Applied Surface Science 526 (2020) 146730

Contents lists available at ScienceDirect

Applied Surface Science

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

Full Length Article

First-principles study of mechanical, electronic and optical properties of T

Janus structure in transition metal dichalcogenides
⁎
Vuong Van Thanha, , Nguyen Duy Vana, Do Van Truongb,c, Riichiro Saitod,
⁎
Nguyen Tuan Hungd,e,
a
Department of Design of Machinery and Robot, School of Mechanical Engineering, Hanoi University of Science and Technology, Hanoi, Viet Nam
b
Department of Mechatronics, School of Mechanical Engineering, Hanoi University of Science and Technology, Hanoi, Viet Nam
c
International Research Center for Computational Materials Science, Hanoi University of Science and Technology, Hanoi, Viet Nam
d
Department of Physics, Tohoku University, Sendai 980-8578, Japan
e
Frontier Research Institute for Interdisciplinary Sciences, Tohoku University, Sendai 980-8578, Japan

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

Keywords: Using first-principles calculations, we investigate mechanical, electronic and optical properties of so-called Janus
Janus transition metal dichalcogenides structure for monolayer transition metal dichalcogenides (TMDs), MXY (M = Mo, W; X or Y = S, Se, Te; X ≠ Y),
Ideal strength in which chalcogen atoms at both side of the TMDs are not the same elements. Our calculated results indicate
Density functional theory that WSSe shows the highest stiffness and the most ideal strength among the Janus TMDs due to their strongest
Optical absorption
ionic bond. In the unstrain cases, WSeTe, WSSe and MoSeTe are direct-gap semiconductors, while MoSSe, MoSTe
and WSTe are indirect-gap semiconductors. The energy band gaps of the Janus TMDs decrease with increasing of
the tensile strain due to the coupling between the p and d orbitals of the X/Y and M atoms, respectively.
Furthermore, the tensile strain effectively modulates the optical absorption of the Janus TMDs. For example, the
optical absorption of MoSSe is three times stronger at a photon energy of 2.5 eV. The calculated results of Janus
TMDs provide useful information for applications in nanoelecromechanical, optoelectronic, and photocatalyst
devices.

1. Introduction
Two-dimensional (2D) transition metal dichalcogenides (TMDs)
have been promising for nanoelectronic, optoelectronic and photo-
catalytic devices due to their unique properties [1–6], such as an in-
direct-to-direct band gap transition, [7–9], valley-selective circular di-
chroism [10] and multi-excitons [11]. Monolayer TMDs are direct-gap
semiconductors in a visible range from 400 nm (3 eV) to 700 nm
(1.8 eV) [12]. Thus, the monolayer TMDs might be promising materials
for optoelectronics applications, in which the energy band gap and the
band structures are essential properties for discussing the performance.
In oder to control these properties, applying strain on the monolayer
TMDs has been widely investigated both theoretically and experimen-
tally [13,14]. Yue et al. [15] shows that MoS2 has a direct-to-indirect
transition at a strain ∼ 1% and a semiconductor-to-metal transition at a
strain ∼ 10%. By using density functional theory (DFT), Scalise et al.
[16] also theoretically showed that MoS2 shows a direct-to-indirect
transition at a tensile strain up to ∼ 2% . As for WX2 TMDs (X = S, Se,
and Te), the energy band gaps are closed when the tensile strain reaches
10% for WS2, and 11% for WSe2 and WTe2 [17]. Theoretically, the
effect of strain on the optical properties of the 2D TMDs have been
widely investigated [17–20], in which real part of the dielectric con-
stant, reflectance index, and refractive index of the WX2 are enhanced
with increasing the strain [17]. These results show that strain en-
gineering is an effective tool to tune the electronic and optical prop-
erties of the TMDs [15–20].
Recently, Janus MoSSe, which is defined by a sandwiched S-Mo-Se
layer structure, has been successfully synthesized [21,22] using a che-
mical vapor deposition. Janus TMD is labeled by MXY (M = Mo, W; X
or Y = S, Se, Te; X ≠ Y). Compared with the conventional TMDs, the
electronic properties of the Janus TMD have novel features due to the
structural symmetry-breaking [23,24]. Since the top and bottom atomic
layers of the Janus TMDs consist of different atoms, internal electric
field induced by the dipole moment separate an electron–hole pair,
which is helpful for application of water splitting [25]. Wang et al. [26]
also showed that the 2D Janus TMDs are semiconductors with a energy
band gap range from 1.36 to 1.97 eV and that they observe strong op-
tical absorption at the visible-light region (1.61 to 3.10 eV). The effect

⁎
Corresponding author at: Frontier Research Institute for Interdisciplinary Sciences, Tohoku University, Sendai 980-8578, Japan (N.T. Hung).
E-mail addresses: thanh.vuongvan@hust.edu.vn (V.V. Thanh), nguyen@flex.phys.tohoku.ac.jp (N.T. Hung).

https://doi.org/10.1016/j.apsusc.2020.146730
Received 17 February 2020; Received in revised form 7 May 2020; Accepted 17 May 2020
Available online 26 May 2020
0169-4332/ © 2020 Elsevier B.V. All rights reserved.
V.V. Thanh, et al.
of strain on the electronic structures and transport properties of the
Janus TMDs has also been considered by the DFT calculations and
Boltzmann equation [27], respectively, in which the transport proper-
ties are improved by applying strain. Therefore, the strain engineering
is a helpful tool to improve the electronic and optical properties not
only for the TMDs but also for the Janus TMDs. In the analysis, the
mechanical properties such as the mechanical breakdown and ideal
strength, which can be defined by a maximum value of the stress that
the materials can achieve by applying the strain, are important para-
meters. Although many studies have focused on synthesis, electronic
and optical properties of the 2D Janus materials [21–23,26–33], their
mechanical properties have not been clarified yet, in particular ideal
strength and mechanical breakdown. These properties would be im-
portant for synthesizing the Janus material and its application to the
device. Thus, the theoretical analysis of mechanical property of the 2D
Janus TMDs is necessary. Further, understanding the electronic and
optical properties of the Janus TMDs under the tensile strain is also
necessary to investigate for nanoelectronic, optoelectronic, and photo-
catalytic applications.
In the present paper, we investigate the mechanical, electronic and
optical properties of the Janus TMDs MXY as a function of the tensile
strain using first-principles calculations. We show that the Janus TMDs
show anisotropic behavior for uniaxial tensile strain. We also discuss
the effect of the strain on the electronic and optical properties of the
Janus TMDs.
2. Computational methods
In this study, we perform the first-principles calculations based on
the DFT using Quantum ESPRESSO [34]. A cut-off energy for the wave
function is taken to be 60 Ry. k -point grid in the Brillouin zone is set by
a 16 × 16 × 1 grid for all Janus TMDs in the Monkhorst–Pack method
[35]. Both the local-density approximations (LDA) [36] and the gen-
eralized-gradient approximation (GGA) [37] are performed for dis-
cussing mechanical properties and electronic (or optical) properties,
respectively. The energy band gap is corrected by the Heyd-Scuseria-
Ernzerhof (HSE) hybrid functional [38]. It is because the results of the
GGA generally underestimate the mechanical properties compared with
those by the LDA. In particular, Cooper et al. [39] discussed this be-
havior for the monolayer MoS2. On the other hand, the GGA + HSE is
better than the LDA to evaluate the whole band structure of the 2D
Janus TMDs [40].
The atomic structures of the Janus TMDs are shown in Fig. 1. The
periodic boundary condition is applied in all the models, in which a
Fig. 1. The top view (a) and front view (b) of the Janus TMDs. The x and y
directions correspond to the armchair and zigzag directions, respectively. (c)
The first Brillouin Zone of the Janus TMDs. Under tensile strain, the original
crystal symmetry is broken, thus M′ and K′ become no longer equivalent to M
and K, respectively.
2
Applied Surface Science 526 (2020) 146730
vacuum space of 30 Å in the direction perpendicular to the monolayer
(z direction) is set to avoid interactions between adjacent layers. To
obtain optimized atomic configurations of the Janus TMDs, the atomic
positions and cell vectors are relaxed using the Broyden-Fletcher-
Goldfarb-Shanno (BFGS) minimization method [41–44]. The model is
considered as a optimized structure when the Hellmann–Feynman
forces and all components of the stress are less than 0.0005 Ry/a.u. and
0.05 GPa, respectively.
The Themo-pw code [45] is used to calculate the elastic constants Cij
of the Janus TMDs. The calculated stresses for a 2D material are ex-
pressed as a 2D force per length in the units of N/m by taking the
product of the 3D Cauchy stresses (in the units of N/m2) and the super-
cell thickness of 30 Å [46]. The Young modulus, Y, and the Poisson
ratio, ν , of the 2D material are expressed by [47–49]
2 2
C11 − C12 C12
Y= , and ν = .
C11 C11 (1)
σi ∊i
To investigate the ideal strength and ideal strain (i.e. the strain
at the maximum stress) of the Janus TMDs under the strains, a tensile
strain is applied to the structures by elongating the cell in uniaxial di-
rection ( x , y ) with an increment of 0.02 of the tensile strain until the
structure is broken. Here, the dimensionless tensile strain is defined by
ε = (L − L0)/ L0 , where L and L0 are the length of the unit cell for the
strained and unstrained structures, respectively.
To obtain the optical properties of the Janus TMDs under the tensile
strain, we calculated the optical absorption coefficient α (ω) using the
following equation [50]
1/2
4πe ⎧ [ε12 + ε22 ]1/2 − ε1 ⎫
α (ω) = ,
hc ⎨
⎩ 2 ⎬
⎭ (2)
where ε1 (ω) and ε2 (ω) are real and imaginary parts of the dielectric
function, respectively, c is the speed of light in the vacuum and ω is the
angular frequency of light.
3. Results and discussion
3.1. Structure and stability of Janus TMDs
In Table 1, we list the optimized lattice parameters of the Janus
TMDs MXY by using the LDA, in which the lattice parameters of MoXY
and WXY have quite similar values to each other. The lattice constants
of the Janus TMDs are arranged as follows MSSe < MSTe < MSeTe
(M = Mo, W), respectively. The lattice constant of MoSSe is 3.23 Å,
which is in a good agreement with the previous theoretical results
[21,30,51,52], indicating that the present calculations are consistent.
The lattice constant of MoSSe lies between that of MoS2 (a = 3.19 Å)
and MoSe2 (a = 3.31 Å) [48]. We note that the buckling height (h, see
Fig. 1(b)) of MoSSe (3.22 Å) is larger than that of MoS2 (3.12 Å [51],
3.16 Å [53]) and smaller than that of MoSe2 (3.35 Å [51],3.34 Å [53]).
Although the atomic structures of the Janus TMDs have been opti-
mized, they do not guarantee the elastic and dynamic stabilities [54].
Therefore, we need to analyze the phonon dispersion and the elastic
stability conditions for the Janus TMDs. In Fig. 2, we show the phonon
dispersions of all Janus TMDs. It can be seen from the insets of Fig. 2
that WSeTe, MoSeTe, MoSSe, MoSTe are dynamically stable without
any imaginary phonon frequency, while WSSe and WSTe show very
small negative (imaginary) frequencies (∼ −1 cm−1) around the
Γ -point, which may indicate a structural instability. Cheng et al. [53]
pointed out that these negative frequencies are related to a bending of
the X/Y plane in the Janus structures, and they showed MoSTe and
MoSeTe are unstable with negative frequencies ∼ −1 cm−1. Since the
difference in the method between Cheng et al. and us are GGA and LDA,
respectively, a small value of the imaginary phonon frequency is sen-
sitive. Nevertheless, since the Janus TMDs are synthesized on the sub-
strate [21], the instability for bending can be avoided experimentally.
V.V. Thanh, et al. Applied Surface Science 526 (2020) 146730

Table 1
i
Lattice constants a (Å), buckling heights h, elastic constants Cij (N/m), the Young modulus Y (N/m), the Poisson ratios ν , 2D stress σxx (N/m) (∊ixx ) and σ yy
i
(N/m) (∊iyy )
of the Janus TMDs.
Materials a h C11 C12 C66 Y ν i
σxx (∊ixx ) i
σ yy (∊iyy )

MoSSe 3.23 3.22 126.78 20.61 53.07 123.43 0.163 15.75 (0.27) 9.06 (0.17)
MoSTe 3.32 3.33 119.82 25.32 47.25 114.47 0.211 13.13 (0.26) 7.32 (0.15)
MoSeTe 3.36 3.47 96.57 20.67 37.95 92.15 0.214 13.07 (0.28) 6.57 (0.15)

WSSe 3.22 3.31 141.27 22.41 59.43 137.72 0.159 17.03 (0.27) 10.49 (0.17)
WSTe 3.32 3.32 133.62 26.25 53.70 128.46 0.196 14.73 (0.27) 8.68 (0.17)
WSeTe 3.38 3.45 111.03 17.31 46.86 108.33 0.156 14.22 (0.30) 7.77 (0.17)

Moreover, for MoSSe, the calculated out-of-plane A1 and in-plane E′
modes are 285 cm−1 and 356 cm−1, which agree well with the ob-
served Raman peaks at 288 cm−1 and 355 cm−1 [21], respectively.
Compared with MoS2 (A1 = 406 cm−1 and E′ = 387 cm−1), the shift of
the A1 mode is larger than that of the E′ mode. It is because that the A1
optical mode might be related to the out-of-plane symmetry-breaking,
while the E′ mode is in-plane oscillation of the bond length [21,25].
Next we discuss the elastic stability of the Janus TMDs. The neces-
sary and sufficient conditions of the elastic stability of the 2D materials
are C11 > |C12 | > 0 and C66 > 0 [55]. As shown in Table 1, we get that
C11 > |C12 | > 0 and C66 > 0 for all Janus TMDs. Therefore, the Janus
TMDs have the stable structures judging from these conditions. By using
Cij , the Young modulus Y and the Poisson ratio ν of the Janus TMDs are
calculated by Eq. (1) and are also listed in Table 1. Y of the Janus TMDs
decreases with increasing atomic number of metal ZM (ZMo < ZW ), that
is, Y(MSSe)> Y(MSTe)> Y(MSeTe) (M = Mo or W). Therefore, MoSSe
and WSSe are the stiffest materials in the Janus MoXY and WXY com-
pounds with Y = 123.43 GPa and Y = 137.72 GPa, respectively. Li
et al. [31] also reported a high value of Y(MoSSe) about 106 − 113 GPa.
3.2. Ideal strength and failure behaviors of Janus TMDs
In Figs. 3(a) and (b), we plot the stress-strain curves of the Janus
TMDs in the x and y directions, respectively. We can see that the Janus
TMDs show an anisoptropic behavior for σ , that is, σxx ≠ σyy when
∊xx = ∊yy , where x and y are the armchair and zigzag directions, re-
spectively. The ideal strain in the armchair direction becomes up to
0.26 − 0.30 , which is larger than that of the zigzag direction about
0.15 − 0.17 as shown in Table 1. This anisotropic behavior is also ob-
served in MoS2 [56,57] with the ideal strains are 0.28 and 0.18 for the
armchair and zigzag directions, respectively. Li et al. [56] showed that
the anisotropic behavior in MoS2 comes from the fact that the dis-
placement of the S atoms makes the zigzag Mo-S chain more flat than
that in the homogeneous structure under zigzag strain, while there is a
small displacement under the armchair strain. When we discuss the
strain effect, we should consider structural phase transition for a given
stress. In order to check the stability, we optimize structures of MoSeTe
with a supercell 2a × 2 3 a at ∊xx = 0.28 and ∊yy = 0.15 for armchair and
zigzag directions, respectively. As shown in Fig. S1 (Supplementary
data), the calculated results indicate no structural transition for the
both cases, which is consistent with the previous works for monolayer
MoS2 [59,39].
Since the ideal strain provides a large resistance to the tensile load,
the ideal strength of the Janus TMDs along the armchair direction is
larger than that along the zigzag direction, as shown in Figs. 3(a) and
(b). In the armchair direction, WSSe is the strongest in the Janus TMDs,
i
with σxx = 17.03 N/m. Bertolazzi et al. [58] reported the average value
of the ideal strength about 15 ± 3 N/m of MoS2 by using nano-in-
dentation in an atomic force microscope. In this present study, the ideal
i i
strength of MoSSe reaches σxx = 15.75 N/m (or σxx = 25.6 GPa with a
layer thickness d 0 = 6.145Å [48,59]) at the ideal strain ∊ixx = 0.27 ,
which is in a good agreement with the experimental observations (22±
4 GPa) [58]. The ideal strength and ideal strain are obtained from the
stress–strain relationship in Figs. 3(a) and (b), and are listed in Table 1.
In order to understand why WSSe has a highest ideal strength, we plot
the ideal strength as a function of the ionicity I as shown in Fig. 3(c).
The I of the Janus TMDs MXY is calculated by the Pauling expression as
1
I = 1 − exp ⎡− (χM − χXY )2⎤,
⎣ 4 ⎦ (3)

Fig. 2. Phonon dispersions of the Janus TMDs by the LDA calculation at the equilibrium state. The insets show a magnified view of the acoustic branches around the
Γ - point.

3
V.V. Thanh, et al.
Fig. 3. Engineering stress of the Janus TMDs by the LDA calculation as a function of tensile strain: σxx and σyy along (a) armchair and (b) zigzag directions,
respectively.
where χM is the electronegativities of the M atoms and χXY is the
average electronegativities of the X and Y atoms (i.e.
χXY = (χX + χY )/2 ) [60,61]. A large value of the I indicates more ionic
character in the Janus TMD [62]. As shown in Fig. 3(c), the relationship
between the ideal strength and the I shows as a linear function for each
i i
direction, in which are σxx = 0.51I + 10.4 and σyy = 0.47I + 4.4 for
armchair and zigzag directions, respectively. Based on the relationship
I ∝ σ i , the Pauling ionicity I can be used as an important parameter to
evaluate the stiffness and ideal strength of the ionic materials. Since
WSSe has a highest I values about 13, it exhibits the highest ideal
strength. It is noted here that I of MoS2 is 12 [61].
In order to understand the deformation mechanism of the Janus
TMDs, the bond lengths between M and X/Y atoms as a function of
tensile strains in both armchair (solid symbol) and zigzag (open
symbol) directions are plotted in Fig. 4. Without strain (∊xx = ∊yy = 0 ),
the M (Mo, W)-Te bond lengths of MXY are larger than the M-S and M-
Fig. 4. The M (Mo, W)- S, M-Se and M-Te bond lengths of the Janus TMDs as a function of strain for the x (armchair) and y (zigzag) directions, respectively.
4
Applied Surface Science 526 (2020) 146730
Se bond lengths, respectively. For the tensile strain, the M-S, M-Se and
M-Te bond lengths increase with increasing strain in the armchair di-
rection, while they decrease in the zigzag direction. Since the change of
the bond lengths along the armchair direction is larger than that along
zigzag direction, the ideal strain along the armchair direction is larger
than that along the zigzag directions as shown in Figs. 3(a) and (b).
3.3. Strain effect on electronic properties of Janus TMDs
In Fig. 5, we show the band structures of the Janus TMDs for
∊xx = ∊yy = 0 by using the GGA + HSE calculation. The obtained results
show that WSeTe, WSSe and MoSeTe are direct-gap semiconductors
with the bottom of conduction band (CBM) and the top of valence band
(VBM) at the K point in the Brillouin zone, while MoSSe, MoSTe and
WSTe are indirect-gap semiconductors with an energy band gap from
1.42 eV (MoSTe) to 2.3 eV (WSSe). In Fig. 5, the CBM and VBM are
V.V. Thanh, et al. Applied Surface Science 526 (2020) 146730

Fig. 5. Band structures of the Janus TMDs by the GGA + HSE calculation without strain (∊xx = ∊yy = 0 ). The Fermi level is set to be zero and the arrow connects the
top of valence band and the bottom of conduction band for each Janus TMD.

connected by arrow for each Janus TMD. The energy band gap of
MoSSe is 2.08 eV, which is in a good agreement with the previous
theoretical value of 2.1 eV [25]. Since the energy difference between
the two valleys of the conduction band at the K point and along K-Γ line
is very small, e.g. 0.1 eV for MoSSe, the direct- or indirect-gap is sen-
sitive to the approximations of exchange–correlation energy or spi-
n–orbit coupling (SOC). For example, by using GGA + SOC, Liu et al.
[63] showed that MoSSe and WSSe are direct-gap semiconductors,
whereas other Janus TMDs are indirect-gap semiconductors. On the
other hand, Wang et al. [26] used the HSE functional and SOC to cal-
culate the electronic structures, and they showed that all Janus TMDs
except MoSSe are indirect-gap semiconductors.
In Figs. 6 (a) and (b), we show the band structures of MoSeTe at the
different tensile strains in the armchair and zigzag directions, respec-
tively. As we see from Fig. 6, the band structure of MoSeTe is
significantly modified by the strain, which is in a good agreement with
the previous studies [27]. For ∊ = 0 , MoSeTe is a direct-gap semi-
conductor with the band gap of 1.75 eV, which is consistent with the
previous theoretical study (1.71 eV) using the HSE [25] method. When
the strain increases gradually, the energy band gap at the K-point
monotonically decreases. At ∊ = 0.04 , MoSeTe becomes an indirect-gap
semiconductor with band gap of ∼ 1.45 eV for both armchair and zigzag
directions. These results suggest that not only band gap but also di-
rect–indirect transition of MoSeTe occur by applying strain. The band
structures of the other Janus TMDs (MoSSe, MoSTe, WSeTe, WSSe and
WSTe) are also calculated by using the GGA + HSE calculation, as
shown in Figs. S3 to S7 in Supplementary data.
In Fig. 7, the energy band gaps of the Janus TMDs are plotted as
functions of the strain for (a) the armchair and (b) zigzag directions.
Since the Janus structures are unstable at a critical strain, we only

Fig. 6. Band structures of the monolayer MoSeTe by the GGA + HSE calculation for the tensile strains ∊ = 0 , 0.04, 0.08 and 0.12 for (a) armchair and (b) zigzag
directions, respectively. The Fermi level is set to be zero and the arrow connects the top of valence band and the bottom of conduction band for each strain.

5
V.V. Thanh, et al.
Fig. 7. Energy band gaps of the Janus TMDs by the HSE calculation as a
function of tensile strain in (a) the armchair and (b) zigzag directions, respec-
tively.
consider the strain up to the ideal strain for each Janus TMD (refer
Table S1 for the GGA case). We note that the ideal strains obtained by
using the GGA and LDA show a difference of about 10%, as shown in
Table S1 and Fig. S3. Chang et al. [40] showed that the electronic states
at the top of the valence band and the bottom of the conduction band
are given by couplings between p orbitals of X/Y atoms and d z 2, d x 2 − y 2 ,
and d xy orbitals of M atoms. Therefore, the change of the X-M-Y bond
angle under the strain will modify the couplings of orbitals. For a tensile
strain, the X/Y atoms move toward the M atoms and the X-M-Y bond
angle is reduced, which lead to weaken the coupling between the p and
out-of-plane d z 2 orbitals and to strengthen the coupling between the p
and in-plane d x 2 − y 2 and d xy orbitals. As a result the electronic energies at
the Γ and K points increase and decrease by the tensile strain, respec-
tively. Thus the energy band gap of the Janus TMDs decreases with
increasing the tensile strain. In addition, the direct-to-indirect transi-
tions also occur for MoSeTe at ∊ = 0.04 , as shown in Fig. 5.
3.4. Strain effect on optical properties of Janus TMDs
In Figs. 8(a) and (b), we show the optical absorption α (ω) of the
Janus TMDs by using the GGA + HSE calculation at the unstrain
(∊xx = ∊yy = 0 ) in the energy range from ℏω = 0 to 5 eV, in which α (ω)
is calculated by Eq. (2). We find that α (ω) exhibits a strong anisotropy
along the polarization directions (α// (ω) xx = α// (ω) yy > α⊥ (ω) zz ). In the
visible-light region, α (ω) of the Janus TMDs along the in-plane
(α// (ω) xx = α// (ω) yy ) direction is much larger than that of the out-of-
plane (α⊥ (ω) zz ) direction with one order of magnitude, which is con-
sistent with the previous DFT calculations using the HSE + SOC method
[26]. For the in-plane direction, the Janus TMDs exhibit strong ab-
sorption when the photon energy is more than 2 eV, as shown in
Fig. 8(a). The optical absorption of all the Janus TMDs reaches around
15 × 10 4 − 30 × 10 4 cm−1 at the visible-light region, which is in a good
agreement with the earlier DFT results [25], and the values are com-
parable to CdTe and CIGS materials [65]. Since the photocurrent J (ω) is
proportional to the optical absorption coefficient, J (ω) ∝ α (ω) , [66] the
Fig. 8. Optical absorption of six Janus MXY monolayers by GGA + HSE calculation at the equilibrium condition (∊xx = ∊yy = 0 ) along the (a) in-plane (α// (ω) ), (b)
out-of-plane directions (α⊥ (ω) ) and (c) JDOS of Janus TMDs. The dash lines denote the range of visible light from 1.61 eV to 3.10 eV.
6
Applied Surface Science 526 (2020) 146730
Janus TMDs might be as a good candidate materials for the photo-
voltaic solar cells. For the out-of-plane, the Janus TMDs has the largest
value of 2.5 × 10 4 cm−1 at 3.1 eV, as shown in Fig. 8(b). In order to
understand the peaks of the absorption spectrum, we calculate the joint
density of states (JDOS) as shown in Fig. 8(c). Here, the JDOS is defined
as [67]
1
JDOS(E ) =
4π 3
∫ d3kδ [Ev (k ) − Ec (k ) − E ], (4)
where k is wave-vector, and Ev (k ) and Ec (k ) are the valence and con-
duction bands, respectively. The JDOS is associated with the transitions
from the valence bands to the conduction bands. Therefore, a large
peak in the JDOS corresponds to the peak in the absorption spectrum as
shown in Figs. 8. From Eq. (4), a peak is found at a photon of energy
E = Ek, v − Ek, c , which corresponds to the two-dimensional Van Hove
singularities in the Brillouin zone. The Van Hove singularities usually
occur at high-symmetry points in the k -space [68]. As discussed in
Section 3.3, however, the electron states at the high-symmetry points
such as K and Γ can be shifted by applying strain. Therefore, the strain
engineering can work as an effective tool to improve the optical prop-
erties of the Janus TMDs.
In Figs. 9(a) and (b), we show the optical absorption of MoSSe for
several strains along the armchair and zigzag directions, respectively.
For tensile strains along the armchair direction, α// (ω) xx is much en-
hanced at around 2.5 eV, while α// (ω) yy and α⊥ (ω) zz do not show a
significant change. As shown in Fig. 9(a), at the photon energy of
2.5 eV, α// (ω) xx increases from 7.5 × 10 4 cm−1 to 28 × 10 4 cm−−1. It is
because that at ∊xx = 0.12, the band gap of MoSSe is reduced by 1.0 eV.
Thus, the peak position of α// (ω) xx at 3.5 eV is shifted to 2.5 eV. The
scenario is similar to the case of tensile strains along the zigzag direc-
tion. That is, the peak position of α// (ω) yy at 3.5 eV is shifted to 2.5 eV.
Therefore, the optical absorption is enhanced around 2.5 eV, in which
α// (ω) yy increases from 8 × 10 4 cm−1 to 31 × 10 4 cm−1 as shown in
Fig. 9(b). The calculated strain-dependent α (ω) of other Janus TMDs,
including MoSeTe, MoSTe, WSeTe, WSSe and WSTe, are shown in Figs.
S8 to S12 in Supplementary data.
4. Conclusions
In summary, we investigate the mechanical, electronic and optical
properties of the Janus TMDs under the strain using the LDA and
GGA + HSE calculations. The obtained results show that WSSe is the
strongest material in the Janus MXY compounds. The calculated
strengths of WSSe are 17.03 N/m and 10.49 N/m for the armchair and
zigzag directions, respectively. Based on the relationship I ∝ σ i , we find
that the Pauling ionicity I can be used as an important parameter to
evaluate the stiffness and the ideal strength of the Janus materials. At
the unstrain condition, the energy band gaps of the Janus TMDs from
1.42 eV to 2.3 eV, in which WSeTe, WSSe and MoSeTe are direct-gap
semiconductors, while MoSSe, MoSTe and WSTe are indirect-gap
semiconductors. When the tensile strain is applied, the band gap of the
Janus TMDs decreases with increasing the strain due to the coupling
between the p and d orbitals of the X/Y and M atoms, respectively.
V.V. Thanh, et al.
Fig. 9. Optical absorption of the monolayer MoSSe as a function of photo energy for several tensile strains (∊ = 0 , 0.04, 0.08 and 0.12) along (a) armchair and (b)
zigzag directions, respectively. The dash lines denote the range of visible light from 1.61 eV to 3.10 eV.
Furthermore, the optical absorption coefficient of the Janus TMDs is
enhanced by applying the tensile strain. The use of various Janus TMDs
under applying strain would allow to create new flexible optoelectronic
devices.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
V.V.T. and D.V.T acknowledge the Vietnam’s National Foundation
for Science and Technology Development (NAFOSTED) with No.
107.02–2016.18. R.S. acknowledges JSPS KAKENHI (No.
JP18H01810). N.T.H. acknowledges JSPS KAKENHI (No. JP20K15178)
and the financial support from the Frontier Research Institute for
Interdisciplinary Sciences, Tohoku University.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
online version, athttps://doi.org/10.1016/j.apsusc.2020.146730.
References
[1] K. Kam, B. Parkinson, Detailed photocurrent spectroscopy of the semiconducting
group vib transition metal dichalcogenides, J. Phys. Chem. 86 (4) (1982) 463–467.
[2] R. Tenne, A. Wold, Passivation of recombination centers in n-WSe2 yields high ef-
ficiency (> 14%) photoelectrochemical cell, Appl. Phys. Lett. 47 (7) (1985)
707–709.
[3] E. Gourmelon, O. Lignier, H. Hadouda, G. Couturier, J. Bernede, J. Tedd, J. Pouzet,
J. Salardenne, MS2 (M= W, Mo) photosensitive thin films for solar cells, Sol. Energ.
Mat. Sol. C. 46 (2) (1997) 115–121.
[4] Y. Zheng, Y. Huang, H. Shu, X. Zhou, J. Ding, X. Chen, W. Lu, The effect of lithium
adsorption on the formation of 1T- MoS2 phase based on first-principles calculation,
Phys. Lett. A 380 (20) (2016) 1767–1771.
[5] J. Du, P. Song, L. Fang, T. Wang, Z. Wei, J. Li, C. Xia, Elastic, electronic and optical
properties of the two-dimensional PtX2 (X= S, Se, and Te) monolayer, Appl. Surf.
Sci. 435 (2018) 476–482.
[6] Z. Cui, K. Ren, Y. Zhao, X. Wang, H. Shu, J. Yu, W. Tang, M. Sun, Electronic and
optical properties of van der Waals heterostructures of g-GaN and transition metal
dichalcogenides, Appl. Surf. Sci. 492 (2019) 513–519.
7
Applied Surface Science 526 (2020) 146730
[7] K.F. Mak, C. Lee, J. Hone, J. Shan, T.F. Heinz, Atomically thin MoS2: a new direct-
gap semiconductor, Phys. Rev. Lett. 105 (13) (2010) 136805 .
[8] I.G. Lezama, A. Arora, A. Ubaldini, C. Barreteau, E. Giannini, M. Potemski,
A.F. Morpurgo, Indirect-to-direct band gap crossover in few-layer MoTe2, Nano
Lett. 15 (4) (2015) 2336–2342.
[9] Y. Sun, D. Wang, Z. Shuai, Indirect-to-direct band gap crossover in few-layer
transition metal dichalcogenides: a theoretical prediction, J. Phys. Chem. C. 120
(38) (2016) 21866–21870.
[10] T. Cao, G. Wang, W. Han, H. Ye, C. Zhu, J. Shi, Q. Niu, P. Tan, E. Wang, B. Liu, et al.,
Valley-selective circular dichroism of monolayer molybdenum disulphide, Nat.
Commun. 3 (2012) 887.
[11] K.F. Mak, K. He, C. Lee, G.H. Lee, J. Hone, T.F. Heinz, J. Shan, Tightly bound trions
in monolayer MoS2, Nature Mater. 12 (3) (2013) 207.
[12] S. Lebegue, O. Eriksson, Electronic structure of two-dimensional crystals from ab
initio theory, Phys. Rev. B. 79 (11) (2009) 115409 .
[13] S.-D. Guo, Y. Wang, Small compressive strain-induced semiconductor-metal tran-
sition and tensile strain-enhanced thermoelectric properties in monolayer PtTe2,
Semicond. Sci. Tech. 32 (5) (2017) 055004 .
[14] X. Chen, G. Wang, Tuning the hydrogen evolution activity of MS2 (M= Mo or Nb)
monolayers by strain engineering, Phys. Chem. Chem. Phys. 18 (14) (2016)
9388–9395.
[15] Q. Yue, J. Kang, Z. Shao, X. Zhang, S. Chang, G. Wang, S. Qin, J. Li, Mechanical and
electronic properties of monolayer MoS2 under elastic strain, Phys. Lett. A. 376
(12–13) (2012) 1166–1170.
[16] E. Scalise, M. Houssa, G. Pourtois, V. Afanas’ev, A. Stesmans, Strain-induced
semiconductor to metal transition in the two-dimensional honeycomb structure of
MoS2, Nano Res. 5 (1) (2012) 43–48.
[17] J. Liu, H. Liu, J. Wang, H. Sheng, G. Tang, J. Zhang, D. Bai, Optical and electronic
properties of dichalcogenides WX2 (X= S, Se, and Te) monolayers under biaxial
strain, Physica B: Condensed Matter. 568 (2019) 18–24.
[18] M. Feierabend, A. Morlet, G. Berghäuser, E. Malic, Impact of strain on the optical
fingerprint of monolayer transition-metal dichalcogenides, Phys. Rev. B. 96 (4)
(2017) 045425 .
[19] J. Lee, J. Huang, B. G. Sumpter, M. Yoon, Strain-engineered optoelectronic prop-
erties of 2D transition metal dichalcogenide lateral heterostructures, 2D Mater. 4
(2), 2017, 021016.
[20] M. Farkous, M. Bikerouin, D.V. Thuan, Y. Benhouria, M. El-Yadri, E. Feddi,
H. Erguig, F. Dujardin, C.V. Nguyen, N.V. Hieu, et al., Strain effects on the elec-
tronic and optical properties of van der Waals Heterostructure MoS2/WS2: A first-
principles study, Physica E: Low-Dimens. Syst. Nanostruct. 116 (2020) 113799 .
[21] A.-Y. Lu, H. Zhu, J. Xiao, C.-P. Chuu, Y. Han, M.-H. Chiu, C.-C. Cheng, C.-W. Yang,
K.-H. Wei, Y. Yang, et al., Janus monolayers of transition metal dichalcogenides,
Nat. Nanotechnol 12 (8) (2017) 744.
[22] J. Zhang, S. Jia, I. Kholmanov, L. Dong, D. Er, W. Chen, H. Guo, Z. Jin, V.B. Shenoy,
L. Shi, et al., Janus monolayer transition-metal dichalcogenides, ACS Nano 11 (8)
(2017) 8192–8198.
[23] F. Li, W. Wei, P. Zhao, B. Huang, Y. Dai, Electronic and optical properties of pristine
and vertical and lateral heterostructures of Janus MoSSe and WSSe, J. Phys. Chem.
Lett. 8 (23) (2017) 5959–5965.
[24] W. Zhou, J. Chen, Z. Yang, J. Liu, F. Ouyang, Geometry and electronic structure of
monolayer, bilayer, and multilayer Janus WSSe, Phys. Rev. B 99 (2019) 075160 .
[25] C. Xia, W. Xiong, J. Du, T. Wang, Y. Peng, J. Li, Universality of electronic char-
acteristics and photocatalyst applications in the two-dimensional Janus transition
V.V. Thanh, et al.
metal dichalcogenides, Phys. Rev. B 98 (2018) 165424 .
[26] J. Wang, H. Shu, T. Zhao, P. Liang, N. Wang, D. Cao, X. Chen, Intriguing electronic
and optical properties of two-dimensional Janus transition metal dichalcogenides,
Phys. Chem. Chem. Phys. 20 (27) (2018) 18571–18578.
[27] S.-D. Guo, J. Dong, Biaxial strain tuned electronic structures and power factor in
Janus transition metal dichalchogenide monolayers, Semicond. Sci. Tech. 33 (8)
(2018) 085003 .
[28] L. Dong, J. Lou, V.B. Shenoy, Large in-plane and vertical piezoelectricity in Janus
transition metal dichalcogenides, ACS Nano 11 (8) (2017) 8242–8248.
[29] Y. Ji, M. Yang, H. Lin, T. Hou, L. Wang, Y. Li, S.-T. Lee, Janus structures of transition
metal dichalcogenides as the heterojunction photocatalysts for water splitting, J.
Phys. Chem. C 122 (5) (2018) 3123–3129.
[30] K.D. Pham, N.N. Hieu, H.V. Phuc, B.D. Hoi, V.V. Ilysov, B. Amin, C.V. Nguyen, First
principles study of the electronic properties and schottky barrier in vertically
stacked graphene on the Janus MoSeS under electric field, Comput. Mater. Sci. 153
(2018) 438–444.
[31] X. Li, X. Wang, W. Hao, C. Mi, H. Zhou, Structural, electronic, and electro-
mechanical properties of MoSSe/blue phosphorene heterobilayer, AIP Adv. 9 (11)
(2019) 115302 .
[32] X. Zhao, B. Qiu, G. Hu, W. Yue, J. Ren, X. Yuan, Transition-metal doping/adsorption
induced valley polarization in Janus WSSe: First-principles calculations, Appl. Surf.
Sci. 490 (2019) 172–177.
[33] L. Yu, S. Sun, X. Ye, Electronic and magnetic properties of janus MoSSe/WSSe su-
perlattice nanoribbon: A first-principles study, Phys. Chem. Chem. Phys. 22 (2020)
2498–2508.
[34] P. Giannozzi, S. Baroni, N. Bonini, M. Calandra, R. Car, C. Cavazzoni, D. Ceresoli,
G.L. Chiarotti, M. Cococcioni, I. Dabo, et al., Quantum espresso: a modular and
open-source software project for quantum simulations of materials, J. Phys.
Condens. Matter. 21 (39) (2009) 395502 .
[35] H.J. Monkhorst, J.D. Pack, Special points for Brillouin-zone integrations, Phys. Rev.
B 13 (12) (1976) 5188.
[36] C. Hartwigsen, S. Gœdecker, J. Hutter, Relativistic separable dual-space Gaussian
pseudopotentials from H to Rn, Phys. Rev. B 58 (1998) 3641.
[37] J.P. Perdew, K. Burke, M. Ernzerhof, Generalized gradient approximation made
simple, Phys. Rev. Lett. 77 (18) (1996) 3865.
[38] J. Heyd, G.E. Scuseria, M. Ernzerhof, Hybrid functionals based on a screened
Coulomb potential, J. Chem. Phys. 118 (18) (2003) 8207.
[39] R.C. Cooper, C. Lee, C.A. Marianetti, X. Wei, J. Hone, J.W. Kysar, Nonlinear elastic
behavior of two-dimensional molybdenum disulfide, Phys. Rev. B 87 (3) (2013)
035423 .
[40] C.-H. Chang, X. Fan, S.-H. Lin, J.-L. Kuo, Orbital analysis of electronic structure and
phonon dispersion in mos 2, MoSe2, WS2, and WSe2 monolayers under strain, Phys.
Rev. B 88 (2013) 195420 .
[41] C.G. Broyden, The convergence of a class of double-rank minimization algorithms:
2. the new algorithm, IMA J. Appl. Math. 6 (3) (1970) 222–231.
[42] R. Fletcher, A new approach to variable metric algorithms, Comput. J. 13 (3) (1970)
317–322.
[43] D. Goldfarb, A family of variable-metric methods derived by variational means,
Math. Comput. 24 (109) (1970) 23–26.
[44] D.F. Shanno, Conditioning of quasi-newton methods for function minimization,
Math. Comput. 24 (111) (1970) 647–656.
Applied Surface Science 526 (2020) 146730
[45] A. Dal Corso, Elastic constants of beryllium: a first-principles investigation, J. Phys:
Condens. Matter 28 (7) (2016) 075401 .
[46] Q. Peng, W. Ji, S. De, Mechanical properties of the hexagonal boron nitride
monolayer: Ab initio study, Comput. Mater. Sci. 56 (2012) 11–17.
[47] N.T. Hung, A.R. Nugraha, R. Saito, Two-dimensional MoS2 electromechanical ac-
tuators, J. Phys. D: Appl. Phys. 51 (7) (2018) 075306 .
[48] V. Van Thanh, N.T. Hung, et al., Charge-induced electromechanical actuation of
Mo-and W-dichalcogenide monolayers, RSC adv. 8 (67) (2018) 38667–38672.
[49] V. Van Thanh, N.T. Hung, et al., Charge-induced electromechanical actuation of
two-dimensional hexagonal and pentagonal materials, Phys. Chem. Chem. Phys. 21
(40) (2019) 22377–22384.
[50] X. Li, J. Zhao, J. Yang, Semihydrogenated bn sheet: a promising visible-light driven
photocatalyst for water splitting, Sci. Rep. 3 (2013) 1858.
[51] S.-D. Guo, Phonon transport in janus monolayer mosse: a first-principles study,
Phys. Chem. Chem. Phys. 20 (10) (2018) 7236–7242.
[52] S. Deng, L. Li, O.J. Guy, Y. Zhang, Enhanced thermoelectric performance of
monolayer MoSSe, bilayer MoSSe and graphene/MoSSe heterogeneous nanor-
ibbons, Phys. Chem. Chem. Phys. 21 (33) (2019) 18161–18169.
[53] Y. Cheng, Z. Zhu, M. Tahir, U. Schwingenschlögl, Spin-orbit-induced spin splittings
in polar transition metal dichalcogenide monolayers, EPL (Europhysics Letters) 102
(5), 2013, 57001.
[54] R.A. Cowley, Acoustic phonon instabilities and structural phase transitions, Phys.
Rev. B 13 (1976) 4877.
[55] F. Mouhat, F. Coudert, Necessary and sufficient elastic stability conditions in var-
ious crystal systems, Phys. Rev. B 90 (2014) 224104 .
[56] T. Li, Reply to ”Comment on “ideal strength and phonon instability in single-layer
MoS2”’, Phys. Rev. B 90 (2014) 167402 .
[57] R.C. Cooper, J.W. Kysar, C.A. Marianetti, Comment on ”ideal strength and phonon
instability in single-layer MoS2”, Phys. Rev. B 90 (2014) 167401 .
[58] S. Bertolazzi, J. Brivio, A. Kis, Stretching and breaking of ultrathin MoS2, ACS nano
5 (12) (2011) 9703–9709.
[59] T. Li, Ideal strength and phonon instability in single-layer MoS2, Phys. Rev. B. 85
(23) (2012) 235407 .
[60] L. Pauling, The Nature of the Chemical Bond vol. 260, Cornell University Press
Ithaca, NY, 1960.
[61] S.P. Hind, P.M. Lee, Kkr calculations of the energy bands in NbSe2, MoS2 and alpha
MoTe2, J. Phys. C: Solid State Phys. 13 (1980) 349.
[62] N. T. Hung, L. Yin, P. D. Tran, R. Saito, Simultaneous anionic and cationic redox in
Mo3S11 polymer electrode of sodium-ion battery, J. Phys. Chem. C. 123 (51), 2019,
30856-30862.
[63] H. Liu, Z. Huang, C. He, Y. Wu, L. Xue, C. Tang, X. Qi, J. Zhong, Strain engineering
the structures and electronic properties of Janus monolayer transition-metal di-
chalcogenides, J. Appl. Phys. 125 (2019) 082516 .
[65] M.R. Kim, D. Ma, Quantum-dot-based solar cells: recent advances, strategies, and
challenges, J. Phys. Chem. Lett. 6 (1) (2014) 85–99.
[66] M. Bernardi, M. Palummo, J.C. Grossman, Extraordinary sunlight absorption and
one nanometer thick photovoltaics using two-dimensional monolayer materials,
Nano Lett. 13 (2013) 3664–3670.
[67] C. Kittel, Introduction to solid state physics, Wiley, New York, 1976.
[68] D. Brust, J.C. Phillips, F. Bassani, Critical points and ultraviolet reflectivity of
semiconductors, Phys. Rev. Lett. 9 (1962) 94.