Vacuum 192 (2021) 110434

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DFT computation of two-dimensional CdO/GaS van der Waals

heterostructure: Tunable absorption spectra for water splitting application
Hongyuan Zhao, Enling Li *, Chang Liu, Yang Shen, Pengfei Shen, Zhen Cui, Deming Ma
School of Science, Xi’an University of Technology, Xi’an, 710048, China

A R T I C L E I N F O A B S T R A C T

Keywords: Based on first-principles calculation, we systematically investigated the electronic structure, charge transfer, and
vdW heterostructure optical properties of the CdO/GaS van der Waals (vdW) heterostructure, and which are effected by applied
GaS monolayer mechanical strain. Heyd-Scuseria-Ernzerhof (HSE06) is used to accurately calculate the electronic structure, and
Density functional theory (DFT)
the results show the CdO/GaS heterostructure is a semiconductor with a direct band gap (1.79 eV), which possess
Photocatalysis
type-II band alignment, and is in favor of the separation of photogenerated carriers and extend their lifetime. The
suitable band gap and band edge position of the CdO/GaS heterostructure promise application prospect in
photocatalyst for water splitting. The significant advantages of the CdO/GaS heterostructure for photocatalytic
performance in whole sunlight spectrum are obtained by applying biaxial strain to the heterostructures.

1. Introduction graphite (graphene) with excellent performance in 2004 [3], because

of its excellent electrical and optical properties [4–6], researchers from
With the over-exploitation and abuse of fossil fuels, the problems of all over the world have been attracted research interest. Then other
crude oil resources depletion and air pollution have become prominent. two-dimensional semiconductor materials, the compound semi­
As the above-mentioned problems continue to worsen, the need to find a conductor, such as GaN [7–11], BC2N [12–14], MoS2 [15–17], and C3N4
new type of clean energy has become very urgent. Hydrogen is an ideal [18–20] etc., elemental semiconductor, such as black phosphorus
renewable energy, compared with the fossil fuels that are non-renewable [21–24], α- and β- Beryllium [25] etc., were successfully prepared in
and producing a lot of pollutants after burning, hydrogen is an ideal experiment or maturely researched performance in theory [26–31].
renewable energy that is clean, abundant reserves, high energy yield and Since then, some researchers have modified the surface of the intrinsic
high energy storage [1]. These characteristics also make hydrogen a material and obtained more prominent properties [32–34], which
major factor in the ideal energy source in the future. However, nowa­ marked that they have become a breakthrough in solving some special
days, industrial hydrogen is mostly produced by using natural gas and problems. In the field of hydrolysis photocatalysis, the two-dimensional
water vapor through high temperature and high pressure, resulting in a semiconductor materials have high ration of exposed surface atoms,
great waste of resources. How to produce hydrogen efficiently and large specific surface area, and short carrier migration distance, which
without wasting of resources is still a huge challenge. make the two-dimensional semiconductor materials having a natural
Currently, some scientific studies have confirmed that the use of advantage in photocatalytic water splitting [35]. An effective water
photocatalysts can reduce hydrogen ions in water to hydrogen. This splitting photocatalyst should have an appropriate band edge position
method is an effective way to solve the above-mentioned problems. and band gap. Generally, not only the valence band maximum (VBM)
According to the published research results, semiconductor photo­ must be lower than the oxidation potential of water, but also the con­
catalysts have become popular candidates for water splitting applica­ duction band minimum (CBM) must exceed the reduction potential of
tions because of their high conduction band potential and low valence water, simultaneously, the band gap must be greater than 1.23eV water
band potential simultaneously with proper band gap [2]. However, the splitting energy. Even so, for some two-dimensional semiconductors,
high carrier recombination rate and low atomic specific surface area such as graphene-like carbon nitride [36] (g-CN), transition metal oxide
make the photocatalytic effect of three-dimensional semiconductors [37–39] (CdO, ZnO), although g-C6N6 has a wide direct band gap
unsatisfactory. Since the successful separation of two-dimensional (3.22eV) which makes it have strong absorption in ultraviolet light but

* Corresponding author.
E-mail address: lienling@[Link] (E. Li).

[Link]
Received 5 June 2021; Received in revised form 7 July 2021; Accepted 7 July 2021
Available online 10 July 2021
0042-207X/© 2021 Published by Elsevier Ltd.
H. Zhao et al. Vacuum 192 (2021) 110434

no whole sunlight. In addition, CdO has a more suitable band gap [√̅̅̅̅̅̅̅̅̅̅̅̅̅̅ ]12
(2.10eV), but its valence band potential is slightly higher than the √̅̅̅ ε21 + ε22 − ε1
a(ω) = 2ω (1)
oxidation potential of water. The band edge potential and the band gap 2
can be tuned by applying mechanical strain to adapt to the water
decomposition reaction. In the other hand, due to the limited thickness Where ε1 and ε2 are the real and imaginary parts of the dielectric
of two-dimensional materials, photoinduced electrons and holes are function, and ω is the photon frequency. The optical properties were
usually has short lifetime resulting in high recombination, which is the obtained from the frequency dependent dielectric response theory
disadvantage of water decomposition. An efficient photocatalyst is not including local field effects in the random-phase-approximation (RPA)
only produce a suitable band gap to absorb sunlight more effectively, but [50].
also effectively separate electron-hole pairs in space. Some 2D/2D het­
erostructures are usually meets the conditions, which have a type-II 3. Results and discussion
band alignment, the CBM (or the VBM) in one layer is higher than the
relative position of the other layer [40], and the band gaps are just right The schematic diagrams along the c-direction (top view) and a-di­
response to sunlight. rection (side view) of the unit cell of CdO/GaS heterostructure are
In recent years, the two-dimensional group III metal mono­ shown in Fig. 1 (a) and (b) respectively. Along the a-direction, CdO
chalcogenide (such as GaS monolayer) has attracted more researchers exhibits a monolayer planar structure while GaS exhibits a sandwich-
attention because of its higher electron mobility and higher optical like structure; along the c-direction, both materials exhibit a hexago­
response. It is well known that high carrier mobility accelerates the nal structure. The stacking order is that sulfur (S) atoms and gallium
separation and transfer of charges to the surface, which is advantageous (Ga) atoms are vertically located on oxygen (O) atom and cadmium (Cd)
for photogenerated carriers to participate in their respective half- atom, respectively. Subsequently, we optimized and calculated the lat­
reactions in the photocatalytic process [41,42]. In addition, the suc­ tice constants under the two relaxed structures. The optimized lattice
cessfully synthesized two-dimensional ultra-thin GaS has also confirmed constants of the CdO monolayer are a = b = 3.68 Å and of the GaS
its properties, but the inappropriate band gap (3.3 eV) of the monolayer are a = b = 3.63 Å, which are in good agreement with the
two-dimensional GaS leads to inefficient utilization in solar radiation results obtained by previous research work (a = b = 3.59 Å of the CdO
spectrum [1], and the indirect band gap of GaS causes electrons to monolayer [51], and a = b = 3.58 Å of the GaS monolayer [52]). Sub­
interact with the crystal lattice during the transition process, which sequently, when the heterostructure is formed, its lattice constant be­
greatly reduces the absorption coefficient. Fortunately, although CdO comes 3.66 Å. Since the lattice constants of the two structures are
has the VBM energy level that higher than the oxidation potential of similar, we calculated that the lattice mismatch between the two ma­
water splitting, but it has a more suitable band gap (2.07eV) and high terials (CdO monolayer and GaS monolayer) is 1.58%, which is less than
electron mobility. So, expectations for CdO/GaS two-dimensional het­ 3%. This shows that within the controllable range of the structure, the
erostructure has an appropriate band edge position and band gap, as electronic properties of the heterostructure will not be affected [53].
well as type II band alignment and high optical response promising an To determine the most stable structure, the binding energy has been
excellent application prospect for hydrolysis photocatalysis. calculated with different interlayer spacing and the results have sum­
Based on this, the electronic structure, charge transfer, optical marized as shown in Fig. 2 (a). The binding energy (EB) of the CdO/GaS
properties of CdO/GaS heterostructure, and which are effected by bilayer heterostructure is calculated as follows:
applied mechanical strain are systematically investigated using the first-
principles based on density functional theory (DFT) framework in this EB = [Etotal − (E1 + E2 )] (2)
paper. The much more sensitive optical response and the satisfactory
Where the Etotal is the total energy of the bilayer van der Waals hetero­
type-II band alignment indicate that the CdO/GaS heterostructure is a
structure, E1 is the energy of the CdO monolayer, and E2 is the energy of
very promising photocatalyst for hydrogen production. The findings will
the GaS monolayer. As shown in Fig. 2(a), the lowest binding energy is
propose a deep insight into the improved photocatalytic performance,
− 1.63 eV, and the corresponding interlayer spacing is 3.4 Å. In addition,
which may further contribute to the design of the GaS monolayer-based
we also calculated the thermal stability of the CdO/GaS heterostructure
nanocomposite photocatalysts.
with the interlayer spacing 3.4 Å at a temperature of 300k. As shown in
Fig. 2(b), due to the existence of thermal excitation, the heterostructure
2. Computational details
initially showed a certain distortion (the energy fluctuates). However, as
the number of optimization steps increases, the structure does not
We use the Vienna ab initio simulation package (VASP) to perform
appear obvious damage, and then the system energy stabilized. The
first-principles calculations based on density functional theory (DFT)
insert in Fig. 2 (b) is the optimized structure of the CdO/GaS hetero­
[43,44]. The projected augmented wave method (PAW) [45] uses
structure from molecular dynamics calculation, there is only a small
Perdew-Burke-Ernzerhof (PBE) [46] generalized gradient approxima­
dislocation and distortion but no bond breakage. These shows that the
tion (GGA) [47] for describe the exchange-correlation interaction and
CdO/GaS heterostructure still maintains the basic configuration at room
core electrons. In addition, we use Heyd-Scuseria-Ernzerhof mixing
temperature and will not affect its electronic properties. Based on the
function (HSE06) [48] to accurately calculate the electronic structure
above results, we consider that the CdO/GaS heterostructure with the
and optical properties. When Grimme’s DFT-D3 method [49] is used to
interlayer spacing 3.4 Å is most stable, and this configuration will be the
consider the weak dispersion force, a 20 Å vacuum space is set to
research object in the following studies.
separate adjacent layers. The energy cut off of 550 eV is selected for the
As shown in Fig. 3, the band structures of the CdO monolayer, the
base set plane-wave by using the energy convergence criterion at 10− 5
GaS monolayer, and the CdO/GaS heterostructure have calculated by
eV and the force set at 0.02 eV/Å, and all geometry structures are
PBE and HSE06 methods. As shown in Fig. 3 (a), based on PBE method,
completely relaxed. The cell relaxation is performed for the 1 × 1 cell
the VBM and CBM of the CdO monolayer are both located at the center of
CdO/GaS van der Waals (vdW) heterostructure containing 2Ga, 2S, 1O,
the first Brillouin zone (Γ-point), showing a direct band gap 0.82 eV, but
and 1Cd atoms. The 16 × 16 × 1 k-point meshes employed in the DFT
the band gap is 2.07 eV calculated by HSE06 method. From Fig. 3 (b),
calculations are generated according to Monkhorst-Pack scheme.
more complicated situations appear in the GaS layer, the band near the
To evaluate the light absorption capacity, the absorption coefficient
VBM of the GaS monolayer appears the “Mexican hat” shaped band [54,
can be calculated by the following formula:
55] at the Border of the first Brillouin zone (M-point), at the same time,
the VBM appears at the midpoint between the center of the Brillouin

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H. Zhao et al. Vacuum 192 (2021) 110434

Fig. 1. The optimized structure of the CdO/GaS heterostructure along the side (a) and top view (b). The O atoms, Cd atoms, S atoms, and Ga atoms are marked in
bule, pink, yellow, and green, respectively.

Fig. 2. (a) Binding energy with different interlayer spacing; (b) energy and atomic model of the CdO/GaS heterostructure calculated by molecular dynamics method
at 300 K.

Fig. 3. (a) The band structure of the CdO monolayer, the red solid line calculated using PBE and the green solid line calculated using HSE06. (b) The band structure
of the GaS monolayer, the red solid line calculated using PBE and the blue solid line calculated using HSE06. (c) The band structures of the CdO/GaS heterostructure,
the red solid line calculated using PBE and the green solid line calculated using HSE06.

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H. Zhao et al. Vacuum 192 (2021) 110434

zone (Γ-point) and the farthest point of the Brillouin zone (K-point). The to their own conduction bands. Due to the potential energy gap caused
CBM of GaS appears at point M and exhibits a wide indirect band gap of by the misalignment of the bands after the heterostructure constructed,
2.45 eV based on PBE method. The Eg of both monolayers calculated the photogenerated electrons in the CdO layer are more inclined to
using PBE method are obviously different from the experimental value transfer to the conduction band of the GaS layer with lower electron
and previously reported (Eg of CdO is 2.10eV [37]; Eg of GaS monolayer potential energy; the photogenerated holes in the valence band of the
is 3.24eV [1]). This is because PBE method underestimate the energy GaS layer are more inclined to transfer to the valence band of the CdO
range of the conduction band, so the band gap lower than the experi­ layer with higher electron potential energy. This process is excited by
mental value. The band gap of CdO monolayer is 2.07 eV and the band light (hν) and driven by the potential energy difference, as shown in
gap of GaS monolayer is 3.27 eV obtained using HSE06 method, which Fig. 5 (a).
are consistent the experimental value and previously reported, so HSE06 The band edge positions of the CdO monolayer, the GaS monolayer,
method will have used in the following studies. and the CdO/GaS heterostructure are shown in Fig. 5(b). The oxidation
In Fig. 3 (c), the band structure of the CdO/GaS heterostructure, the potential and the reduction potential of water are marked by blue dotted
“Mexican hat” shaped band of the GaS layer in the valence band near the lines. The CBM of CdO monolayer is at − 3.47eV, which is higher than
Fermi level disappears, and the band gap is 1.79eV calculated by HSE06 the reduction potential of water, the VBM(-5.51eV) is also higher than
method, which is lower than both values of the two materials. To further the oxidation potential of water. Therefore, the CdO monolayer cannot
analyze the band structure of the GaS/CdO heterostructure, we calcu­ be applied in the water splitting reaction. The band edge of GaS
lated the contributing state band structure for each layer of the heter­ monolayer satisfies the water redox potentials, but due to its huge band
ostructure and density of states (DOS) using HSE06 method, as shown in gap (3.27eV), the electron will be excited in the UV region only, not in
Fig. 4. Fig. 4 (a) show that the CBM and VBM of the heterostructure are visible light region, so it does not take advantage of sunlight. In addition,
contributed by the GaS layer and CdO layer respectively, forming a type the indirect band gap of GaS is disadvantageous to absorption coeffi­
II band alignment. As seen in Fig. 4 (b), the CBM is dominated by the Ga- cient, as well as photoelectric conversion efficiency and photocatalytic
4s, Ga-4p, and S-3p orbitals of the GaS monolayer, and the VBM consists performance. Fortunately, the band edge of the CdO/GaS hetero­
of O-2p orbital of the CdO monolayer. This type-II band alignment will structure satisfies the water redox potentials, and has a direct band gap
result in the separation of electrons and holes reducing the complexation 1.79eV, which is advantageous to absorption coefficient, as well as
of electrons and holes, improving photoelectric conversion efficiency photoelectric conversion efficiency and photocatalytic performance,
and photocatalytic performance. So, the GaS/CdO heterostructure is a thus the sunlight is used efficiently.
better alternative in photocatalytic water splitting and high efficiency To further explore the mechanism of the effect of the electric po­
photoelectric conversion material. tential difference between bands on the lifetime of photogenerated
To further illustrate the dynamic behavior of photo-generated car­ carrier, we studied the electrostatic potential and average planar charge
riers on the CdO/GaS heterostructure interface and the process involved density difference of the CdO/GaS heterostructure. The electrostatic
in photocatalysis, we have studied the photo-generated carrier migra­ potential of the CdO/GaS heterostructure is shown in Fig. 6 (a), and
tion and a schematic diagram of the catalytic process on the CdO/GaS there is a potential difference Δv = 1.97 eV between the CdO layer and
heterostructure interface, as shown in Fig. 5. The electrons in valence the GaS layer, so there is an interlayer electric field between two layers,
band of the CdO and GaS layers will be excited by light (hν) to transition which will have a significant effect on the lifetime of photogenerated

Fig. 4. (a) The band structure of the CdO/GaS heterostructure. Green and blue represent the contributions of CdO and GaS respectively. (b) The partial density of
states (PDOS) of the CdO/GaS heterostructure.

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H. Zhao et al. Vacuum 192 (2021) 110434

Fig. 5. (a) Schematic diagram of the principle of hydrolysis photocatalysis; (b) the energy level positions of CdO, GaS and CdO/GaS heterostructures.

Fig. 6. (a) The electrostatic potential of the CdO/GaS heterostructure. (b) The average plane charge density difference of the CdO/GaS heterostructure. The inset is
the charge density difference of the CdO/GaS heterostructure. Yellow and cyan regions represent the accumulation and dissipation of the electrons respectively. and
the iso-surface value is 0.0002 e⋅A− 3.

carriers. The electrons excited by light (hν) will transfer from the high regions and the poor optical response of CdO monolayer, the CdO/GaS
conduction band potential layer (CdO layer) to the lower conduction heterostructure has a stronger optical response in the visible and near-
band potential layer (GaS layer) in the action of interlayer electric field ultraviolet light regions, which is a perfect photocatalyst with brilliant
(due to potential difference between the two layers). Fig. 6 (b) shows the prospects.
average plane charge density difference, and the inset of Fig. 6 (b) shows The electronic structures and optical properties of the materials can
the charge density difference of the CdO/GaS heterostructure. The CdO vary depending on the applied mechanical strains. So, strain engineering
layer is acts as an electron donor to transfer 0.0085|e| electrons to the can be an attractive approach to tune the electronic and optical prop­
GaS layer, which is acceptor. The transferred electrons cannot return to erties of 2D materials [56–58]. In here, we discuss the effect of the
the valence band and recombine with holes due to interlayer electric electronic and optical properties of the CdO/GaS heterostructure
field. Finally, when light begins to cause the reaction to occur and applied − 7%–7% biaxial strain. The band structures of the CdO/GaS
persist, the photogenerated electrons and holes in different material heterostructure applied mechanical strains are shown in Fig. 8, for easier
layers continuously catalyze the decomposition of water. comparison, we have marked the location of the energy band edges of
Considering that sunlight is applied to drive the water splitting re­ the intrinsic sign with red lines in each figure. When appling tensile
action, the optical properties of the CdO/GaS heterostructure should be strain, the band structure of the CdO/GaS heterostructure still maintains
investigated, especialy in visible light region. The imaginary part ε2 (ω) a direct band gap and has a type II band alignment, and the band gap
of the dielectric constant for the CdO monolayer, the GaS monolayer, decreases as the tensile strain increasing. However, the band gap of the
and CdO/GaS heterostructure are shown in Fig. 7(a), we can see there is CdO/GaS heterostructure tends to increase first (− 1%) and then
a generous response in visible light region. The first three dielectric decrease with the increase of the compressive strain. And when the
peaks of the CdO/GaS heterostructure are located at 2.23 eV, 2.79 eV, compressive strain is greater than 1%, the band type changes from the
and 3.20 eV, respectively. The peaks correspond to the energy band with direct band gap of Γ→Γ to the indirect band gap of Γ→M.
approximately 0.95 eV in the conduction band, it shows the energy Obviously, applying mechanical strain cannot change the type II
required for the electron transition from the O-2p orbital of the valence band alignment of the CdO/GaS heterostructure. When compressive
band to the Ga-4p, Ga-4s, and S-3p orbitals of the conduction band. The strain and tensile strain are applied, only the relative potential energy of
absorption coefficient of the CdO/GaS heterostructure obtained based a certain point on the path of the Brillouin zone changes. For instance, as
on the dielectric function of HSE06 is illustrated in Fig. 7(b), and the the compressive strain increases, the energy range of the band at the
absorption coefficient peaks at 387 nm, 442 nm, and 554 nm correspond boundary of the Brillouin zone (M-point) gradually decreases and finally
the first three dielectric peaks in the visible light region. Compared with replaces the Γ-point as the bottom of the conduction band. The results
the stronger optical response of GaS monolayer near-ultraviolet light indicate that mechanical strain can tune the energy band structure of the

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H. Zhao et al. Vacuum 192 (2021) 110434

Fig. 7. (a) The imaginary part of the dielectric constant and (b) the absorption coefficient of the CdO monolayer, GaS monolayer, and the CdO/GaS heterostructure,
and show the solar flux of 1.5G.

Fig. 8. Band structure of the CdO/GaS heterojunction with biaxial strains applied. Fig. (a), (b), (c), and (d) represent tensile strains of 1%, 3%, 5%, and 7%,
respectively; Fig. (e), (f), (g), and (h) represent compression strain of − 1%, − 3%, − 5%, and − 7%, respectively. The red lines are the band structures of the intrinsic
CdO/GaS heterostructure.

CdO/GaS heterostructure, and the band structure modulated by spectrum. As the tensile biaxial strain increases, the peaks redshift, and
applying mechanical strain may be more suitable for aplication in some the absorption coefficient is enhanced by applying strain in visible light
fields than the intrinsic structure. Fig. 9 shows the band gaps with the region. Conversely, as the compressive biaxial strain increases, the peaks
appling mechanical strain. blueshift, and the absorption coefficient decreases in the visible light
The absorption spectrums of the CdO/GaS heterostructure applying region but increase in near UV. So, the CdO/GaS heterostructure has an
mechanical strain are shown in Fig. 10. There are peaks in the near ul­ excellent optical response in visible light region when applying tensile
traviolet and visible light regions, especially in the visible light region biaxial strain and has an excellent optical response in near UV when
and almost covering the entire visible light region of the incident solar applying compressive biaxial strain. These are significant to the

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H. Zhao et al. Vacuum 192 (2021) 110434

interests or personal relationships that could have appeared to influence

the work reported in this paper.

Acknowledgments

This work was partially supported by the National Natural Science

Foundation, China (No.11904285), Industrial Key Project Foundation of
Xi’an, China (No.2019217814GXRC014CG015-GXYD 14.2), the Na­
tional Natural Science Foundation of Natural Science Basic Research
Plan in Shaanxi Province of China (No.2021JM-345), China Post­
doctoral Science Foundation (No.2020M683684XB) and Scientific
Research Program of Shaanxi Provincial Education Department
(No.21JK0789).

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