arsenene-based van der Waals heterostructures

Heterostructures based on van der Waals (vdW) materials have atomically ultrathin nanostructures and no dangling bonds on the sur-
face, allowing facial creation of various interfaces.92–96 Stacking 2D arsenene-based materials into vdW heterostructures,95–107 such
as arsenene/GaS,97 arsenene/graphene,98,99 group-V and group-IV layers,100,101 arsenene/transition-metal dichalcogenide,102–105
arsenene/FeCl2,106 and etc., are expected to provide a route to rationally design and tune the properties of materials.
The lattice constants of the b-As and GaS monolayers were similar to each other. By stacking the two monolayers, three
different heterostructures can be obtained in terms of AA, ABS, and ABGa stacking orders, as shown in Figure 8a–c, respec-
tively.97 The HSE06 calculations have been implemented to evaluate the electronic properties of the heterostructure, and the
calculated results of the pristine arsenene (2.21 eV) and pristine GaS (3.24 eV) monolayers were also shown for comparison
(Figure 8d–e).97 As illustrated in Figure 8f, the arsenene/GaS heterostructure was an indirect-gap semiconductor with 2.09 eV
bandgap and its valence band maximum (VBM) (dominated by arsenene) and CBM (mainly from GaS) were found to have
type-II band alignment.
Xia et al.98 investigated the Schottky barrier of the arsenene/graphene vdW heterostructures influenced by the interlayer
coupling. The Dirac-like dispersions at the Fermi level were shown to be generally maintained. A transition from the p-type
(a) (c)
d=2.51Å
4
a=91.87°
2
PBE-SOC
Energy (eV)
a=3.61Å
Eg–i Eg–d=1.40eV HSE-SOC Eg–d
Top view 0 Eg–i=0.70eV
Eg–d=2.33eV
Eg–i=1.54eV
–2
3.27Å 4.67Å
–4
Side view Γ M K Γ
(b) (d)
2
b=3.63Å
Eg–d=0.33eV
a=4.71Å 0
Energy (eV)
PBE-SOC
Top view
HSE-SOC
d1=2.48Å
–2
d2=2.51Å β=100.27°
3.23Å 5.66Å
–4
Δ=2.43Å
Γ X S Γ Y S
Side view
FIGURE 7 The optimized configurations and band structures of bilayered arsenene. (a) and (b) The structures of AA-stacked b-As or w-As bilayer and the
related geometric parameters. (c) and (d) Band structures of b-As and w-As bilayers obtained by Perdew-Burke-Eruzerhof–spin-orbit coupling (PBE-SOC)
and Heyd-Scuseria-Ernzerhof (HSE-SOC) functionals. (Reprinted with permission from Reference 87. Copyright 2016 American Physical Society)
ZHAO ET AL. 11 of 23
(a) (b) (c)
d d d
AA-stacking ABS-stacking ABGa-stacking
(d) 4 Arsenene GaS As/GaS

(e) (f)
3
2
2.12 eV 3.24 eV 2.09 eV
Energy(eV)
1
As
0
GaS
–1
–2
–3
K Γ M K K Γ M K K Γ M K
FIGURE 8 (a)–(c) Top and side views of AA-, ABS-, and ABGa-stacked A/G heterostructures. As, Ga, and S atoms are denoted in pink, seagreen, and
yellow colors, respectively. (d)–(f ) Band structures of arsenene, GaS, and the corresponding A/G heterostructure calculated at HSE06 level. (Reprinted with
permission from Reference 97. Copyright 2016 Royal Society of Chemistry)
Schottky barrier (0.18 eV) to the n-type barrier (0.31 eV) can be obtained as a result of reduction of the interlayer coupling,
with the distance increasing from 2.8 to 4.5 Å. Wang et al.101 investigated group-V and group-IV heterostructures, which
were weakly bounded by small binding energies between the arsenene/antimonene and the graphene/silicene monolayers.
Preserved well in those heterostructures are characteristics of both group-IV layer (as the Dirac-like dispersion around the
Fermi level) and group-V monolayer (as the semiconductor). Eventually a Schottky contact was obtained at the metal–
semiconductor interface for the group-V/group-IV vdW heterostructure.101 The arsenene/FeCl2 vdW heterostructure was
reported to have spin splitting at the CBM of arsenene, owing to the interfacial coupling of As-p with Cl-p, Fe-d states.106
Furthermore, DFT calculations with vdW corrections demonstrated that the silicene/AsSb heterostructure has little lattice
mismatch and a large bandgap opening (about 213–563 meV) as a result of interface dipole induced inversion symmetry
broken.107
In the arsenene-based vdW heterostructures, the electronic structures of the individual monolayers are generally well pre-
served upon binding, which is an important behavior for 2D vdW heterostructures. The target of computational investigation
of the vdW heterostructures is to accurately predict their band alignment. For instance, the vdW heterostructures with type-II
band alignment can be useful for photovoltaic applications. The combination of arsenene with other 2D materials thus pro-
vides rich possibilities to tailor the electronic band alignment of vdW heterostructures. Moreover, the formation of the
arsenene-based vdW heterostructures may also improve the stability of the nanostructure, in analogy to the black phosphorus
sheet. Owing to the tunable electronic properties of the arsenene-based vdW heterostructures described above, more computa-
tional investigation of the arsenene-based vdW heterostructures should be conducted. A deep understanding of their properties
is of vital importance to the computational design of relevant nanodevices.
5 | POTENTIAL APPLICATIONS
5.1 | Arsenene-based 2D topological insulators

Topologically electronic states in 2D materials have attracted tremendous research interests. Two-dimensional topological
insulators (TIs) are characterized by their nontrivial band topology and the gapless edge states within the bulk gap. As a result,
the search for novel 2D TIs with stable structures and sizable bandgap is of great interest. The nontrivial topological state can
be characterized by topological invariant Z2 number and calculated by the following formula:“0”
þ ð
1
Z2 = dkAðk Þ− d kΩzðkÞ modð2Þ
2
ð1Þ
2π ∂HBZ HBZ
Due to the existence of mod(2) term, the Z2 number only takes two quantized values “0” and “1,” which corresponds to
topologically trivial and nontrivial states, respectively.108
In 2006, Bernevig, Hughes and Zhang have proposed a guiding principle to find TIs by using the band inversion criterion.
A topological phase transition will be induced by inverting the band order between occupied and unoccupied states of oppo-
site parities at the time-reversal-invariant momenta (TRIMs). They have predicted that the topological nontrivial state can be
realized in HgTe/CdTe quantum wells (QWs).109 Encouragingly, the quantum spin Hall (QSH) state was observed experimen-
tally in such QWs after their theoretical prediction.110 The calculation of Z2 invariants could be simple for 2D materials with
inversion symmetry. The Z2 number can be obtained by computing the parity eigenvalues at the four TRIMs, as proposed by
Fu and Kane:111
Y
N Y
4
δðKi Þ = ξ2m
i
; ð −1Þυ = δðKi Þ = δðΓÞδðMÞ3 ð2Þ
m=1 i=1
In above equation, N is the number of occupied bands, δ is the product of parity eigenvalues at the TRIM points, and the
parity eigenvalues are ξ = 1. The SOC is found to be extremely weak in graphene, therefore the experimental observation
of the 2D TI phase in the pristine graphene seems to be very difficult.112 In contrast, some other graphene-like materials may
naturally have strong SOC to enable opening large topological band gaps.113,114
5.1.1 | Strain- and electric field-induced topological phase transition

Strain engineering is a widely used strategy for driving normal insulator into TI.115 In the pristine-buckled arsenene, all five
valence electrons of the As atom are fully saturated, leading to an insulating electronic structure. By performing DFT compu-
tations, Zhang et al.116 and Wang et al.117 have predicted that the bandgap of arsenene is essentially closed under 12% tensile
strain, and the s-p inversion takes place as the strain is larger than 12%. The band inversion mentioned above is usually a sym-
bol of the emergence of topologically phase transition. However, the practical applications of the strain-driven topological
state in arsenene are limited by the large critical strain.
Several investigations have been devoted to the bandgap engineering of bilayer graphene and silicene and phosporene via
applying a transverse electric field. The experimental implementation of a vertical electric field resembles to the gate voltage
used in the field-effect transistors. Mardanya et al.118 have studied four arsenic monolayer allotropes (with 1.21–3.0 eV band
gap obtained by GW calculations) and demonstrated that the enhancement of transverse electric field could induce band inver-
sion at the Γ point, which gives rise to a topologically nontrivial state, as shown in Figure 9. The band inversion was con-
firmed by plotting the charge density distribution of the VBM and CBM.118 With the electric field induced band inversion, the
bandgap opened at the band crossing points when the SOC is switched on. Interestingly, the α-As was converted to a topologi-
cal semimetal. The topologically electronic states modulated by the electric field could support spin-momentum locked gap-
less states at the edges.
5.1.2 | Functionalized 2D arsenene-based TIs

In addition, various chemical functionalization routes have been proposed to predict the nontrivial topological state in the
functionalized arsenene,65,67,69,70,72,73,75,76 similar as demonstrated for stanene- and germanene-based materials.8,113,119 The
arsenene chemically functionalized with substituent groups R=CH3, F, and OH were predicted to be 2D TIs.65
As demonstrated in Figure 10a–c, the subbands of AsF, AsOH, and AsCH3 around the Fermi level are mainly composed
of the px,y orbitals of the As atoms, similar to that of the monolayer AsH.67 The pz orbital of As atom orbital is filtered by
chemical functionalization, thus the Dirac cone shown in Figure 10e is dominated by the px,y orbitals of As. Moreover, when
the SOC is switched on, the degeneracy of the subband at K-point is split, causing a direct 100–160 meV bandgap opening.65
(a) (b)
1 1
Energy (eV)
Energy (eV) 0 0
–1 –1
Y Γ XY Γ X K Γ MK Γ M
(c) (d)
1 1
Energy (eV)
Energy (eV)
0 0
–1 –1
Y Γ XY Γ X Y Γ X Y Γ X
FIGURE 9 Charge density distributions at the Γ point of band structures for (a) α-As (1.2 and 1.5 V/Å), (b) β-As (1.2 and 1.5 V/Å), (c) γ-As (0.7 and 1.0 V/
Å), and (d) δ-As (0.6 and 0.9 V/Å). Band inversions under external electric fields are given in the right panels within each figure. The spin-resolved bands
with the SOC switched on at the Γ point are displayed in each inset. The SOC band gap of α-, γ-, and δ-As along the ΓY direction is 6, 1.8, and 6 meV,
respectively. β-As monolayer exhibits 15 meV SOC band gap along the ΓK direction. (Reprinted with permission from Reference 118. Copyright 2016
American Physical Society)
(a) 1.5 (d)

1.0
AsF CBM VBM
0.5 As: s
As: px=py
E-EF(eV)
As: pz
0.0
0.15 eV F: s
F: px=py b a
–0.5 F: pz
w/o SOC
–1.0 w SOC
–1.5 c
Γ K M Γ Γ K M
(b) 1.5 (e) 1.5
AsOH b a
1.0
1.0
0.5
E-EF(eV)
As: s
As: px=py
0.0 0.16 eV As: pz 0.5
OH: s
E-EF(eV)
–0.5 OH: px=py

OH: pz
–1.0 0.0
–1.5
Γ K M Γ Γ K M –0.5
(c) 1.5
AsCH3
1.0 –1.0
0.5 As: s
E-EF(eV)
As: px=py –1.5

0.0 0.16 eV As: pz Γ
–M M
CH3: s (f)
–0.5 CH3: px=py
CH3: pz
–1.0 Γ – + – + + – – + – + – + (+)
3M + – + – + + + – – – + + (–)
–1.5
Γ K M Γ Γ K M
FIGURE 10 (a)–(c) Band structures (left), orbital-resolved electronic band structures (middle) and the decomposed charge density isosurfaces (right) of AsF,
AsOH, and AsCH3 monolayers, respectively. (d) The AsF armchair nanoribbon. (e) Band structure of the AsF armchair nanoribbon with the width of 8.8 nm.
(f ) The parities of occupied bands at four time-reversal-invariant momenta (TRIMs) for the AsF monolayer. (Reprinted with permission from Reference 65.
Copyright 2017 Royal Society of Chemistry)
The topological edge states were observed in Figure 10d–f for the functionalized arsenene.65 By using Equation (2), the Z2
number was calculated to have a nontrivial invariant ν = 1. Therefore, the chemically functionalized arsenene monolayers are
2D TIs.
Subsequently, Zhang et al.70 have demonstrated that the fluorinated monolayer has a bandgap of 0.16 eV due to the SOC
and the topologically nontrivial state, which is in sharp contrast to the monolayer AsSb.120,121 They have investigated the
atomically thin β-SbAs polymorph and found that the SOC effect is significant, leading to reduction of about 200 meV in its
band gap.70 Moreover, the bandgap of β-SbAs was able be closed and reopened by using biaxial tensile strain, with the topo-
logical invariant Z2 = 1.
Soon after the predictions of fluorinated arsenene,65,70 the halogenated arsenene (R=F, Cl, Br, and I) films have been theo-
retically investigated in detail.72 All the halogenated arsenene were predicted to be TIs with varied bandgap from 194 meV
(for the light element R=F) to 255 meV (for the heavier group R=I with stronger SOC effect).
More recently, the arsenene oxide was theoretically predicated to have excellent stability and electronic structural flexibility.
The maximum bandgap of AsO was reported to be 89 meV, which can be increased to 130 meV by applying a biaxial strain.75
In fact, the functionalized materials should be integrated into nanodevices, and the film must be deposited on an appropriate sub-
strate in experiments. Figure 11a has illustrated the complex structures of the 2D AsO material on the BN sheet, bearing 4.96%
lattice mismatch for the h-BN substrate.75 Shown in Figure 11b is the electronic structure of the AsO/h-BN heterostructure with
the application of 6% tensile strain. The predicted BN/AsO/BN heterostructure is expected to allow the dissipationless charge/
spin transport, implying the possibility of building AsO/BN-based quantum transport devices (Figure 11c).
Li et al.76 proposed that the iodinated group-V binary monolayers (ABI2) possess the bulk bandgap of about 0.409 eV,
allowing their real application at room temperature. The nontrivial topological characters were derived from antibonding px,y
orbitals at K point. In addition, the topological properties of these functionalized binary monolayers can be tuned by strain
engineering and electric field. The possibility of finding strain-induced Dirac states was reported in the monolayered As and
Sb and the bilayered P, As, and Sb, which was different from the possible occurrence of Weyl semimetal states in bulk phases
of P and As.122
Through interlayer interaction, the electronic structures of 2D-layered materials can be effectively modulated. Very
recently, the change of stacking order could render the bilayered AsF heterostructure to simultaneously possess Rashba spin
splitting and topologically nontrivial electronic states.73 The introduction of built-in electric field and SOC caused an obvious
splitting of the band structure at K point in the AA-stacked AsF (Figure 12a). The Rashba parameter αR was estimated to be
1.67 eVÅ, comparable to that of Pt–Si nanowire (1.36 eVÅ). The AB-stacked AsF bilayer was predicted to be a gapless
semimetal when the SOC is turned off (Figure 12b). After the SOC effect was considered, a nontrivial bandgap could be
achieved at the K point.73 The application of tensile strain and electric field caused variations of band gap splitting and nontri-
vial electronic states of the bilayered AsF,73 exhibiting potential usages in novel electronics such as spin field-effect transistors
and QSH insulators.
In view of the growing field of arsenene-based 2D TIs, the various predicted giant bandgaps with the SOC effect are
expected to be utilized under the room temperature and can be used as potential candidates for QSH device. Future break-
throughs lie in the experimental fabrication of these 2D TIs. It is noticed that the presence of QSH in monolayer-bismuthene
positioned at SiC substrate was proposed by computations in 2015,123 and its experimental confirmation was subsequently
achieved in 2017.124 Therefore, the computational design of chemically functionalized As-based nanomaterials with nontrivial
(a) (b)
1.0
0.5
Energy (eV)
0.0
(c)
de
de
–0.5
tro
Sample
tro
ec
ec
El
El
spin h-BN
AsO
I
–1.0
Dielectric substrate M K Γ M
FIGURE 11 (a) and (b) Optimized structures and SOC band structures under 6% tensile strain of AsO/h-BN quantum well. (c) Schematic illustration for the
BN/AsO/BN heterostructure. (Reprinted with permission from Reference 75. Copyright 2017 American Physical Society)
(a) CBM AB-Stacking CBM

2 2
SOC OFF SOC ON
1 1
E+EF(eV)
ER
Eg: 0.052 ER: 0.025
0 Eg 0
Eg: 0.069
VBM VBM
–1 –1
–2 –2
Γ K M Γ Γ K M Γ
(b) CBM CBM

AB-Stacking
2 2
SOC OFF SOC ON
1 1
E+EF(eV)
Eg: 0.00 ER: 0.00

0 Eg: 0.14
0
VBM VBM
–1 –1
–2 –2
Γ K M Γ Γ K M Γ
FIGURE 12 (a) and (b) Band structures bilayered AsF with AA- and AB-stacking. Band decomposed charge density isosurfaces of CBM and VBM without
(left) and with the SOC (right) are also given. The isovalue is 0.005 e/Bohr3. (Reprinted with permission from Reference 73. Copyright 2017 Springer-Verlag
Berlin Heidelberg)
electronic states could provide solid theoretical reference for researchers, and furthermore, the experimental observations of
QSH in As-based nanostructures are expected to be approached in future.
5.2 | Strain engineering

Prospects for potential applications of monolayer arsenene were also explored through the studies of responses to external
strain, electric field, magnetic field, and light stimuli. Strain exerted on arsenene nanomaterials is able to change geometric
structures and affect the electronic orbital hybridization, charge distribution, and bond strength,20,21,87,88,125–127 paving the
way for achieving novel electronic properties of the monolayer arsenene.
When applying an electromagnetic field, arsenene monolayer may bear low light emission efficiency due to its indirect
bandgap feature. Fortunately, monolayer b-As and w-As were found to undergo an intriguing transition from indirect-gap to
direct-gap semiconductor at a relatively tiny in-plane biaxial strain of 4%21 and in-plane uniaxial tensile strain 1%,20 respec-
tively. For in-plane compressive strains larger than 10%, the w-As can be transformed from a semiconductor to a metal owing
to the strong mixing of the conduction and valence bands.21 Remarkably, a Dirac cone was predicted to appear with in-plane
strain for w-As.24 Similar to the in-plane strain modulations mentioned above, the out-of-plane vertical strain was also applica-
ble in electronic band gap modulation of monolayer arsenene. Such vertical compressive stress could be perpendicularly
exerted on the arsenene-based materials in experiment. Upon the employment of out-of-plane compressive strains, the w-As
monolayer experienced a transition from an indirect-gap semiconductor to a metal.125 Generally speaking, in-plane strain
directly changes the lattice constants and other in-plane geometric parameters, while out-of-plane vertical strain directly modu-
lates the buckling heights of layered arsenene materials. In addition, strain could be utilized to effectively modulate other
physical quantities, such as the effective mass of electrons, which is highly anisotropy in w-As monolayers and adjustable
under strain modification.125
The indirect band gaps of b-As bilayer were demonstrated to be effectively modulated through in-plain biaxial strains.88
Under compressive strains, the band gap of bilayer arsenenes initially increased, and then rapidly decreased to zero. For few
layers w-As,89 the strain effect on the electronic structures indicated that the distinct energy shift could be induced for the
indirect and direct band edges. Thus, a transition from indirect-gap to direct-gap semiconductor was found to emerge in the w-
As few layers. In addition, the change of the band gap was nonmonotonic.
In heterostructures of b-As and transition-metal dichalcogenides (b-As/MX2: M=Mo, W and X=S, Se), the lattice mis-
match was negligible to according DFT geometry optimizations.112 As shown in Figure 13a–d, as the interlayer distance
increases, the binding energy of heterostructures turned to be decreased, suggesting that all the optimized heterostructures
were stable. Furthermore, all the constructed b-As/MX2 heterostructures were demonstrated to have band gaps larger than
1 eV.102
Inspecting from Figure 13e, the electronic properties of various heterostructures can be efficiently modulated through
external tensile strain and electric field. When the direction of electric field was changed from positive to negative, the sponta-
neous electric polarization may impact band gaps of the heterostructures, owing to the different electronegativity between As
and X atoms. The band gaps of b-As/MX2 heterostructures were found to be reduced with the increment of exerted strains
(Figure 13f). In the case of arsenene/graphene heterostructure,99 the Schottky barrier height and the Schottky contacts along
with Ohmic contacts were shown to be effectively controlled under the vertical electric fields at the interface. With the vertical
electric field changing from −0.9 to 0.5 V/Å, AA- and AB-stacked arsenene/silicene heterostructures were reported to exhibit
direct band gaps decreasing from 328 meV to 0 and 80 meV to 0, respectively.100 Modulation of the interlayer distance was
also demonstrated to be applicable to modify the electronic structures of arsenene/MoS2. Under an external electric field, the
arsenene/FeCl2 heterostructure106 was found to be transformed into a Schottky contact, and the barrier height was reported to
be continuously varied.
The strain engineering can be experimentally achieved by substrate lattice constant mismatch. Some novel physical phe-
nomena associated with strain engineering have been observed more recently. For instance, the excitonic properties of TMDC
are found to be strongly dependent on the strain, and the width and the asymmetric line shape of excitonic resonances for the
TMDC monolayers128 can be well controlled by applying strain. Many studies have shown that 2D nanostructures can sustain
large mechanical strain without being disrupted. Thus, both the controlled modifications of their electronic structures and the
exciton effects are expected to be achieved for the As-based 2D materials as well.
5.3 | Optical absorption in UV and visible ranges

Efficient light absorption materials are required for a variety of photovoltaic and optoelectronic applications to operate
over a wide energy window. For the monolayer b-As, the optical absorption was strong within the visible to ultraviolet
light range (Figure 14a).129 The highly anisotropic feature of the w-As monolayer was similar to another member of
group V, phosphorene.129,131 It was also shown that the imaginary dielectric function of w-As had a wide energy window
of absorption.
The optical absorption of various defect configurations indicated that the mono-vacancies enhanced optical transitions.55
Other functionalized arsenene systems, like adsorption and covalent chemical decoration, also had excellent UV–Vis
(ultraviolet–visible) light absorption property. The introduction of organic molecules on arsenene monolayer was able to
improve the light absorption function. For instance, the light absorption bands of TCNQ/arsenene and TTF/arsenene systems
were even red-shifted to the infrared region.62 The AsR (R=H, F)65 monolayers may be used as photovoltaics, because the cal-
culated optical absorbance had the maximum absorption peak at 1.6 eV. The hole-doped arsenene monolayer and bilayer were
predicated to possess ferromangetic ground states.132 The Stoner electronic instability of the systems may be attributed to the
van Hove singularity at the valence band edge.133
The excellent optical absorption in the wavelength range of the solar spectrum is of great importance to the photovoltaic
applications. However, currently the computational investigations only focused on the light absorption as a function of fre-
quency. The calculation results of the photocurrent in comparison with its dark current for the arsenene-based optoelectronic
devices are still lacking. Moreover, it is timely to address the relationship between the arsenene-based nanostructure and light
conversion efficiency, which is crucial to the computational design of optoelectronic devices. In general, the fabricated solar
cells exhibit multilayer nanostructures. As a result, the modeling device under considerations should be extended to the more
practical multilayered nanostructures for solar light absorption in different frequencies.
5.4 | Thermoelectric properties

An alternative approach to cope with growing energy demands is the conversion of the waste heat into electricity by using
thermoelectric devices.134,135 TIs are promising for thermoelectrics due to their topological protection, which enables an effec-
tive decoupling between electrons and phonons, thus realizing the concept of “electron-crystal phonon-glass”.136–138 Various
novel thermoelectric effects have been demonstrated experimentally in TIs.139–141 The thermoelectric efficiency can be evalu-
ated by its figure of merit,
(a) (b)
0.08 1.40 0.10 1.60
1.333 eV 1.502 eV
1.33 0.08 1.52
0.06
Band gap (eV)

Energy (ev)
Band gap (eV)
Energy (ev)
0.06
1.26 1.44
0.04
0.04
1.19 1.36
0.02
0.02
4.043 Å 4.076 Å 1.28
1.12
0.00 0.00
1.05 1.20
3.2 3.6 4.0 4.4 4.8 3.2 3.6 4.0 4.4 4.8
Interlayer distance (Å) Interlayer distance (Å)
(c) 1.35 (d)

0.05 0.05 1.24
1.32
0.04 1.272 eV 0.04 1.22
Band gap (eV)

Band gap (eV)
1.29 1.190 eV
Energy (ev)
Energy (ev)
0.03 0.03 1.20

1.26
0.02 0.02 1.18
1.23
0.01 0.01 4.208 Å 1.16
4.291 Å
1.20
0.00 0.00 1.14
1.17
3.6 4.0 4.4 4.8 3.6 4.0 4.4 4.8
Interlayer distance (Å) Interlayer distance (Å)
(e) (f)
1.6 As/MoS2 As/MoS2
As/WS2 As/WS2
As/MoSe2 As/MoSe2
1.2 As/WSe2 As/WSe2
Band gap (eV)
0.8
0.4
0.0
–0.8 –0.6 –0.4 –0.2 0.0 0.2 0.4 –10 –5 0 5 10 15

Electric field (V/Å) Biaxial strain (%)
FIGURE 13 (a)–(d) Variation curves of binding energy and band gap with interlayer distance d of b-As/MoS2, b-As/WS2, b-As/MoSe2 and b-As/WSe2,
respectively. (e) and (f ) Variation curves of band gaps with electric field and biaxial strain for various heterostructures. Purple, yellow, and blue balls denote
As, X, and M atoms, respectively. (Reprinted with permission from Reference 102. Copyright 2017 American Chemical Society)

ZT = S2 GT= Kel + Kph ð3Þ
where S is the Seebeck coefficient, G is the electric conductance, and T is the temperature. The electronic (phononic)
thermal conductance is denoted by Kel(ph). Note that instead of using conductivity quantities, conductance
quantities are applied to describe thermoelectric properties of nanomaterials and TIs.136,142 By using DFT calculations
(a) (b) (c)

10.0 p-type n-type p-type n-type
PBE-RPA - x,y
HSE-RPA - x,y
1.5
G0W0-RPA - x,y 0.8 1.5
7.5 0.8 P P
As 1.0 As
0.4
Sns 1.0 0.5 Sns
ɛ2 (ω)
ZT
ZT
0.0 0.0
5.0 0.4 1.5×1019 1.4×1019 1.3×1019 1.2×1019
0.5
2.5
0.0 0.0
1019 1017 1013 1015 1017 1019 1019 1017 1013 1015 1017 1019
0.0 n2D (m–2) n2D (m–2)
7.5 (d) (e)
PBE-RPA - z 3.0 5.0
HSE-RPA - z
G0W0-RPA - z P 4.0 P
5.0 As As
2.0
ɛ2 (ω)
ZTmax SnS 3.0 SnS
ZTmax
2.5 2.0
1.0
1.0
0.0 0.0 0.0

0 2 4 6 8 10 0 200 400 600 800 0 200 400 600 800
hw (eV) Temperature (K) Temperature (K)
FIGURE 14 (a) The imaginary dielectric function of b-As monolayer. (Reprinted with permission from Reference 129. Copyright 2016 American Physical
Society) (b) and (c) Figure of merit varied with respect to the carrier concentration at 300 K along zigzag and armchair direction, respectively. (d) and
(e) Temperature dependence of ZTmax along zigzag and armchair charge transport direction for w-As monolayer. (Reprinted with permission from Referenec
130. Copyright 2016 American Chemical Society)
in combination with Boltzmann transport theory, the thermoelectric properties of w-arsenene have been
investigated.130,143–148
The figure of merit at 300 K for phosphorene, arsenene (w-As), and SnS monolayers along zigzag (ZZ) and armchair
(AC) direction was systematically studied, as shown in Figure 14b and c.130 The calculated anisotropic thermal conductivity
at room temperature is 30.4 W/mK along the ZZ, larger than that (7.8 W/mK) of AC directions.143,144 The temperature depen-
dence of ZTmax is presented in Figure 13d and e.130 It was noted that the arsenene exhibited larger ZT values than phosphor-
ene. In the case of b-As monolayer, ZT was evaluated to be of 0.17 at a temperature of 700 K, suggesting an excellent
thermoelectric response.145 Upon doping, b-As monolayers could become competitors of well-established thermoelectric
materials (ZT = 0.8). The n-type doped As monolayer possessed superior thermoelectric properties relative to the p-type
doped As monolayer.52 Based on the theoretical works discussed above, the arsenene-based materials are anticipated to have
great potential in thermoelectric applications. Resorting to the rapid development of the fabrication techniques, the high ther-
moelectric performance of arsenene monolayers are expected to be realized in the laboratory.
5.5 | Electrical transport performance

Combining DFT calculations and a tight-binding model, Giovanni et al.149 have investigated field effect transistors based on
2D arsenene and predicted that these materials are promising candidate for digital application with high-performance. Accord-
ing to ab initio quantum transport calculations, the sub-10 nm arsenene tubes can meet performance requirements of the Inter-
national Technology Roadmap for Semiconductors with low power.150
As is well known, the electrical contacts play an important role in the electron transport of 2D semiconductor devices.
Wang et al.151 have computationally studied the electrical contact properties of monolayer arsenene with different electrodes
by using quantum transport calculations. It was found that the Schottky contact is n-type in Sc-, Ti-, Ag-, Cu-, and Au-
arsenene junctions. In contrast, p-type Schottky contact was obtained for arsenene-Pd and -Pt junctions. These predicted works
show that arsenene monolayers may have great potential as nanoelectronic devices, thereby will motivate researchers to
explore the arsenene-based functional materials.
5.6 | Arsenene-based catalysis

Today, the demand for clean energy has never been greater, given the ever increasing human population and energy consump-
tion. This demand has stimulated researchers to search for high-efficient photocatalytic and electrocatalytic material. For
example, by using the GW calculations, Wang group152 has demonstrated that several arsenene-based heterostructures paired
with molybdenum disulfide (MoS2), tetracyano-quinodimethane (TCNQ), or tetracyanonaphtho- quinodimethane (TCNNQ),
that is, As/TCNNQ, As/MoS2, and As/TCNQ, possess type-II band structure with excellent optical absorption, thereby having
potential for photocatalytic applications such as water splitting. The band edges of arsenene were found to be higher than
those of MoS2, TCNQ or TCNNQ material, promoting the separation of electron-hole pairs. Owing to the different band align-
ments, photogenerated electrons and holes in arsenene can easily move to the other layers of heterostructures in the opposite
directions. During the oxidation and redox reactions in different layers of heterostructures, the electron-hole recombination
could be significantly suppressed.
Besides photocatalysis, the use of excess electricity generated from renewables to split water into oxygen and hydrogen is
of great value as hydrogen molecule is considered as one of the cleanest energy suppliers. Very recently, DFT calculations
have been carried out to investigate the electrocatalytic activity of pristine and functionalized arsenene for hydrogen evolution
reaction (HER) and oxygen evolution reaction (OER).153 The dopants, including B, N, O, Ge, Ga, and Se atoms, were demon-
strated to enhance the catalytic activity by substituting one of the As atoms in arsenene. In comparison to pristine arsenene,
the HER activity was increased by 82% for O-doped arsenene and OER activity by 87% for B-doped arsenene. Considering
the persistent demand for clean and renewable energies in the catalysis field, our predicted works may offer a new chance to
design better arsenene-based 2D photo- and electro-catalytic materials.
6 | C O N C L U S I ON S AN D O U T L O O K S
In summary, we have reviewed the recent progress in the computational modeling of the tunable mechanical, electronic, opti-
cal, thermoelectric, and magnetic properties as well as topological electronic states for 2D/1D arsenene-based materials. Com-
putational studies have made great contributions to the understanding and rational design of novel arsenene-based
nanomaterials. However, the challenge of turning these computational designs into practical device applications should not be
understated.
Firstly, although the plasma-assisted process fabrication of multilayer arsenene nanoribbons36 has accelerated fundamental
experimental studies, the synthesis of isolated arsenene monolayers remains a primary barrier for future advancements. The
massive fabrication of arsenene with unique functions is a challenging issue. The practical applications of arsenene-based
nanoelectronics and optoelectronics fundamentally rely on the fabrication of high-quality samples. Although the proposed
light-promoted exfoliation in photo-responsive arsenene systems may give a hint for the fabrication of few-layered or even
monolayered arsenene,37 other novel strategies for 2D arsenene fabrication are highly desired.
Next, the presence of various defects is inevitable during the synthesis of arsenene-based nanomaterials, and it has signifi-
cant influences on the electronic, mechanical, transport, and optical properties. Recently, doping, adatom, and vacancy defects
on the electronic structure have been extensively investigated. However, the investigations related to the dislocation defects
are rarely reported. In particular, the effects of various defects on the electron transport of the arsenene-based nanomaterials
are less explored, and this issue is of vital importance to the practical applications of electronic devices.
Another challenge toward integrating arsenene into functional devices is the selection of reliable and practicable substrates.
In practice, various substrates could fundamentally alter the performance of arsenene-based device. A complete understanding
of substrate effects on the performance of arsenene-based device is yet to be developed. Therefore, computational design and
experimental efforts associated with choosing appropriate substrates need to be properly addressed to elaborate the optoelec-
tronic and electronic performances.
Moreover, 2D materials have been shown to exhibit remarkable performances as electrocatalysts and photocatalysts, in
sharp contrast to their inert bulk counterparts. Efforts have been made in developing arsenene-based catalytic field, but current
progress is still far from sufficient. On the aspect of electrocatalysis, the interactions of arsenene-based nanomaterials with
H2O molecules are still not clear. The electrocatalytic mechanism of HER and OER for 2D arsenene-based materials is still
unknown to the theoretical and experimental researchers, thereby demanding more efforts in the future.
As a 2D-elemental material in group-VA family, the unique physicochemical properties and various allotropes of 2D
arsenene-based materials may facilitate the design of many other functional devices, such as photodetectors, gas sensors, lith-
ium and sodium batteries, etc. Benefiting from the band gap and high carrier mobility, 2D arsenene-based materials are
expected to serve as promising candidates for photodetectors.154 Moreover, the adsorption of gas molecules (like NO and
NO2) onto arsenene monolayer is predicted to induce significant modulation of density of states near the Fermi level, suggest-
ing possible application as gas sensors.59 Through previous experimental and theoretical investigations, the arsenic materials
were reported to act as a promising alternative to graphite anode materials in lithium- and sodium-ion batteries.155 Electron–
phonon coupling of the Li-intercalated bilayer arsenene is anticipated to lead to a superconductor with transition temperature
Tc = 8.68 K, paving the way for exploring 2D superconductivity.156 All these relevant fields associated with arsenene deserve
more attentions. We hope this overview will stimulate more research efforts in studying arsenene-based 2D materials, from
both experimental and theoretical aspects.
ACKNOWLEDGMENTS
This work was supported by the National Key R&D Program of China (2017YFB0702600, 2017YFB0702601) and the
National Natural Science Foundation of China (No. 21673111, 11404037, 51535005). X.C.Z. is grateful to the UNL Holland
Computing Center for support. Y.X. acknowledges support from the Ministry of Science and Technology of China (Grant No.
2018YFA0305603), Tsinghua University Initiative Scientific Research Program and the National Thousand-Young-
Talents Program.
CONFLICT OF INTEREST
The authors have declared no conflicts of interest for this article.
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How to cite this article: Zhao J, Qi Z-H, Xu Y, et al. Theoretical studies on tunable electronic structures and potential
applications of two-dimensional arsenene-based materials. WIREs Comput Mol Sci. 2018;e1387. https://doi.org/10.
1002/wcms.1387

Zhao 2018

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Received: 6 April 2018 Revised: 19 June 2018 Accepted: 20 June 2018

Theoretical studies on tunable electronic structures and potential

Tunable band structures

Near-Infrared Visible region

UV-Vis optional absorption

2.1 | Free-standing monolayer arsenene

(a) Buckled (b) Puckered

(c) Planar (d) Tricycle-shaped (e) Square and octagon rings

2.2 | Exfoliation strategy

AB@two arsenene bilayers (0.15/nm2 and 0.30/nm2)

(c) (d) (e)

AB-OC10H21@two arsenene bilayers (0.15/nm2 and 0.30/nm2)

(f) 240 (g) 28 (h) 240 32

3.1 | Doping, defect, and adsorption

C s 1.987, 1.99 1.0 — 44,45

C a-V 1.94 2.0 — 58

P a-BH 2.30 1.0 — 58

Cl a-T 2.39 1.0 — 58

Ti a-B 2.34 0.0 — 58

As a-BV 2.43 1.0 — 58

Se a-T 2.24 0.0 — 58

Sb a-T 2.53 1.0 — 58

H a-T 1.57 1.0 — 58

Li a-TH 2.59 0.0 — 58

B a-TH 2.02 1.0 — 58

C a-TH 1.86 0.0 — 58

N a-BrH 1.79 1.0 — 58

O a-TH 1.70 0.0 — 58

Al a-TH 1.73 0.0 — 58

Si a-BrH 2.60 0.0 — 58

P a-TH 2.34 1.0 — 58

Cl a-T 2.37 1.0 — 58

Ti a-TH 2.49 2.0 — 58

Ga a-TH 2.67 0.0 — 58

Ge a-V 2.48 0.0 — 58

As a-V 2.41 1.0 — 58

Se a-TH 2.27 0.0 — 58

Sb a-V 2.57 1.0 — 58

3.2 | Covalent chemical decoration

Ti-doped V-doped Cr-doped Mn-doped

Fe-doped Ni-doped Cu-doped Zn-doped

4.42 3.1 4.25

4.32 2.3 3.85

3.4 4.8 3.8

2.2 4.2 2.6

1.4 3.8 1.8

Planarization induced unique

R= H, F/Cl/Br/I, OH, CH3, etc

Buckled structure Quasi planar structure

3.3 | Boundary modulation

4.1 | Arsenene bilayers and multilayers

4.2 | Arsenene-based van der Waals heterostructures

(a) (b) (c)

AA-stacking ABS-stacking ABGa-stacking

(d) 4 Arsenene GaS As/GaS

5.1 | Arsenene-based 2D topological insulators

5.1.1 | Strain- and electric field-induced topological phase transition

5.1.2 | Functionalized 2D arsenene-based TIs

(a) 1.5 (d)

–0.5 OH: px=py

As: px=py –1.5

(a) CBM AB-Stacking CBM