Chemical Physics Letters 730 (2019) 277–282

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Chemical Physics Letters

journal homepage: www.elsevier.com/locate/cplett

Research paper

Tailoring the electronic properties of graphyne/blue phosphorene T

heterostructure via external electric field and vertical strain
⁎
Yusheng Wanga,c, , Nahong Songb,c, Xiaohui Yanga, Jing Zhanga, Bin Xua, Meng Lid,
Yafeng Zhengb, Dapeng Yanga
a
College of Physics and Electronics, North China University of Water Resources and Electric Power, Zhengzhou, Henan 450046, China
b
College of Computer and Information Engineering, Henan University of Economics and Law, Zhengzhou, Henan 450000, China
c
International Joint Research Laboratory for Quantum Functional Materials of Henan, and School of Physics and Engineering, Zhengzhou University, Zhengzhou 450001,
China
d
College of Science, Zhongyuan University of Technology, Zhengzhou 450007, China

H I GH L IG H T S

• Graphyne/blue phosphorene heterostructures is a type-I semiconductor.

• Electric fields and biaxial strains can tailor the electronic structures.
• Transition of direct-indirect and semiconductor-metal.
• Transition of type-I and type-II.

A R T I C LE I N FO A B S T R A C T

Keywords: We design novel graphyne/blue phosphorene van der Waals (vdW) heterostructures (G/BP) under the external
Blue phosphorene electric fields (Efield) and strains. It is demonstrated that the G/BP is a type-I semiconductor with a direct band
Semiconductor gap of approximately 0.378 eV. The external Efield and strains not only have important effects on the band
Band alignment structure which undergoes a fascinating direct-indirect and semiconductor-metal transitions, but also influence
Heterostructure
the band alignment which experiences transition from type-I to type-II. In brief, the features of tunable bandgap
and controllable band alignment endow G/BP with potential for application in future optoelectronic devices.

1. Introduction
Recently, interest in heterostructures composed of at least two dif-
ferent types of two-dimensional (2D) materials has been growing
sharply. In terms of stacking methods, heterostructures can be divided
into two types: vertical vdW heterostructures [1–7] and lateral het-
erostructures [8,9]. The vertical vdW heterostructures is fabricated by
stacking a 2D monolayer material on another monolayer or few-layer
material, and the interaction between the layers is vdW force. In con-
trast to vertical vdW heterostructures, lateral heterostructure is formed
by standing side by side with different 2D materials in plane, and the
interaction between the different 2D materials is the covalent bond.
Generally, these heterostructures possess much better properties than
their parent materials. Many studies reported that the vdW hetero-
structures can give rise to attractive physical phenomena and lead to
revolutionary future devices such as tunneling [10] and bipolar
transistors [11], flexible optoelectronic devices [12] and so on. There-
fore, the heterostructures have provided new approaches for creating
new materials and designing new devices both theoretically and ex-
perimentally.
As one of 2D carbon allotropes, graphyne has attracted much at-
tention since it is first proposed by Baughamn et al. in 1987 [13]. There
exist several different graphyne structures such as α-, β-, γ- and 6, 6, 12-
graphyne, according to the various arrangements of acetylenic linkages
and percentage of the inserted acetylenic linkages (eC^Ce) [14–19].
Among the different types of graphyne, only γ-graphyne has an obvious
direct bandgap and possesses the most energetically stable structure
[20–24], which makes γ-graphyne more suitable than other graphynes
for the future applications in optoelectronics and stimulates lots of
theoretical and experimental researches. On the other hand, as the
rising star, blue phosphorus (blue P) exhibits outstanding properties
including exceptionally high carrier mobility and a tunable bandgap.

⁎
Corresponding author at: College of Physics and Electronics, North China University of Water Resources and Electric Power, Zhengzhou, Henan 450046, China.
E-mail address: wangyusheng@ncwu.edu.cn (Y. Wang).

https://doi.org/10.1016/j.cplett.2019.06.005
Received 19 April 2019; Received in revised form 3 June 2019; Accepted 3 June 2019
Available online 05 June 2019
0009-2614/ © 2019 Elsevier B.V. All rights reserved.
Y. Wang, et al.
Lately, it is reported that the blue P with puckered honeycomb layered
structure, was also successfully fabricated by molecular beam epitaxial
growth on the Au(1 1 1) substrate [25]. The experimental successful
preparation of blue P promoted a flourish of theoretical and experi-
mental investigations into blue P-based materials, especially the BP-
based heterostructures, such as blue P/TMDs [26,27], blue P/graphene
[1,28], blue P/ GaN [29], blue P/arsenene lateral heterostructures [30]
and blue P/Mg(OH)2 [31]. Hence, motivated by the above-mentioned
studies, we constructed a novel vertical heterostructures that consist of
the γ-graphyne and blue P monolayers, named G/BP. Therefore, in this
paper, we first focus on structural and electronic properties of G/BP
vdW heterostructure. Next, we investigate how biaxial strains and
electric fields tune the band gaps, band-edge positions of the G/BP vdW
heterostructure to increase the potential application in elec-
tronic devices.
2. Computational details
First-principles calculations based on density functional theory
(DFT) were performed in order to investigate the properties of the G/BP
vdW heterostructure by using the Vienna Ab-initio Stimulation Package
(VASP) [32–34].The generalized gradient approximation (GGA) with
the Perdew-Burke-Ernzerhof (PBE) is utilized for the exchange-corre-
lation potential [35]. Moreover, in order to take into account interac-
tions between blue P and graphyne layers, the DFT-D2 approach within
the Grimme scheme is adopted to correctly describe the vdW correction
[36,37]. The atomic structures and charge distributions are visualized
by using VESTA package [38]. The atomic valence configurations are
s2p2 for C, s2p3 for P in the G/BP, respectively. The plane wave energy
cutoff is set to be 500 eV to ensure the convergence of total energy. An
enough large vacuum layer of 20 Å along the z direction (perpendicular
to the G/BP) is added to avoid the interaction between periodic images.
All of the structures are fully relaxed with a force tolerance of 0.01 eV/
Å. The first Brillouin zone is sampled with 17 × 17 × 1 and
21 × 21 × 1 Monkhorst-Pack grids for structure optimization and
electronic state calculation. The band structures are calculated by em-
ploying the Gaussian smearing method along the high symmetric point
of Г(0 0 0), M(0 0.5 0), K(0.333 0.666 0), respectively.
To evaluate the most stable stacking manner, the binding energy
(Eb) between the stacking layers in the G/BP was calculated as follows
Eb = [E(G/BP)-E(BP)-E(graphyne)]/n, where E(G/BP) is the total en-
ergy of the G/BP vdW heterostructure, E(BP) and E(graphyne) is the
energy of the blue P and the graphyne monolayer, respectively. n is the
total number of the C atoms in a graphyne primitive cell. The charge
density difference (△ρ(z)) along the z direction is defined as
△ρ(z) = ρ(G/BP)-ρ(graphyne)-ρ(BP), where ρ(G/BP), ρ(graphyne) and
ρ(BP) are the charge densities of the G/BP, isolated graphyne and BP
monolayer, respectively.
3. Results and discussion
To test the validity of the above scheme and parameters, we first
calculate the structural parameters of pristine blue P and graphyne
monolayers. After complete relaxation, the optimized lattice constants
of blue P and graphyne are 3.278 Å and 6.886 Å respectively, which are
in good agreement with the previous results [39,40]. The G/BP is
constructed by placing a 2 × 2 blue P supercell above the graphyne
primitive cell. To minimize the lattice mismatch between graphyne and
blue P monolayers, we set the average lattice constant (6.721 Å) as the
starting point. The lattice constant for graphyne is compressed from
6.886 Å to 6.721 Å, while the 2 × 2 blue P supercell is stretched from
6.556 Å to 6.721 Å, leading to an acceptable lattice mismatch of 2.45%,
which is small enough to form experimentally heterostructures with a
precise stacking. There are many possible stackings obtained by moving
the blue P layer along the x or y directions (Fig. 1). For the sake of
simplicity, three typical configurations are considered as shown in
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Chemical Physics Letters 730 (2019) 277–282
Fig. 1(c)–(e), labeled as A-, B-, and C-stacking. As for A-stacking, the
hexagonal C ring of the bottom graphyne layer is surrounded by the
puckered hexagonal P ring of the top blue P layer as shown in Fig. 1(c).
For B-stacking, one of the lower P atoms of the puckered hexagonal P
ring is located at the center of the hexagonal C ring of the bottom
graphyne layer as shown in Fig. 1(d). For C-stacking, one of the lower P
atoms of the puckered hexagonal P ring is placed above the C atom of
the hexagonal C ring in Fig. 1(e). In order to compare the relative
stabilities of the A-, B-, C-stackings, we calculate the change of their
interface binding energies (Eb) with the interlayer distance. The results
show that, with the change of interlayer distance, the lowest Eb of the
G/BP are −108.17 meV, −103.08 meV, −107.32 meV for A-, B-, and
C-stacking, respectively. It is well known that a more negative value
indicates a more energetically favorable stacking. In addition, the cor-
responding interlayer distance d is 3.38 Å, 3.62 Å, 3.47 Å for A-, B-, and
C-stacking, respectively. Obviously, the A-stacking is the most favorable
configuration with the lowest binding energy and the shortest inter-
layer distance. Therefore, we focus on the most stable A-stacking in the
following. Moreover, the total energy varies with the variation of the
interlayer distance of the heterostructure is shown in Fig. S1. It is found
that the value of interlayer distance is about 3.38 Å.
To further understand the interactions between blue P and gra-
phyne, the deformation charge density difference ((DCD, △ρ(z)) is vi-
sually depicted in Fig. 2(a). The isosurface of the charge density dif-
ference is inserted in Fig. 2(a). The yellow and blue colors indicate the
charge accumulation and depletion of the G/BP heterostructure re-
spectively. One can see clearly from Fig. 2(a) that the blue P donates
electrons to the graphyne layer, which leads to n-doping effect on
graphyne layer. It is well known that the more electronegative an ele-
ment is, the stronger its ability to gain electrons is. The C (2.55) atom
has greater electronegativity than P (2.19) atom, leading P atom do-
nating electrons to C. To make a quantitative analysis of the charge
transfer, we also perform the Bader charge analysis [41]. The results
show that about 0.034 e is transferred from the blue P to graphyne
layer. Such a small transferring charge indicates that the Coulomb in-
teraction between blue P and graphyne is not strong. In addition, in
order to explore its interlayer properties, we plot the plane-averaged
electrostatic potential along the perpendicular direction (z) of the G/
BP, graphyne and blue P in Fig. 2(b)–(d). The work function of the G/BP
is 4.87 eV, which is smaller than the values of blue P (5.95 eV) and
graphyne (5.08 eV). The tremendous potential drop across the G/BP
heterostructure is found to be 16.18 eV, which is much larger than that
of many other heterostructures, such as blue P/BSe (1.4 eV) [39], blue
P/g-GaN (7.31 eV) [29], blue P/graphene (5.84 eV) [1], graphene/
WSe2 (10.89 eV) [42] and so on. As everyone knows that the larger
potential difference manifests the stronger electric field. Therefore,
there exists an enough electrostatic field between blue P and graphyne
to be convenient for charge injection, resulting in better device per-
formance.
Next, to comprehensively understand the properties of the G/BP, we
analyze its band structure. The pure graphyne is a direct band gap
semiconductor with the VBM and CBM at the M point (see Fig. 3(a)),
while the separate blue P monolayer is indirect band gap semiconductor
with the VBM and CBM at the K and A points respectively (see
Fig. 3(b)). The corresponding bandgaps are 0.459 eV and 1.940 eV,
respectively, which are in agreement with the previous theoretical re-
sults [43,44]. Comparing with the band gaps of the pristine blue P and
graphyne monolayers, the band gap of the G/BP is reduced to 0.378 eV
(see Fig. 3(c)), which is smaller than that of the value 0.831 eV calcu-
lated by more accurate hybrid functional method within HSE06 scheme
[45]. However, HSE06 incurs extremely expensive computational costs.
Furthermore, it is well-known that although DFT could not calculate the
band gap correctly, it is still able to predict the correct trend and to
properly demonstrate the physical mechanisms. Thus, the selected
functional of PBE is reliable for the following studies of G/BP. At the
same time, comparing with graphyne, the VBM and CBM of the G/BP
Y. Wang, et al. Chemical Physics Letters 730 (2019) 277–282

Fig. 1. The top view of (a) graphyne, (b) blue

phosphorene. The top view and side view of the G/
BP heterostructure with three different stacking: (c)
A-stacking, (d) B-stacking, (e) C-stacking. The wine
red and blue balls represent C and P atoms, re-
spectively. (For interpretation of the references to
colour in this figure legend, the reader is referred to
the web version of this article.)

Fig. 2. (a) The planar-averaged differential charge density of the G/BP het-
erostructure (△ρ(z)). The electrostatic potentials for (b) the G/BP hetero-
structure, (c) the monolayer graphyne, (d) monolayer BP. The inset in (a) shows
charge density difference with an isovalue of 0.0025 e/Å3. The yellow and blue
Fig. 3. Band structures for (a) monolayer graphyne, (b) monolayer BP, (c) the
regions denote the gain and loss of electrons, respectively. The green and purple
G/BP heterostructure, (e) PDOS of the G/BP heterostructure.
dashed lines denote Fermi level (EF) and the vacuum level (EV). (For inter-
pretation of the references to colour in this figure legend, the reader is referred
to the web version of this article.) indicate that a controllable band gap in the G/BP heterostructure can be
obtained by this approach (see Fig. 4(a)). For the negative Efield, with
share similar characteristics, which indicates the formation of the type-I the Efield increase from 0 to −0.16 V/Å, the band gap slowly decreases
semiconductor. From the partial density of states (PDOS) of the G/BP, from 0.38 eV to 0.31 eV. Then, it declines approximately linearly and
eventually turns metallic at −0.26 V/Å. For the positive Efield, the band
as shown in Fig. 3(d), we can clearly see that C-2pz orbitals contribute
gap slightly increases to 0.387 eV at +0.18 V/Å, afterwards, it rapidly
entirely to the VBM and CBM of the G/BP, which is consistent with the
linearly decreases to zero at +0.3 V/Å. The negative threshold electric
analysis of the band structures.
fields of the G/BP is −0.26 V/Å, which is smaller than the positive
To gain further insight and explore the possible applications, it is
threshold +0.3 V/Å. The reason for different positive and negative
necessary to study how the electric field (Efield) tune the electronic
threshold electric fields may be that electrons and holes are localized
properties of the G/BP. Therefore, an external vertical Efield is applied in
separately at the C and P edges, respectively, leading to form a spon-
the G/BP. The direction of Efield from the graphyne layer to blue P is
taneous electric polarization along the negative direction in the inter-
taken as the positive direction (along the z direction). The results
layer spacing of the G/BP heterostructure.

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Y. Wang, et al.
Fig. 4. (a) The band gap of the G/BP as a function of external Efield, (b) the band
edges of graphyne and blue P in the G/BP as a function of external Efield.
VBMBP(G) and CBMBP(G) are the VBM and CBM of blue P (graphyne) in the G/BP
heterostructure. (c)–(f) the band structures of the G/BP heterostructure under
different values of external Efield: (c) −0.26VÅ−1, (d) −0.16 VÅ−1, (e) + 0.2
VÅ−1, (f) 0.3 V Å−1. (For interpretation of the references to colour in this figure
legend, the reader is referred to the web version of this article.)
Fig. 4(b) displays band edges dominated by blue P and graphyne
under various Efield. The CBM and VBM of blue P (graphyne) of the G/
BP are denoted as CBMBP and VBMBP (CBMG and VBMG) respectively.
One can see clearly that the CBM and VBM of blue P decrease linearly
with Efield, while the CBM and VBM of graphyne manifest an invisible
change. Interestingly, the G/BP experiences a transition from type-I to
type-II under various Efield. In detail, in the case of the negative Efield,
once the Efield exceeds −0.14 V/Å (see Fig. 4(d)), the CBM and VBM at
M point are from the graphyne and blue P, respectively, leading a
transition from type-I to type-II. In the case of the positive Efield, on the
contrary, the CBM comes from blue P, while the VBM is dominated by
the graphyne when Efield exceeds +0.2 V/Å (see Fig. 4(e)). Hence, the
G/BP heterostructure becomes to type-II semiconductor when Efield
exceeds +0.2 V/Å. At the same time, it is worth emphasizing that the
CBM moves from M to A point gradually with an increase of Efield, while
the VBM keeps at M point. Hence, the band gap becomes indirect when
Efield is between +0.2 V/Å and +0.3 V/Å.
It has been reported that one-dimensional and two-dimensional
materials can sustain much larger strain than the corresponding bulk
crystals [46]. Moreover, the electronic properties of blue P based het-
erostructures can be modulated effectively by applying external strains
[2,30,44]. Therefore, it is necessary to explore the effect of small biaxial
strain on the electronic structures of G/BP heterostructure. When the
biaxial strain ranges from −10% to +15% with an increment of 1%,
namely, both compressive strain and tensile strain, are applied, the
geometrical structure integrity of the G/BP is well maintained, in-
dicating that the G/BP can withstand the biaxial strain and is stable in
the elastic regime. Fig. 5(a) presents the variation of band gap as a
function of biaxial strain. One can see that the biaxial strain has an
obvious influence on the band gaps. In the case of compressive strain,
the band gaps exhibit oscillating behavior. The band gap first decreases
to 0.056 eV at −4% compressive strain. Then, the band gap increases to
0.339 eV at −7% compressive strain. Finally, it rapidly reduces to zero
at −10%. This peculiar oscillating phenomenon will be explained in
detail in the band edge states below. In the case of tensile strain, the
band gap increases almost linearly to 0.614 eV with the increasing
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Chemical Physics Letters 730 (2019) 277–282
Fig. 5. (a) The band gap of the G/BP heterostructure as a function of strain λ,
(b) the band edges of graphyne and blue P in the G/BP heterostructure as a
function of strain λ . VBMBP(G) and CBMBP(G) are the VBM and CBM of blue P
(graphyne) in the G/BP heterostructure. The band structures of the G/BP het-
erostructure under different values of strain λ in the biaxial strain, (c) −10%,
(d) −8%, (e) −4%, (f) +8%. (For interpretation of the references to colour in
this figure legend, the reader is referred to the web version of this article.)
tensile strain at +7%. When the strain tensile exceeds +7%, the band
gaps rapidly decline to 0.03 eV at +11%, then it cannot obviously
change with the tensile strain increase to +15%.
Interestingly, there exists a direct-to-indirect gap transition under
different strains. More specially, the band gap remains direct with VBM
and CBM at M point under strain from −4% to +8%. However, The
VBM and CBM of the G/BP deviate from M point and moves towards Г
points gradually with an increase of compressive strain from −4% to
−8%. What’s more, the VBM moves to Г point and the CBM lies still
between M and Г points at −8%. Hence, the band gap becomes indirect
under compressive strain above −4% (see Fig. 5(d) and (e)). When the
compressive strain reaches to −10%, the bandgap converts to zero,
leading the G/BP heterostructure to being metal. For the tensile strain
above +8%, the CBM is still at M point, while the VBM gradually
moves from M point towards the Г point, denoted as C in Fig. 4(f).
Hence, the G/BP becomes an indirect band gap semiconductor once the
tensile strain exceeds +8%.
In order to explore the band alignment of the G/BP heterostructure,
the band edges of the G/BP heterostructure under different strains are
calculated and shown in Fig. 5(b). We can see that there exists the band
arrangement transition. The VBM and CBM of the G/BP are only from
the graphyne when the strain is between −7% and 7%, resulting in the
G/BP still being a type-I heterostructure. The G/BP experiences a
transition from type-I to type-II when compressive strain reaches up to
−8%, due to the VBM and CBM are localized on blue P and graphyne,
respectively. However, as for tensile strain, the G/BP is a type-II het-
erostructure only in the small range of +8% to +10%. Furthermore,
With the tensile strain increasing to above +10%, the type-II hetero-
structure transforms to type-I with both the VBM and CBM being from
graphyne, which can be strictly confirmed in Fig. 5(b).
We also studied the electronic properties of G/BP under the vertical
strain. The band gap varies with the variation of the interlayer distance
of the heterostructure (Fig. 6). When the interlayer distance is 2.0 Å, the
heterojunction exhibits metallicity. With the increase of interlayer
distance, the bandgap increases gradually. When the interlayer distance
increases to 2.4 Å, the bandgap reaches its maximum value of 0.47 eV.
After that, the bandgap decreases gradually. When the interlayer
Y. Wang, et al.
Fig. 6. Band structures for G/BP with different interlayer distance. (a) 2.00 Å,
(b) 2.05 Å, (c) 2.45 Å, (d) 3.90 Å. (e) the band gap of the G/BP heterostructure
as a function of interlayer distance.
Fig. 7. Optical absorption coefficients of G/BP.
distance is greater than 3.9 Å, the bandgap remains constant at 0.37 eV.
This is because when the interlayer spacing is large, the interaction
between graphyne and BP is small and the electronic structure does not
change. In addition, there exists an indirect-to-direct gap transition at
the interlayer distance of 2.4 Å.
The carrier mobility of the heterostructure has a great effect on the
performance of electronic devices [47]. Here, we evaluate the effective
mass of holes and electrons of G/BP according the following equation:
∂ 2E
m∗ = ℏ2 ( )−1
∂k 2
where ℏ is Planck’s constant and k is the wave vector in momentum
space. The effective masses in G/BP are 0.14 me alone the x direction
(3.52 me alone the y direction) for holes and 1.63 me alone the x di-
rection (1.38 me alone the y direction) for electrons, which are larger
than that in graphene [48].
To evaluate the optical properties of G/BP, we calculate the ab-
sorption coefficients α(E) through the equation:
4πE
α (E ) = 0.5((ε12 + ε22)0.5 − ε1)
hc
where ε1 and ε2 are the real and imaginary parts of the dielectric
function, respectively [49,50]. It is found that G/BP allows the high
absorption coefficients (approximately 105 cm−1) and broad
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Chemical Physics Letters 730 (2019) 277–282
wavelength range of optical absorption from infrared to ultraviolet
(Fig. 7). The strong visible and ultraviolet light absorption will provide
obvious advantages for G/BP implied potential applications in devices
for photodetection and photovoltaic structures using in solar cells
[51–54].
4. Conclusion
In conclusion, by means of density functional theory computations,
we have systematically investigated the structural and electronic
properties of the G/BP heterostructure. Our calculations indicate that
the A-stacking with the largest binding energy and the shortest inter-
layer distance is the most stable. Moreover, we find that the G/BP is
direct bandgap semiconductor with type-I band alignment, due to CBM
and VBM of the G/BP at M point are uniquely from the graphyne layer.
Furthermore, we study the effects of the external Efield and strain on the
electronic properties of G/BP. Interestingly, the band gap is sensitive to
biaxial strain and the external Efield. More specifically, the semi-
conductor-to-metal transition is observed when the Efield of 0.3 V/Å and
−0.26 V/Å are applied. At the same time, a change of direct to indirect
band gap is found under a +0.2 V/Å Efield. In addition, the G/BP is
type-II semiconductor when the Efield is between −0.26%V/Å and
−0.16%V/Å (+0.2 V/Å and +0.3 V/Å). Similarly, the G/BP undergoes
a transition from type-I semiconductor with direct bandgap to type-II
semiconductor with indirect bandgap under different strains. A mod-
erate −4% compression strain and +8% tensile strain can trigger the
direct-to-indirect band gap transition. Moreover, the G/BP is type-II
semiconductor when the stains are between +8% to +10% and −10%
to −8%. In a word, the bandgap can be effectively modulated via
various Efield and strain. These results open a new avenue for applica-
tion of the G/BP vdW heterostructure in future spintronic and elec-
tronic devices.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests.
Acknowledgements
The work was support by the National Natural Science Foundation
of China (Grant Nos. 11404112, U1604131, 61841702), Funding
scheme for young teachers in colleges and universities in Henan pro-
vince (Grant No. 2017GGJS077).
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.cplett.2019.06.005.
References
[1] M. Sun, J.-P. Chou, J. Yu, W. Tang, Phys. Chem. Chem. Phys. 19 (2017) 17324.
[2] W.X. Zhang, W.H. He, J.W. Zhao, C. He, J. Solid State Chem. 265 (2018) 257.
[3] J. Heo, H. Jeong, Y. Cho, J. Lee, K. Lee, S. Nam, E.-K. Lee, S. Lee, H. Lee, S. Hwang,
S. Park, Nano Lett. 16 (2016) 6746.
[4] C. Xia, J. Du, M. Li, X. Li, X. Zhao, T. Wang, J. Li, Phys. Rev. Appl. 10 (2018)
054064.
[5] W. Zhang, D. Chang, Q. Gao, C. Niu, C. Li, F. Wang, X. Huang, C. Xia, Y. Jia, J.
Mater. Chem. C 6 (2018) 10256.
[6] C.V. Nguyen, H.D. Bui, T.D. Nguyen, K.D. Pham, Chem. Phys. Lett. 724 (2019) 1.
[7] P. Zhang, X. Yang, W. Wu, L. Tian, H. Cui, K. Zheng, J. Jiang, X. Chen, H. Ye, Chem.
Phys. Lett. 700 (2018) 114.
[8] L. Peng, C. Wang, Q. Qian, C. Bi, S. Wang, Y. Huang, A.C.S. Appl, Mater. Interfaces 9
(2017) 40969.
[9] E.S. Souza, W.L. Scopel, R.H. Miwa, Phys. Chem. Chem. Phys. 20 (2018) 17952.
[10] T. Roy, M. Tosun, X. Cao, H. Fang, D.-H. Lien, P. Zhao, Y.-Z. Chen, Y.-L. Chueh,
J. Guo, A. Javey, ACS Nano 9 (2015) 2071.
[11] N. Huo, J. Kang, Z. Wei, S.-S. Li, J. Li, S.-H. Wei, Adv. Funct. Mater. 24 (2014) 7025.
[12] O. Lopez-Sanchez, E. Alarcon Llado, V. Koman, A. Fontcuberta i Morral,
Y. Wang, et al. Chemical Physics Letters 730 (2019) 277–282

A. Radenovic, A. Kis, ACS Nano 8 (2014) 3042. [35] J.P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 77 (1996) 3865.
[13] R.H. Baughman, H. Eckhardt, M. Kertesz, J. Chem. Phys. 87 (1987) 6687. [36] S. Grimme, J. Comput. Chem. 27 (2006) 1787.
[14] A.L. Ivanovskii, Prog. Solid State Chem. 41 (2013) 1. [37] S. Grimme, J. Antony, S. Ehrlich, H. Krieg, J. Chem. Phys. 132 (2010).
[15] N. Narita, S. Nagai, S. Suzuki, K. Nakao, Phys. Rev. B 62 (2000) 11146. [38] K. Momma, F. Izumi, J. Appl. Crystallogr. 44 (2011) 1272.
[16] L.D. Pan, L.Z. Zhang, B.Q. Song, S.X. Du, H.J. Gao, Appl. Phys. Lett. 98 (2011) [39] B.-J. Wang, X.-H. Li, R. Zhao, X.-L. Cai, W.-Y. Yu, W.-B. Li, Z.-S. Liu, L.-W. Zhang, S.-
173102. H. Ke, J. Mater. Chem. A 6 (2018) 8923.
[17] G. Li, Y. Li, H. Liu, Y. Guo, Y. Li, D. Zhu, Chem. Commun. 46 (2010) 3256. [40] S. Ma, C.X. Zhang, J. He, P. Zhou, K.W. Zhang, C. He, L.Z. Sun, Comp. Mater. Sci. 91
[18] Q. Peng, A.K. Dearden, J. Crean, L. Han, S. Liu, X. Wen, S. De, Nanotechnol. Sci. (2014) 274.
Appl. 7 (2014) 1. [41] G. Henkelman, A. Arnaldsson, H. Jonsson, Comput. Mater. Sci. 36 (2006) 354.
[19] Z. Li, M. Smeu, A. Rives, V. Maraval, R. Chauvin, M.A. Ratner, E. Borguet, Nat. [42] M. Sun, J.-P. Chou, J. Yu, W. Tang, J. Mater. Chem. C 5 (2017) 10383.
Commun. 6 (2015) 6321. [43] Z. Jian, L. Kun, W. Qian, X.S. Chen, S. Qiang, J. Puru, J. Chem. Phys. 134 (2011)
[20] B.G. Kim, H.J. Choi, Phys. Rev. B 86 (2012) 115435. 174701.
[21] H. Shin, S. Kang, J. Koo, H. Lee, J. Kim, Y. Kwon, J. Chem. Phys. 140 (2014) [44] Q. Yang, C. Tan, R. Meng, J. Jiang, Q. Liang, X. Sun, D. Yang, X. Chen, IEEE Electr.
114702. Device L. 38 (2017) 145.
[22] H. Sevinçli, C. Sevik, Appl. Phys. Lett. 105 (2014) 223108. [45] J. Heyd, G.E. Scuseria, M. Ernzerhof, J. Chem. Phys. 118 (2003) 8207.
[23] Y. Wang, N. Song, T. Zhang, Y. Zheng, H. Gao, K. Xu, J. Wang, Appl. Surf. Sci. 452 [46] R.S. Jacobsen, K.N. Andersen, P.I. Borel, J. Fage-Pedersen, L.H. Frandsen,
(2018) 181. O. Hansen, M. Kristensen, A.V. Lavrinenko, G. Moulin, H. Ou, C. Peucheret,
[24] Y.S. Wang, P. Fei Yuan, M. Li, W. Fen Jiang, Q. Sun, Y. Jia, J. Solid State Chem. 197 B. Zsigri, A. Bjarklev, Nature 441 (2006) 199.
(2013) 323. [47] M.M. Dong, C. He, W.X. Zhang, J. Mater. Chem. C 5 (2017) 3830.
[25] J.L. Zhang, S. Zhao, C. Han, Z. Wang, S. Zhong, S. Sun, R. Guo, X. Zhou, C.D. Gu, [48] M.-Q. Long, L. Tang, D. Wang, L. Wang, Z. Shuai, J. Am. Chem. Soc. 131 (2009)
K.D. Yuan, Z. Li, W. Chen, Nano Lett. 16 (2016) 4903. 17728.
[26] Q. Peng, Z. Wang, B. Sa, B. Wu, Z. Sun, Sci. Rep. 6 (2016) 31994. [49] Z. Guan, C.-S. Lian, S. Hu, S. Ni, J. Li, W. Duan, J. Phys. Chem. C 121 (2017) 3654.
[27] Z.Y. Zhang, M.S. Si, S.L. Peng, F. Zhang, Y.H. Wang, D.S. Xue, J. Solid State Chem. [50] C. Xia, W. Xiong, J. Du, T. Wang, Y. Peng, J. Li, Phys. Rev. B 98 (2018) 165424.
231 (2015) 64. [51] B. Yang, J. Chen, F. Hong, X. Mao, K. Zheng, S. Yang, Y. Li, T. Pullerits, W. Deng,
[28] J. Zhu, J. Zhang, Y. Hao, Jpn. J. Appl. Phys. 55 (2016) 080306. K. Han, Angew. Chem. Int. Ed. 56 (2017) 12471.
[29] J. Guo, Z. Zhou, T. Wang, Z. Lu, Z. Yang, C. Liu, Curr. Appl. Phys. 17 (2017) 1714. [52] B. Yang, J. Chen, S. Yang, F. Hong, L. Sun, P. Han, T. Pullerits, W. Deng, K. Han,
[30] Q. Li, X. Ma, L. Zhang, X.G. Wan, W. Rao, J. Phys. D: Appl. Phys. 51 (2018) 255304. Angew. Chem. 130 (2018) 5457.
[31] B.-J. Wang, X.-H. Li, X.-L. Cai, W.-Y. Yu, L.-W. Zhang, R.-Q. Zhao, S.-H. Ke, J. Phys. [53] B. Yang, F. Hong, J. Chen, Y. Tang, L. Yang, Y. Sang, X. Xia, J. Guo, H. He, S. Yang,
Chem. C 122 (2018) 7075. W. Deng, K. Han, Angew. Chem. Int. Ed. 58 (2019) 2278.
[32] G. Kresse, J. Hafner, Phys. Rev. B 47 (1993) 558. [54] B. Yang, X. Mao, F. Hong, W. Meng, Y. Tang, X. Xia, S. Yang, W. Deng, K. Han, J.
[33] G. Kresse, J. Furthmüller, Comput. Mater. Sci. 6 (1996) 15. Am. Chem. Soc. 140 (2018) 17001.
[34] G. Kresse, J. Furthmüller, Phys. Rev. B 54 (1996) 11169.

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