Research Article
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Dramatically Enhanced Second Harmonic Generation in
Janus Group-III Chalcogenide Monolayers
Shi-Qi LI, Chuan He, Hongsheng Liu, Luneng Zhao, Xinlong Xu,* Maodu Chen, Lu Wang,
Jijun Zhao, and Junfeng Gao*
2D materials are excellent platforms for nonlinear optical (NLO) response,
especially second harmonic generation (SHG), due to its large surface to
volume ratio and sub-nanometer thickness. The SHG susceptibility strongly
relies on the symmetry of materials. Constructing Janus structures can break
the out-of-plane mirror symmetry, bringing about asymmetric charge distribu-
tion and leading to a built-in electric field. Consequently, SHG response along
the out-of-plane direction can be improved. In the current work, combining
first-principles calculations with independent particle approximation, the
SHG response of nine Janus group-III chalcogenide monolayers (M2XX’,
MM’X2) are systematically evaluated. Both extraordinary in-plane and out-of-
plane SHG response are revealed in all the Janus structures. Besides, cation
MM'X2 Janus structures exhibit systemically higher SHG response than that
of anion M2XX’ due to stronger dipole. Among them, GaInTe2 possesses
extremely high out-of-plane SHG response with d31 up to 10490.4 pm V−1 at
photon energy (PE) of 4.7 eV, enabling promising applications in ultraviolet
NLO devices. The SHG intensity polar plots from Janus structures display
unusual rotational symmetry at different PEs allowed by the out-of-plane SHG
components. This work provides theoretical guidelines for further experi-
mental explorations in 2D group-III monochalcogenide Janus structures and
paves the way for their utilization in NLO devices.
S.-Q. LI, H. Liu, L. Zhao, M. Chen, J. Zhao, J. Gao
Key Laboratory of Materials Modification by Laser
Ion and Electron Beams (Dalian University of Technology)
Ministry of Education
School of Physics
Dalian 116024, China
E-mail: gaojf@dlut.edu.cn
C. He, X. Xu
Shaanxi Joint Lab of Graphene
International Collaborative Center on Photoelectric Technology
and Nano Functional Materials
Institute of Photonics & Photon-Technology
Northwest University
Xi’an 710069, China
E-mail: xlxuphy@nwu.edu.cn
L. Wang
Institute of Functional Nano & Soft Materials (FUNSOM)
Jiangsu Key Laboratory for Carbon-Based Functional Materials & Devices
Soochow University
Suzhou, Jiangsu 215123, China
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adom.202200076.
DOI: 10.1002/adom.202200076
Adv. Optical Mater. 2022, 10, 2200076 2200076 (1 of 8)
1. Introduction
Nonlinear optical (NLO) phenomena
under intense optical excitation plays an
important role in photonic applications
including ultrafast lasers,[1] frequency con-
version, modulators,[2] switches, and so
forth.[3,4] 2D NLO materials have attracted
high interest because of their peculiar
properties such as nontrivial second-order
nonlinear susceptibility,[5–9] broadband
optical response,[10,11] strong excitonic
effects,[12] low-cost top-down fabrication,
integration technologies, etc. Being a rep-
resentative family in 2D materials, group-
III monochalcogenides (MX, M = Ga, In;
X = S, Se, Te) have been widely investigated.
They exhibit high carrier mobility,[13–15]
high photoresponsivity,[13,16,17] and good
environmental stability,[18] which allow
extensive applications in transistors,[15,17,19]
nanoelectronics, and optoelectronics with
good mechanical flexibility.
As one of the leading NLO responses,
second harmonic generation (SHG) is
widely studied and applied in various
electronic, optoelectronic, and detecting
devices. Unfortunately, the SHG strongly depends on the spa-
tial symmetry of the crystal,[20] i.e., it only exists in noncen-
trosymmetric structures. In addition, phase-matching condi-
tion needs to be satisfied that enhances the SHG responses as
light propagates in the bulk. Compared with conventional 3D
bulk systems, it has to be noted that 2D layers can be advanta-
geous for SHG. First, 2D systems can be precisely controlled
by layer modification that would greatly reduce the defect
level.[21–23] Second, the atomic thickness of 2D layers automati-
cally guarantees phase matching,[24] hence the SHG signal is
usually strong enough for observation and utilization. Strong
SHG responses from various 2D monolayers have been dem-
onstrated, including MoS2,[25,26] WS2,[27] GaSe,[8] and h-BN.[28]
However, these materials possessing out-of-plane mirror sym-
metry (or glide symmetry) that hinders the out-of-plane compo-
nents of SHG matrix symmetrically. For example, there are only
three equivalent in-plane second-order nonlinear coefficients in
MoS2[6] and h-BN with odd layer number as they belong to D3h1
symmetry with mirror symmetry.[28] If one can break the out-of-
plane symmetry, there will be more space for SHG component
tunability and utility. To date, out-of-plane SHG response has
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been detected in some nanosheets with spontaneous vertical
electric dipole like α-In2Se3[29] and penta-ZnS2.[30]
Constructing Janus monolayers by breaking the out-of-
plane inversion and mirror symmetry, is one efficient way to
generate the out-of-plane NLO response.[31,32] Inspiringly, the
Janus structure MoSSe was experimentally realized by Lu and
Zhang independently through controlled selenization of MoS2
or sulfurization of monolayer MoSe2 in a typical chemical
vapor deposition setup.[33,34] Another Janus compound, PtSSe
was also synthesized and exhibited strong Rashba spin–orbit
coupling.[35] During the fabrication and production, out-of-
plane SHG susceptibility spectra enable ultrafast, simple, and
noninvasive characterization of their vertical polarization, lat-
tice symmetry, layer number, chemical bonding, and stacking
sequence. Many promising properties[28–34] have been reported
in these Janus monolayers, such as topological spin texture,[36]
enhanced out-of-plane piezoelectric polarizations,[37] asymmet-
rically flexoelectric gating effect,[38] etc. As we mentioned above,
Janus monolayers are expected to enhance the NLO response,
however, the related studies on Janus group-III monochalcoge-
nide (MX) monolayers are still rare.
In this paper, choosing MXs as sample, nine Janus struc-
tures are designed with out-of-plane mirror symmetry removed
in order to gain stronger and broadband SHG response. Based
on first-principles calculations combined with independent par-
ticle approximation, the SHG response from the pristine MX
monolayers and their Janus structures are evaluated. We indi-
cate that GaInTe2 exhibit exceptionally strong SHG response,
with its out-of-plane second nonlinear coefficients as high as
10 490.4 pm V−1 at PE of 4.7 eV. Beyond, different from pristine
MXs, SHG intensity polar plots for these Janus structures as a
function of crystal orientation can exhibit threefold, sixfold, or
even onefold rotational symmetry at different photon energies
due to the out-of-plane elements.
2. Results and Discussion
2.1. The Structures and Charge Redistribution of Janus
Derivatives of MX Monolayers
As shown in Figure 1a, pristine monolayer MX have a hex-
agonal structure with two vertically bonded metal–atom layers
sandwiched between two chalcogen-atom layers. When the
chalcogen atoms in top layer are replaced by different chal-
cogen atoms, anion Janus monolayers of M2XX’ (M = Ga, In; X,
X’ = S, Se, Te) are constructed (Figure 1b). Whereas the cation
Janus MM’X2 (M, M’ = Ga, In; X = S, Se, Te) can be formed
via substituting one layer of metal atoms by another type of
metal atoms (Figure 1c). These monolayers are thermodynami-
cally and dynamically stable indicated by formation energy and
phonon dispersion calculations.[47] Clearly, atom substitution
leads to structural differences between the upper and bottom
metal-chalcogen-atom layer, resulting in the breaking of mirror
symmetry. The height of the upper and bottom metal–chal-
cogen–atom layer of these structures are denoted as h1 and h2
(Figure 1c), respectively. They can be calculated by the differ-
ence of Cartesian coordinates Z of corresponding atoms. h1
and h2 are the same in pristine MX (Figure 1a, Figure S1a–f,
Supporting Information), while in Janus structures, they are
distinctively different (Figure 1b-c, Figure S1g-o, Supporting
Information). For example, h1 = h2 = 1.28 Å in GaTe, while in
GaInTe2, h1 (1.23 Å) < h2 (1.45 Å). The details for the changes of
h1 and h2 are listed in Table S1 (Supporting Information).
The structural deformations certainly result in the related
charge redistributions, which is clearly demonstrated in differ-
ential charge density in Figure 1d–f, where the cyan/pink sec-
tions represent the electron accumulation/depletion. Referring
the isolating atoms, charge transfers after bonding mainly occur
in the upper and bottom metal-chalcogen-bond (Te-Ga, Se-Ga,

Figure 1. Atomic structures of a) pristine MX monolayers, b) M2XX’, and c) MM’X2, respectively. The M, M”, X, and X’ atoms are represented by light
blue, dark green, yellow, and orange balls, respectively. Bonding differential charge density of d) GaTe, e) Ga2SeTe, and f) GaInTe2. The cyan and pink
zones represent the electron accumulation and depletion regions, respectively. Isosurface is 0.005 |e| bohr−3. 2D plots of bonding charge density dif-
ference and planar-averaged electron density difference Δρ(Z) for g) GaTe, h) Ga2SeTe, and i) GaInTe2.

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Te-In) layers (Figure 1d–f, Figure S1, Supporting Information).
For all pristine MXs (Figure S1a–f, Supporting Information),
such as GaTe (Figure 1g), the charge transfer for the upper
and bottom layer is the same with image symmetry. However,
for both anion M2XX’ and cation MM’X2 Janus structures, the
replaced atoms introduce structural asymmetry, resulting in
the charge redistribution, and the center of charge is off the
center of the geometry. Therefore, a robust dipole between the
upper and bottom metal-chalcogen-atom layers is generated
(Figure S1g-o, Supporting Information). For anion M2XX’ Janus,
we use Ga2SeTe as a sample, the amount of charge depletion in
the upper Te-Ga layer is larger than that in the bottom layer
(Figure 1e,h). The same situation is revealed in cation MM’X2
Janus, such as GaInTe2, whereas the difference between the
two layers becomes even larger (Figure 1f,i). Planar-averaged
electron density difference Δρ(Z) and related total charge
amount ΔQ (of Ga2SeTe (Figure 1h) and GaInTe2 (Figure 1i)
further indicate asymmetry charge distribution between upper
and lower part, different from the symmetric charge distribu-
tion of initial MXs (Figure 1g). Such an array of permanent
dipoles can introduce built-in electric field, which certainly
affects the electronic and nonlinear optical properties.[31,32,48]
2.2. SHG Response From Anion Janus Structure
We then calculated the band structures of all the MXs, anion Janus
M2XX’, and cation Janus MM’X2 based on HSE06 (Figure S2,
Supporting Information) to obtain more accurate SHG
Figure 2. Photon energy-dependent nonvanishing second-order nonlinear coefficients in a) GaSe, b) GaTe, and c,d) Ga2SeTe. e) Band structure of
Ga2SeTe at the HSE06 level. f,g) The partial charge densities of the corresponding bands labeled in (e) with an isosurface value of 0.007 |e| bohr−3.
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response. The bandgaps (Eg) acquired by HSE06 (E HSE g
06
), PBE
PBE
(E g ), and the scissor correction values (ΔEg) are listed in
Table S1 (Supporting Information). The second-order nonlinear
coefficients as a function of photon energy of monolayer GaSe
and GaTe are depicted in Figure 2a,b. Obviously, only three ele-
ments are nonzero with the relationship: d16 = d21 = −d22, indi-
cating the crystal symmetry of them belonging to D3h1 space
group without an inversion center.[8,49,50] This is in good agree-
ment with previous reports.[51]
We first explored the second nonlinear coefficient in anion
Janus M2XX’. Taking Ga2SeTe as an example, intriguingly,
except for the in-plane d16, d21, and d22 (Figure 2c), five addi-
tional out-of-plane elements d15, d24, d31, d32, and d33 (Figure 2d)
appear were allowed by the breaking of mirror symmetry. This
feature is also reflected by its space group C3v1. Meanwhile,
these elements satisfy the relationship: d16 = d21 = −d22, d15 = d24,
and d31 = d32.
The in-plane nonlinear response of Ga2SeTe is different from
that of GaSe and GaTe, although they are at the same amplitude
(103). In the visible region (1.63–2.47 eV), there is an enhance-
ment in d22 spectra compared with that of GaSe (Figure 2a). But
the d22 element of Ga2SeTe is smaller than that of GaTe, indi-
cating this enhancement comes from Te. Another increase hap-
pens within a narrow ultraviolet region (3.52–3.6 eV). Mean-
while, the magnitude of d22 in Ga2SeTe is the same as that in
GaSe within this region. Clearly, this enhancement originates
from Se. Generally speaking, the in-plane elements in Ga2SeTe
integrate the superiority of GaTe in visible region and GaSe in
ultraviolet region.
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The out-of-plane nonlinear optical response in Ga2SeTe is
much more extraordinary than that of in-of-plane. Among the
five out-of-plane second-order nonlinear coefficients, the scale
of d33 is the largest. The value of d15 and d31 are both at the
magnitude of 102 pm V−1. The maximum values in d15, d31, and
d33 follow the sequence max(d33) (1691.47 pm V−1) > max(d15)
(387.35 pm V−1) > max(d31) (321.21 pm V−1). And these maxi-
mums locate at 3.84, 2.02, and 3.84 eV, respectively.
There are several prominent peaks in the out-of-plane
SHG spectra which are labeled as I (2.02 eV in d15 spectra), II
(2.98 eV in d33 spectra), and III (3.84 eV in d33 spectra). These
peaks result from the van Hove singularity in joint density of
states at the high-symmetry point or along the high-symmetry
paths. The inter-band contributions for these peaks are explored
on the basis of the underlying band structure as shown in
Figure 2e. Two photons transition between the highest valence
band and the lowest conduction band along M to K results in
peak I. Two transition processes between the highest valence
band and the lowest conduction band along K to Г and Г to
M both make contribution to peak II as Figure 2e shows. Peak
III comes from transition with two photons from the highest
valence band to fifth conduction band along the high-symmetry
line (M to K).
The partial charge for the start point and endpoint in the
band structure of these transitions are also plotted. Take peak
III as an example, charge distributes unequally near the upper
Se and down Te atom layer at the start point (Figure 2f). After
transition, most of the charge transfer to Ga atoms, only a
small part resides at Se and Te atoms (Figure 2g). The partial
charges for other transitions have also been plotted in Figure S3
(Supporting Information). Clearly, the charge distributions are
all asymmetric. On the contrary, the charge distributes sym-
metrically for the transitions of the prominent peaks in pristine
GaSe (Figure S4, Supporting Information) and GaTe (Figure S5,
Supporting Information), which indicates that the out-of-plane
elements come from the transition between the charge asym-
metric bands. Besides, the charge density distribution changes
significantly after the transition, which leads to a large transi-
tion dipole moment and dipole moment difference between
the ground state and the crucial excited states along the out-of-
plane direction.
2.3. SHG Response from Cation Janus Structures
Similar with anion Ga2SeTe, the SHG spectra of cation Janus
GaInTe2 reveals the similar C3v1 space group with eight nonzero
second nonlinear coefficients including three in-plane compo-
nents: d16 = d21 = -d22 and five additional out-of-plane compo-
nents: d15 = d24, d31 = d32, d33. And the value of d22 of GaInTe2
is also at the same magnitude as that of its pristine GaTe and
InTe. Intriguingly, different from Ga2SeTe, in-plane SHG
response from GaInTe2 is strengthened within a wider energy
range including visible (2.3–2.79 eV) and ultraviolet (3.13–
3.24 eV, 4.14–5 eV) region compared with that of both GaTe and
InTe. On the one hand, the upper limit of nonlinearity is pro-
portional to E g−4 , 2D materials with smaller gaps tend to pos-
sess larger second nonlinear coefficients.[52] The bandgap of
GaInTe2 (1.87 eV) is smaller than that of GaTe (2.1 eV) and InTe
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(2.01 eV; Table S1, Supporting Information). On the other hand,
the built-in electric field makes the carrier near-visible and
ultraviolet bands more easily to be excited, leading to a stronger
SHG response.
Excitingly, the maximum values in out-of-plane d33 spectra
is drastically increased to 10 490.41 pm V−1 (Figure 3d), which
is 10–100 times higher than those of others. Other out-of-plane
SHG response is also significantly stronger than that of anion
Ga2SeTe. This can be explained by the vertical intrinsic polari-
zation induced by structural asymmetric. The vertical distance
of In-Ga is smaller than that of Se-Te, thus GaInTe2 possesses
a shorter dipole distance, resulting in stronger dipole moment
and built-in electric field. The bonding differential charge densi-
ties also verify this tendency (Figure 1). As shown in Figure 3d,
the d31 is the largest component with the value > 4000 pm V−1
in a wide energy range. In the overall energy range we consider,
the value of d31 is larger than those of the in-plane components.
There are many peaks in the ultraviolet region in d31 spectra, the
d31 value can reach 6772.65 pm V−1 at 3.23 eV, 7790.11 pm V−1 at
4.84 eV, and 10 490.41 pm V−1 at 4.74 eV. Beyond d31, d33 element
also surpasses the in-plane d22 in a wide energy range [(2.94–
3.38 eV), (3.6–4.16 eV)]. The sequence of the maximum values
in d15, d31, and d33 spectra switch to max(d31) (10 490.41 pm V−1) >
max(d33) (4887.03 pm V−1) > max(d15) (697.05 pm V−1). The ratio
between these maximums with their corresponding d22 can
reach 99.6, 6, and 0.25.
The origin of the three highest peak, including peak I at
2.14 eV, peak II at 3.23 eV, and peak III at 4.74 eV (Figure 3d),
is investigated based on the band structures (Figure 3e). These
peaks result from the Van Hove singularity in joint density of
states at the high-symmetry point or along the high symmetry
paths. Two photons transition between the highest valence
band and the second conduction band along K to Г results in
peak I. Two transition processes between the highest valence
band and the 4th conduction band along M to K make contribu-
tion to peak II. Peak III comes from transition with two pho-
tons from the highest valence band to higher conduction band
along the high-symmetry line (M to K).
The charge distributions of these transitions are also
depicted in Figure 3f,g and Figure S6 (Supporting Informa-
tion). At start point of transition III, charge distributes on both
upper Ga-Te and down In-Te layers. After transition, charge
mainly distributes on the upper Ga-Te layer. Similarly with
Ga2SeTe, the charge distributions are significantly asymmetric,
while the partial charge for inter-band transitions contributing
to the prominent peaks in pristine GaTe (Figure S5, Supporting
Information) and InTe (Figure S7, Supporting Information) are
all symmetric. Therefore, the out-of-plane elements come from
the transition between the charge asymmetric bands.
2.4. Comparison SHG Response between Cation MM’X2
and Anion M2XX’ Janus Structures
Except for Ga2SeTe and GaInTe2, SHG response from other
anion M2XX’ (Ga2SSe, Ga2STe, In2SSe, In2STe, and In2SeTe)
and cation MM’X2 (GaInS2 and GaInSe2) are all carefully
explored, comparing with related pristine MX (GaS, InS, and
InSe) (see Figure S8 and S9, Supporting Information). All the
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Figure 3. Photon energy-dependent nonvanishing second-order nonlinear coefficients in a) GaTe, b) InTe, and c,d) GaInTe2. e) Band structure of
GaInTe2 at the HSE06 level. f,g) The partial charge densities of the corresponding bands labeled in (e) with an isosurface value of 0.007 |e| bohr−3.

locations of prominent peaks and their corresponding values
of in-plane elements d22, out-of-plane elements d15, d31, and d33
in MXs, Janus M2XX’, and MM’X2 are provided in Tables S2
and S3 (Supporting Information). Because of the space group
of D3h1, the second nonlinear coefficients of all the MXs exhibit
three nonzero elements with the relationship: d16 = d21 = -d22.
Other elements are very small and can be ignored (Figure S10,
Supporting Information).
Just the same as Ga2SeTe and GaInTe2, the elements in the
second nonlinear coefficients for other Janus structures also
satisfy the relationship:d16 = d21 = −d22, d15 = d24, d31 = d32. SHG
spectra for the remaining components (Figure S10, Supporting
Information) indicate they should be neglected. Therefore, the
second-order nonlinear coefficients of Janus structures could
In2SeTe is larger than that of InSe within visible region [(1.42 –
2.25 eV) and is larger than that of InTe within ultraviolet region
[(3.2–3.7 eV)]. As for MM’X2, except for GaInTe2 mentioned
above, there is nearly no apparent enhancement in in-plane
SHG spectra compared with pristine MXs.
For out-of-plane coefficients, the SHG response of cation
MM’X2 is systemically higher than anion M2XX’ Janus struc-
ture. This is because cation Janus have shorter dipole dis-
tance than anion (See figure 1e,f). The maximum values of
out-of-plane d15, d31, d33 and the ratio between them with the
corresponding in-plane in every Janus structure are plotted in
Figure 4a,b, respectively. The maximum values in all the Janus
structure satisfy: max(d31GaInTe2
) (10 490.41 pm V−1) > max(d33 In2STe
)
−1
(2582.03 pm V ) > max(d15 ) (1980.41 pm V ) > max(d33 )
In2SeTe −1 Ga2SeTe

be expressed as: (1691.47 pm V−1) > max(d33 GaInSe2

) (1362.49 pm V−1) > max(d33 Ga2SSe
)
−1
(1333.93 pm V ) > max(d33 ) (1072.46 pm V ) > max(d33
In2SSe −1 GaInS2
)
 0 0 0 0 d15 − d22  (961.19 pm V−1) > max(d31 Ga2STe
) (837.46 pm V−1). As shown in
dJanus =  − d22 d22 0 d15 0 0  (1) Figure 4b, the ratio between these maximums with the cor-
  responding d22 can vary from 1.44 (d31 Ga2STe Ga2STe
/ d22 ) to 99.6
 d31 d31 d33 0 0 0  GaInTe2 GaInTe2
(d31 / d22 ).
As shown in Figures S8 and S9 (Supporting Information), In most of M2XX’, the out-of-plane elements follow: d33 >
the in-plane elements of all the Janus structures are nearly at d15 > d31. The sequence switches to d15 > d33 > d31 and d31 >
the same magnitude with those of pristine MXs (103 pm V−1). d15 > d33 in In2SeTe and Ga2STe, respectively. As for MM’X2,
Similar to Ga2SeTe, enhancement is also found in in-plane in GaInS2 and GaInSe2, the out-of-plane elements follow:
SHG spectra for other anion Janus M2XX’ within visible and d33 > d31 > d15. In these two Janus structures, the d31 and d15
ultraviolet region. For example, d22 of In2STe is larger than that are very small. The maximum value of d15 in GaInS2 is only
of InS within visible region [(1.35–2.17 eV), (2.26–2.51 eV)], 3.75 pm V−1. However, the d33 in these two structures are both
due to the Te atom. d22 of In2STe is also larger than the d22 of at the same magnitude as the in-plane d22. Therefore, d33/d22
InS and InSe in the ultraviolet region [(3.29–3.47 eV)]. d22 of can be 6.29 and 2.28 in GaInS2 and GaInSe2, respectively.

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Figure 4. The largest value of a) out-of-plane second nonlinear coeffi-
cients and b) their ratio between the corresponding in-plane elements d22
for all the nine Janus structures.
Differently, in GaInTe2, d31 > d33 > d15. Especially, the maximum
value of d33 and d31 in GaInTe2 can be up to 10 490.41 and
4887.03 pm V−1 that are larger than the maximum out-of-plane
d33 (2582.03 pm V−1) of In2STe in M2XX’.
Superior to intrinsic atomic thickness nature of 2D mate-
rials, all the in-plane second-order coefficients of pristine MXs,
Janus M2XX’ and MM’X2 are larger than those of traditional
typical nonlinear crystals, such as LiNbO3[53] and GaAs,[54] by
two to four orders of magnitudes.
Clearly, extraordinary out-of-plane SHG response is revealed
in all the Janus structures with the out-of-plane second coef-
ficients significantly larger than those of typical out-of-plane
NLO materials including penta-ZnS2[30] and MoSSe.[31] Beyond,
the d31 of GaInTe2 within the ultraviolet region is several orders
of magnitudes larger than that of the commercial NLO crystal
[such as β-BaB2O4 (β-BBO),[55,56] LiB3O5 (LBO),[57–59] KBe2BO3F2
(KBBF)][60,61]]. GaInTe2 can be potential ultraviolet candidates
for nonlinear optical device.
2.5. Polar Plot of SHG Intensity of Anion M2XX’ and Cation
MM’X2 Janus Structures
The extraordinary out-of-plane SHG generation from Janus
M2XX’ and MM’X2 monolayers entitle us to obtain the structural
information on them including vertical polarization, crystallo-
graphic axes orientation, and rotational symmetry. By shedding
linearly polarized laser beams onto these materials, different
polarization components of the outgoing SHG response can be
measured. Here, we consider incident geometry with linearly
polarized pump light of an incident angle θ for these fifteen 2D
materials (Figure S11, Supporting Information).
With the calculated nonzero second nonlinear coefficients of
pristine MXs and their relationship (d16 = d21 = d22), the incident
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angle dependent SHG polarization components as a function
of crystal’s azimuthal angle can be further denoted as (details in
the Supporting Information S15):
I // = d22
2
× sin 2 (3φ )cos4 (θ ) (2)
I ⊥ = d22
2
× cos2 (3φ )cos4 (θ ) (3)

I Janus (
∝ − (2sin [θ ] cos [θ ] d15 − cos2 [θ ] sin [3φ ] d22 ) cos [θ ]
(4)
+ (cos2 [θ ] d31 + sin 2 [θ ] d33 ) sin [θ ] )
2
⊥
I Janus ∝ cos2 (3φ )cos4 (θ )d22
2
(5)
Because of the identical crystalline structure of MXs, all the polar
plots of them are the same (Figure S12, Supporting Information).
The parallel and perpendicular components of SHG intensity from
pristine MXs are only related to the in-plane d22. When the incident
angle θ is at 45°, the polarization SHG components exhibit sixfold
rotational symmetry (Figure S12, Supporting Information), which
is in good accordance with the preceding experimental reports.[7,28]
Evidently, due to the spontaneous vertical polarization, the
parallel components of SHG intensity from Janus structures

(I Janus ) depend on both the in-plane second-order nonlinear
coefficients (d22) and the out-of-plane second-order nonlinear
coefficients (d15, d31, and d33). While keeping consistent with
MXs, the perpendicular components are determined only
by d22. Nevertheless, at 0°incident angle, the parallel compo-

nents I Janus ∝ d222
sin 2 [3φ ] and the perpendicular components
⊥
I Janus ∝ d22
2
cos2 [3φ ]d22
2
are only determined by d22. To examine
the evolution of SHG intensity polarization components
induced by the out-of-plane second-order coefficient elements,
the incident angle is set as 45°.
The SHG intensity polar plots for Ga2SeTe at photon energy
(PE) of 2.02, 2.35, 3.84 eV and for GaInTe2 at 2.36, 3.1, 4.74 eV
are shown in Figure 5a–c,d–f, respectively. The rotational sym-
metry of perpendicular components is always sixfold. Due
to different contributions from out-of-plane and in-plane
Figure 5. SHG intensity polar plots in a–c) Ga2SeTe, and d–f) GaInTe2 at
different PE. Their maximum values are also listed at the bottom.
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second-order nonlinear coefficient elements, the rotational
symmetry of parallel SHG intensity components varies with
the photon energies. The parallel components of Ga2SeTe may
exhibit threefold (Figure 5a, 2.02 eV; Figure 5c, 3.84 eV) and six-
fold (Figure 5b, 2.35 eV) rotational symmetry. As for GaInTe2,
threefold (Figure 5d, 2.36 eV; Figure 5e, 3.1 eV) and even one-
fold (Figure 5f, 4.74 eV) rotational symmetry are found in the
parallel components. This peculiar variation of rotational sym-
metry is also revealed in other Janus M2XX’ and MM’X2 mon-
olayers (Figure S13, Supporting Information).
Besides, the sequence of the maximum value between
parallel components and perpendicular components as well
as their difference can be distinct. In Ga2SeTe, only at PE of
2.35 eV, the maximum value of perpendicular component is
larger than the parallel one. The maximum value of SHG inten-
sity in Ga2SeTe can reach 5.48 × 105 pm2 V−2 at PE of 3.84 eV.
As for GaInTe2, at PE of 2.36, 3.1, 4.74 eV, the maximum value
of perpendicular component is always smaller than the par-
allel one. At PE of 4.74 eV, due to extremely large out-of-plane
second coefficient element d31, the parallel component is much
larger than the perpendicular part, and the difference is as large
as 104 pm2 V−2. Therefore, the perpendicular plot seems nearly
shrink to one point. The crystal’s azimuthal angle-dependent
SHG intensity investigation can be an effective tool to charac-
terize out-of-plane SHG response based on Janus structures
and other 2D materials without mirror symmetry.
3. Conclusion
In conclusion, the SHG response of anion M2XX’ and cation
MM’X2 Janus structures are explored in comparison with pris-
tine MXs based on first-principle calculations combined with
independent particle approximation. The extraordinary out-
of-plane SHG response is revealed in all the Janus M2XX’ and
MM’X2 due to the out-of-plane robust dipole effect resulting from
asymmetric charge redistribution. Besides, cation MM’X2 Janus
structures exhibit systemically higher SHG response than that of
anion M2XX’ due to stronger dipole. Among all the Janus struc-
tures, GaInTe2 possess the strongest out-of-plane SHG response
with d31 up to 10 490.41 pm V−1 at PE of 4.7 eV and is expected
to be a candidate for ultraviolet nonlinear optical devices. Several
prominent peaks in out-of-plane elements spectra of representa-
tive Ga2SeTe and GaInTe2 originate from two-photon transitions
between the charge asymmetric bands. The in-plane components
of Janus M2XX’ assemble the characteristics of corresponding
pristine structures, exhibiting broadband nonlinear optical
response. Finally, we find that the SHG intensity polar plots from
Janus structures display different rotational symmetry compared
with their pristine counterpart. To the best of our knowledge,
our work is the first to disclose the dramatically enhancement of
cation MM’X2 so far. Our work demonstrates the colossal advan-
tage of cation Janus in out-of-plane SHG response and paves the
way for Janus structures’ utilization in nonlinear optics.
4. Experimental Section
All the first-principles calculations were conducted via the Vienna ab
initio simulation package code (VASP),[39] utilizing the Perdew–Burke–
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Ernzerhof form of exchange-correlation functional under generalized
gradient approximation (GGA-PBE).[40] The projector-augmented wave
potentials (PAW)[41] were adopted and the cutoff energy for the plane-
wave basis was set to be 500 eV. A vacuum region of 20 Å was applied
to avoid the interaction between periodic images. In all calculations,
convergence criteria for total energy and force were taken as 10−6 eV and
0.01 eV Å−1, respectively. The accurate band structures of MXs and their
derivatives were acquired by the hybrid functional (HSE06).[42] Besides,
scissor corrections[43] setting as the difference between values of band
gaps calculated by PBE and HSE06 were employed to reduce errors of
the second nonlinear coefficients due to ignored many-body effects.
The second-order nonlinear susceptibility χabc(−2ω, ω, ω) (a,b,care
Cartesian coordinates) was calculated with the package developed
by Zhang’s group[44] considering both the pure inter-band transition
contributions χ eabc ( −2ω ,ω ,ω ) and the mixed inter-band and intra-band
transition processes χ iabc ( −2ω ,ω ,ω ) under the independent-particle
approximation. Aversa and Sipe[45] first presented expressions for the
second-order nonlinear susceptibility under a length-gauge analysis,
and subsequently Rashkeev[46] reorganized the second-order nonlinear
susceptibility to include all symmetries. The calculation details are
shown in the Supporting Information S1. In the following sections, the
second-order nonlinear coefficient dμl according to Voigt notation was
adopted to stand for second-order nonlinear susceptibility with the
relationship: dμl = χabc/2.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
S.-Q.L. and C.H. contributed equally to this work. This work was
supported by the National Natural Science Foundation of China (Grant
No. 12074053, 91961204, 12004064), XinLiaoYingCai Project of Liaoning
province, China (XLYC1907163), and by the Fundamental Research
Funds for the Central Universities (DUT21LAB112). The authors also
acknowledge Jiangsu Key Laboratory for Carbon-Based Functional
Materials & Devices, Soochow University and Computers supporting
from Shanghai Supercomputer Center, DUT supercomputing center, and
Tianhe supercomputer of Tianjin center.
Conflict of Interest
The authors declare no conflict of interest.
Data Availability Statement
The data that support the findings of this study are available from the
corresponding author upon reasonable request.
Keywords
2D materials, group-III monochalcogenides, Janus structure, nonlinear
optical, second harmonic generation
Received: January 13, 2022
Revised: March 16, 2022
Published online: May 20, 2022
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