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Effect of stacking order and in-plane strain on

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the electronic properties of bilayer GeSe†

Cite this: Phys. Chem. Chem. Phys.,
2018, 20, 6929
Yuliang Mao, *a Congshen Xu,a Jianmei Yuanb and Hongquan Zhaoc

Germanium selenide as a new layered material is promising for nanoelectronic applications due to its
unique optoelectronic properties and tunable band gap. In this study, based on density functional
theory, we systematically investigated the structure, stability, and electronic properties of bilayer
germanium selenide with four different stacking orders (namely AA-, AB-, AC- and AD-stacking). The
obtained results indicated that the band gap is dependent on the stacking order with an indirect band
Received 28th November 2017, gap for AA- and AC-stacking and direct band gap for AB- and AD-stacking. In addition, we also found
Accepted 8th February 2018 that the band gap of the GeSe bilayer with different stacking orders can be tuned by in-plane strain. The
DOI: 10.1039/c7cp07993a transition between the direct to indirect band gap or semiconductor to metal is tunable. In particular,
the direct band gap of the AB-stacking germanium selenide bilayer can be tuned in a wide energy range
rsc.li/pccp under applied strain along the armchair direction.

Introduction one with a direct band gap.30 Recently, using mechanical

stripping and laser thinning technology, monolayer GeSe had
Graphene, since its isolation, is considered to have great been successfully fabricated by our group.31 Photolumines-
potential applications in nanoelectronics owing to its unique cence (PL) experiments on monolayer GeSe showed that eight
electronic and mechanical properties.1,2 The discovery of continuous peaks are observed in the visible to infrared wave-
graphene3 has boosted the research in two-dimensional (2D) length range, which is highly desirable in solar cell applica-
materials,4–6 such as in silicene,7,8 germanene,9 and transition tions. Our first-principles study indicated that the indirect to
metal dichalcogenides (TMDS).10,11 Recently, it was reported direct band gap transition occurs at the layer number of N = 3
that phosphorene, the monolayer of black phosphorus, has an in few layered GeSe. Furthermore, under the condition of high
inherent direct band gap with high mobility charge carriers and pressure and high temperature, the electrical conductivity of
can be easily exfoliated.12–14 However, it was found that black GeSe is higher than that of both black phosphorus and
phosphorus is easily oxidized when exposed to air.15–17 There- graphene.32 As reported by Zhang et al.,33 there are five poly-
fore, the continuous search for more stable and related semi- morphs of GeSe monolayer: a-GeSe, b-GeSe, g-GeSe, d-GeSe,
conductor materials such as phosphorus has attracted much and e-GeSe. Nanosheets of a-GeSe have been synthesized via
interest. several methods; such nanosheets have potential applications
Due to their high stability, low toxicity18–21 and struc- in photodetector devices.34,35 Due to their different configura-
tures analogous to phosphorene, group-IV monochalcogenides tions, previous studies predicted that the structures of 2D GeSe
(GeS, GeSe, SnS, and SnSe) have attracted increasing attention have two phases, namely, black-phase36,37 and blue-phase.38,39
and exhibit exceptional optoelectronic properties.22–29 Among The first-principles calculations performed by Ji et al.40 demon-
the four types of monochalcogenides materials, GeSe is the only strated that the work function of black-phase GeSe cannot
effectively satisfy the oxidation potential of O2/H2O, but blue-
phase GeSe is a suitable photocatalyst for water splitting.
a
Hunan Key Laboratory for Micro–Nano Energy Materials and Devices,
Compared to the monolayer structure, some 2D bilayer
School of Physics and Optoelectronic, Xiangtan University, Hunan 411105, China.
E-mail: [email protected]
structures such as bilayer phosphorene and MoS2 exhibit more
b
Hunan Key Laboratory for Computation and Simulation in Science and striking properties due to their smaller band gap than a single
Engineering, School of Mathematics and Computational Science, layer sheet.41,42 This implies that 2D bilayer structures provide
Xiangtan University, Hunan 411105, China more opportunities to tune the band gap by strain. In addition,
c
Chongqing Institute of Green and Intelligent Technology, Chinese Academy of
significant carrier mobility has been observed in bilayer phos-
Sciences, 266 Fangzheng Ave, ShuiTu Technology Development Zone,
Beibei District, Chongqing, China
phorene and MoS2.43 Furthermore, the bilayer structure allows
† Electronic supplementary information (ESI) available. See DOI: 10.1039/ various stacking orders due to weak interlayer van der Waals
c7cp07993a (vdW) interactions,44 which provide a new method to tune its

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electronic properties. The above mentioned unique electronic

properties and applications in the bilayer structures stimulated
us to explore and tune the electronic structure of bilayer GeSe.
In this study, considering the four possible stacking orders
in bilayer GeSe, we investigated the structure stability, electro-
nic properties, and strain effect in this 2D bilayer material. It
should be noted that our study is based on the black phase of
2D GeSe, which corresponds to the configuration of a-GeSe.
As reported by Zhang et al.,33 the a-phase of GeSe monolayer is
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the most stable at room temperature among its five polymorphs.

The structure of monolayer GeSe is consistent with the configu-
ration of the GeSe sample synthesized experimentally.31 We
found that different stacking orders can vary the band gap and
change the type of band gap between direct and indirect. In
particular, compared with monolayer GeSe, we found that the
direct band gap of AB-stacking bilayer GeSe can be tuned in a
wide energy range under strain along the armchair direction.

Computational method
Fig. 1 Structure and corresponding charge density of the four bilayer
Electronic structure calculations were performed using density GeSe conformations. (a) AA-stacking, (b) AB-stacking, (c) AC-stacking, and
functional theory (DFT)45 based on the open source code (d) AD-stacking. The top layer of the AA-stacking is stacked on the same
layer in the bottom. The order of AB-stacking is consistent with that in bulk
QUANTUM ESPRESSO.46 The exchange correlation energy was
GeSe. AC-stacking or AD-stacking can be seen as the rotation of the top
described using the generalized gradient approximation (GGA) layer of the AB-stacking along the x- or y-axis by 1801. The green and
with the Perdew–Burke–Ernzerhof (PBE) functional.47,48 To orange balls represent the Ge and Se atoms, respectively. The relaxed
correctly describe the effect of van der Waals (vdW) interac- structural parameters (l1, l2, y1, and y2) of the four different stack structures
tions, the Tkatchenko–Scheffler (TS) vdW functional was are indicated in (a). l1 and l2 are the bond lengths between the Ge atom and
Se atom in the upper layer and the lower layer, respectively. y1 is the angle
applied.49 We also tested the accuracy of other vdW functionals.
of the Ge–Se–Ge bond. y2 is the angle of the Se–Ge–Se bond. a and b are
As indicated in Table S1 in the ESI,† the TS vdW functional was the lattice parameters. d is the smallest interlayer distance.
most suitable for our study. A sufficiently large vacuum region
of 20 Å was used to separate any interaction between neighboring
bilayers along the y-axis. The structure was optimized using the
top layer of the AA-stacking can be observed as stacking on the
method of Broyden–Fletcher–Goldfarb–Shanno (BFGS).50 The
same layer in the lower layer. The order of AB-stacking, as shown
Kohn–Sham orbitals were expanded in a plane-wave basis with
in Fig. 1(b), is consistent with that in bulk GeSe. The AB-stacking
a cutoff energy of 70 Ry. The Brillouin zone (BZ) was sampled
GeSe bilayer was widely investigated in previous studies.53–55
using the Monkhorst–Pack51 mesh with 13  1  13 k-points. For
In bulk GeSe, its unit cell is composed of double-layer slabs with
comparison, the HSE0652 hybrid functional was used to calculate
eight atoms, which is similar with that in black phosphorus.56
the band structures of bilayer GeSe. Binding energy is defined as
Each atom in the double-layers is connected with three
Eb = (E(GeSe)n E(GeSe)up E(GeSe)sub)/4n, where, E(GeSe)up, E(GeSe)sub
adjacent atoms via covalent bonds.57 AC-stacking [Fig. 1(c)] or
and E(GeSe)n are the total energies of upper layer GeSe, lower layer
AD-stacking [Fig. 1(d)] can be observed as the rotation of the
GeSe, and bilayer GeSe, respectively. The in-plane strains are
top layer of the AB-stacking along the x- or y-axis by 1801. After
defined as sx = (a a0)/a and sz = (b b0)/b, where, a0 and b0
relaxation, we obtained the lattice constants and structure
are the lattice constants along the x and z directions under strain,
parameters of the four different stacking configurations as
respectively. Correspondingly, a and b are lattice constants of the
listed in Table 1. As found in Table 1, the lattice constant a,
studied bilayer GeSe with four different stacking orders.
which is along the armchair direction, exhibits a significant
change due to the structural flexibility. However, the lattice
Results and discussion constant b, which is along the zigzag direction, exhibits only a
minor change. The obtained optimized lattice constants of
Stacking structure and stability of bilayer GeSe AB-stacking are in agreement with previous theoretical
Taking 2D monolayer GeSe as a basic building block, we con- results.58 For the structure parameters, the bond lengths l1 and
structed four types of configurations of bilayer GeSe. In our l2 are almost the same in the four bilayer conformations. The
study, the single layer GeSe has an orthorhombic structure, bond angle y2 in bilayer GeSe is slightly different as compared to
which was reported in detail in our recent publication.31 The that in the GeSe crystal, which is larger than the bond angle y1.
four possible stacking structures of bilayer GeSe, namely, AA-, As shown in Table 1, the interlayer distance in AA-stacking is the
AB-, AC-, and AD-stacking are presented in Fig. 1. In Fig. 1(a), the shortest among the four bilayer GeSe conformations, which is

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Table 1 The relaxed structural parameters (l1, l2, y1 and y2) of the four
different stacking structures using the PBE functional. l1 and l2 are the bond
lengths of Ge–Se in the upper layer and lower layer, respectively. y1 is
the angle of the Ge–Se–Ge bend. y2 is the angle of the Se–Ge–Se bond.
a and b are the lattice parameters in each unit cell of AA-, AB-, AC-, and
AD-stacking. h is the interlayer distance. Eb represents the binding energy

a (Å) b (Å) l1 (Å) l2 (Å) d (Å) y1 (1) y2 (1) Eb (meV)

AA 4.22 3.96 2.62 2.62 3.03 96.58 97.35 52.3
AB 4.37 3.94 2.55 2.55 3.12 95.51 96.34 48.1
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AC 4.21 3.97 2.55 2.56 3.40 92.2 97.14 30.3

AD 4.27 3.98 2.55 2.55 3.30 94.14 96.87 37.5

3.03 Å. In the AB-stacking configuration, the interlayer distance

is larger by 0.9 Å than that in the AA-stacking configuration. The
AC-stacking has the longest interlayer distance of 3.45 Å. In the
case of AD-stacking, the interlayer distance is 3.30 Å.
The binding energies of the four different stacking orders
are presented in Table 1. According to our calculations, the
Fig. 2 Calculated band structures for the four possible stacking structures
lowest binding energy of 52.3 meV is achieved in AA-stacking, of bilayer GeSe. For comparison, the results obtained from the PBE
which implies that AA-stacking is the most stable structure functional (black line) and HSE06 method (red line) are plotted together.
among the four conformations of bilayer GeSe. However, the Fermi level is indicated by dotted line. G(0.0, 0.0, 0.0), X(0.5, 0.0, 0.0),
binding energy in the AB-stacking GeSe bilayer is larger by only T(0.5, 0.0, 0.5), and Z(0.0, 0.0, 0.5) are the high symmetric points in the first
Brillouin zone. The black (red) arrows highlight the CBM and VBM positions
4.2 meV than that in AA-stacking, which is 48.1 meV. The
obtained from the PBE functional (HSE06 method), respectively. The
AC-stacking has highest binding energy of 30.3 meV. In the corresponding DOS obtained from the PBE functional and HSE06 method
case of AD-stacking, the binding energy is 37.5 meV. For are plotted on the right side of the band structures.
bilayer phosphorene59 and arsenene,60 which have structures
similar to that of bilayer GeSe, previous results obtained from
theoretical simulation indicated that the AB-stacking is the Our detailed analysis of the PBE results indicates that the
most stable among the different stacking configurations. The bandgap of AA- and AC-stacking are 1.01 eV and 0.98 eV,
possible reason for this is that in AA-stacked bilayer phosphorene respectively. Furthermore, our HSE06 calculations for the above
or arsenene, strong repulsion forces arise from the same type of two stacking conformations indicate that they have an energy
atoms (P or As), while in AA-stacking bilayer GeSe, the Ge atoms gap of 1.35 eV and 1.40 eV, respectively. Normally, the band gap
and Se atoms generate more attractive potential, which leads to calculated from the PBE functional is underestimated. It is
the release of more energy. Furthermore, by analyzing the charge expected that the result of the HSE06 method can be further
density data shown in Fig. 1, we found that in AA-stacking, the Ge validated experimentally. In contrast, for the band structures of
atoms in the upper layer and the Se atoms in the lower layer have AB- and AD-stacking, our results indicate they possess direct
slightly higher significant covalent character than that in the other energy gaps; the obtained band gap from the PBE functional is
stacking cases. Therefore, it is confirmed that the attractive 1.06 eV and 1.13 eV, respectively, while the HSE06 calculations
potential between the Ge atoms in the upper layer and the Se predict energy gaps of 1.58 eV and 1.64 eV, respectively.
atoms in the lower layer is a key factor to achieve the lowest energy Compared to the band gap of 1.0 eV in bilayer phosphorene
in AA-stacking. (based on HSE06),59 the bilayer GeSe has a larger band gap in AB
stacking. This band gap obtained in bilayer GeSe is suitable for
Electronic structure of bilayer GeSe optical absorbance in the visible spectrum as reported earlier.53
The band structures and corresponding density of states (DOS) According to the above discussion, we found that AA-stacking
of the four bilayer GeSe conformations with different stacking possesses an indirect band gap, whereas AB-stacking has a direct
orders are shown in Fig. 2. For comparison, the results from the band gap. It appears from the calculated minor difference of
PBE functional and HSE06 methods are plotted together. In our 4.2 meV in binding energy that both AA- and AB-stacking are
previous study,31 in single layer GeSe, we obtained a direct equivalently stable. However, combined with the PL experiment
band gap of 1.14 eV using the PBE functional. This calculated and first-principles simulation,31 it is found that the indirect to
energy gap is consistent with a previous report in the literature.54 direct band gap transition occurs at few layers less than three.
However, our calculated result obtained from the HSE06 func- The above experimental findings imply that bilayer GeSe
tional for the same single layer GeSe predicted an energy gap of possesses a direct band gap. The observed continuous peaks
1.7 eV. This predicted energy gap is comparable with the result from the visible to infrared wavelength range in the PL
from the PL experiment.31 For bilayer GeSe, among the four spectrum31 of few-layered GeSe provide direct proof for this
different stacking structures, the band structures of AA- and point. Therefore, AB-stacking bilayer GeSe may be more likely
AC-stacking indicate that they possess an indirect band gap. to be prepared experimentally.

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To further understand the electronic structure of the four Strain effect on tuning the band gap
different stacking conformations, in Fig. 2, we also present the Previous theoretical and experimental studies indicated that
DOS and corresponding partial DOS (PDOS). The results applying in-plane strain can tune the band gap of bilayer black
obtained from both the PBE functional and HSE06 methods phosphorus61 and MoS2.62 Stimulated by these findings, we
indicate that the upper valence band (VB) and bottom conduc- further explored the effect of strain by applying in-plane strain
tion band (CB) of all four structures are contributed by both s on bilayer GeSe. As discussed above, AB-stacking has a direct
and p orbitals. It is found that the DOS is primarily composed band gap, which is validated by PL experiment. Therefore, we
of p-orbitals. The valence band maximum (VBM) and conduc- specifically report the results of AB-stacking bilayer GeSe tuned
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tion band minimum (CBM) in the band structures of all the by strain. The calculated results for the variation of the energy
stacking structures are dominated by the 4p states of the Se gap in AB-stacking bilayer GeSe under in-plain strain are shown
atoms and 4p states of the Ge atoms, respectively. The results of in Fig. 4. For the other stacking configurations, the strain
PDOS obtained from both PBE and HSE06 are consistent with effects on their band gaps are summarized in the ESI.†
the above analysis. As shown in Fig. 4(a), if the AB-stacking structure is stretched
The decomposed charge density of the VBM and CBM is along the x-axis from 0% to 8%, the band gap almost linearly
shown in Fig. 3. It can be found that the charge density of the increases from 1.06 eV to 1.35 eV. In contrast, if the AB-stacking
VBM is primarily located around the Se atoms. In contrast, structure is compressed from 0% to 8%, the band gap linearly
our analysis indicates that the CBM is primarily attributed decreases to 0.74 eV. In particular, stretching strain or com-
to the localization of charge density around the Ge atoms. pressive strain will not change the type of direct band gap.
These findings for the VBM and CBM are in agreement It is important that the direct band gap is maintained regard-
with the abovementioned DOS analysis. Furthermore, the less of the in-plain strain along the x-direction. Fig. 4(b) shows
distribution of charge density in the VBM is almost similar the band structures of AB-stacking bilayer GeSe under 1%
in all the studied stacking conformations. However, the compressive strain and 1% tensile strain along the x-direction.
charge density of the CBM shows different character in the It is clearly indicated from the arrow shown in the figure that a
conformations with a direct band gap and in the configura-
tions with an indirect band gap. As shown in Fig. 3(a) and (c),
there is no overlap of the CBM charge density between the
upper and lower GeSe sheets. In contrast, as indicated in
Fig. 3(b) and (d), with AB and AD stacking, there is significant
overlap of the CBM charge density between the Ge atoms in
the upper layer and the Ge atoms in the lower GeSe layer.
Thus, the CBM charge density between the interlayers has an
impact on the type of band gap in bilayer GeSe. This implies
that the CBM charge density between the interlayers is a
key factor that decides the direct or indirect band gap in
bilayer GeSe.

Fig. 4 Variation in the band gap under in-plane strains and corresponding
band structures under certain values of strain obtained by the PBE method.
(a), (c) and (e) show the variation in band gap under applied strain along
sx, sz and sxz respectively. (b) Band structures under sx = 1.0% and sx = 1.0%.
(d) Band structures under sz = 1.0% and sz = 1.0%. (f) Band structures under
sxz = 6.0% and sxz = 1.0%. The positive and negative values in the range of
Fig. 3 Band-decomposed charge densities (based on HSE06) of the VBM 8% to 8% correspond to the tensile and compressive strain, respectively. The
and CBM of the four possible stacking structures of bilayer GeSe. The black arrows in band structure indicate the CBM and VBM position, respec-
isovalue is 0.0015 e Å 3. tively. The Fermi level is set as zero.

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direct band gap of 1.04 eV and 1.10 eV between the VBM and band gap. In addition, the charge density of the CBM is very
CBM can be found under sx = 1% and sx = 1% strain, sensitive to the stacking order, which results in a direct or indirect
respectively. In monolayer GeSe, the band gap can also be band gap. We also found that the band gap of the four types of
tuned by strain. A previous study63 showed that the transition stacking bilayer GeSe could be significantly tuned by in-plane
from direct to indirect band gaps in GeSe monolayer will strain. In AB-stacking, the direct band gap is tunable in a very
continuously occur when in-plane strain is applied, which large energy range under both stretching strain and compressive
implies that it is difficult in a wide energy range to maintain strain along the x-axis. Under 6% compressing strain along the
the direct band gap by applying strain. In contrast, herein, the biaxial direction, a transition from direct to indirect band gap is
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results from in-plane strain along the x-axis in the AB-stacking observed. We also found that the AC- and AD-stacking GeSe
GeSe bilayer indicate that the direct band gap can be tuned in a bilayers have almost similar features as that in AB-stacking when
wide energy range. in-plane strain is applied. For the AA-stacking GeSe bilayer, we
If the strain is applied along the z-direction, as shown in found that the inherent indirect band gap can be tuned to direct
Fig. 4(c), it is found that the band gap increases linearly from band gap if a very small stretching strain is applied along the
1.06 eV to 1.22 eV when stretching strain from 0–8% is applied. biaxial or z-direction.
In contrast, when it is compressed from 0% to 8%, the band
gap decreases rapidly to 0.25 eV. It should be noted that with
the contribution of in-plane compressed strain, the direct band Conflicts of interest
gap in AB-stacked GeSe bilayer changes to indirect. As shown in There are no conflicts to declare.
Fig. 4(d), under 1% compressed strain, the arrow in the plot
clearly shows an indirect band gap of 0.96 eV between VBM and
CBM. However, under 1% stretched strain, the arrow between Acknowledgements
the VBM and CBM indicates a direct energy gap of 1.08 eV. In
Fig. 4(e), when the applied strain is stretched or compressed This study is supported by the National Natural Science Foun-
along both the x- and z-directions, it is found that the band gap dation of China under Grant No. 11471280, No. 11374251, and
increases or decreases faster than that in uniaxial situations. No. 61775214, by the Hunan Provincial Natural Science Foun-
It is also found that the band gap remains direct under the dation of China under grant No. 2016JJ2130, by the Research
applied stretched strains, which is similar with the situations in Foundation of Education Bureau of Hunan Province, China
uniaxial strains. Analogous to the stretching characteristic, the (No. 16A207 and 17A207), and by the Program for Changjiang
energy gap under compressed strain decreases faster than that Scholars and Innovative Research Team in University (IRT13093).
in uniaxial strain. Interestingly, the energy gap reaches zero Calculation time is supported by Special Program for Applied
when the applied biaxial strain is 6% as shown in Fig. 4(f). This Research on Super Computation of the NSFC-Guangdong Joint
implies a transition from semiconductor to metal when the Fund (the second phase).
tensile strain is continually increased. In bilayer phosphorene,
the band gap can also be tuned by in-plane strain.61 However, References
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