Applied Surface Science 545 (2021) 148952

Contents lists available at ScienceDirect

Applied Surface Science

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

Full Length Article

Two-dimensional MoSSe/g-GeC van der waals heterostructure as promising

multifunctional system for solar energy conversion
Yu-Liang Liu a, Ying Shi a, *, Chuan-Lu Yang b, *
a
Institute of Atomic and Molecular Physics, Jilin University, Changchun 130012, People’s Republic of China
b
School of Physics and Optoelectronic Engineering, Ludong University, Yantai 26425, People’s Republic of China

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

Keywords: Developing highly efficient photocatalysts for hydrogen/oxygen evolution reaction (HER/OER) and high-
Photovoltaic performance photovoltaic devices are desirable for solar energy applications. However, it still remains chal­
Heterostructure lenging to design an ideal multifunctional material for these purposes. Here, we propose the MoSSe/g-GeC
Water splitting
heterostructure that can both realize overall water splitting reaction and serve as a potential candidate for
Power conversion efficiency
solar cell. The first-principle calculations reveal that the MoSSe/g-GeC heterostructure possesses type-II band
alignment, efficient charge separation, and noticeable visible-light adsorption, which supports its good photo­
electronic performance. Applying appropriate strain can further promote the photocatalytic and photovoltaic
properties of the MoSSe/g-GeC heterostructure. Especially, 4% compressive strain reduce the Gibbs free energy
change of HER/OER to 0.01 eV/1.98 eV by changing interfacial charge transfer. While under 2% tensile strain,
the power conversion efficiency of the MoSSe/g-GeC heterostructure is improved by around 35%. Our results
indicate that MoSSe/g-GeC heterostructure is a promising multifunctional material for solar harvesting and
contribute to developing more relevant systems.

1. Introduction for the purpose of light-harvesting. To date, various novel type-II het­
erostructures have been developed and shown great potential in pho­
Solar energy conversion technologies, such as hydrogen production tocatalytic water splitting or photovoltaic applications [12–20].
from water splitting and power supply with solar cell, are promising for Recently, 2D Janus transition metal dichalcogenides (TMDs) MXY
alleviating current energy shortage and environmental problems [1–3]. (M = Mo, W; X/Y = S, Se and Te where X ∕ = Y) have been gaining
Since the first successful exfoliation of grapheme [4], two-dimensional extensive attentions due to their distinct physical properties induced by
(2D) materials have been considered as a useful platform to realize mirror asymmetry structure [21–23]. As the first synthesized Janus
these solar technologies because of their fascinating properties, structure, Janus MoSSe monolayer has been successfully prepared by
including tunable bandgap, strong optical absorption, and high carrier replacing top-layer S with Se atoms within MoS2 monolayer through
mobilities [5–11]. For the sake of cost reduction and preparation chemical vapor deposition method system [24,25]. It is reported that
simplification, it is very exciting to develop a multifunctional material monolayer Janus MoSSe holds a strong optical response to visible light
that can not only efficiently achieve overall water splitting reaction but and a suitable band alignment with water redox potentials [26], whereas
also exhibit promising application in photovoltaic devices. However, fewer-layered MoSSe structure has a higher carrier mobility, indicating
rational design such an advanced material with above trifunctionality that Janus MoSSe is promising for designing future optoelectronic and
still remains great challenges. It has been widely identified that verti­ photocatalytic devices [27]. Besides Janus MoSSe, 2D graphene-like
cally stacking different 2D materials to form vdW heterostructure can germanium carbide (g-GeC) also has attracted great interests because
tune the electronic structures of 2D materials and bring new exciting of their direct bandgap nature, and thus shown bright prospect in pho­
properties. In particular, the type-II vdW heterostructures, possessing tovoltaics and optoelectronics [28–30]. Likewise, the g-GeC thin film
staggered band alignment, can accelerate spatial separation of photo- also can be prepared through several experimental methods [31,32].
generated carriers and suppress their recombination, which is suitable The 2D g-GeC not only possesses a stable planar structure but share same

* Corresponding authors.
E-mail addresses: [email protected] (Y. Shi), [email protected] (C.-L. Yang).

https://doi.org/10.1016/j.apsusc.2021.148952
Received 12 November 2020; Received in revised form 23 December 2020; Accepted 4 January 2021
Available online 8 January 2021
0169-4332/© 2021 Elsevier B.V. All rights reserved.
Y.-L. Liu et al. Applied Surface Science 545 (2021) 148952

honeycomb structure with that of Janus MoSSe, resulting in small lattice band gap of donor and conduction band offset, respectively. The short
mismatch. Recent studies on Janus MSSe/g-GeC (M = Mo, W) hetero­ circuit current JSC is obtained by the integral in the limit of 100%
structures revealed the characteristic of Rashba spin splitting and type-II external quantum efficiency, where P(ℏω) is the AM1.5 solar energy flux
band alignment, which is highly desirable for spintronic devices [33]. at the photon energy ℏω.
Furthermore, a series of type-II MoSSe-based heterostructures, such as The change of Gibbs free energy (ΔG) is calculated by the following
MoSSe/WSSe [34,35], MoSSe/WSeTe [36], MoSSe/BP [37] and MoSSe/ equation
XN(X = Ga, Al) [38] also have been successively reported and demon­
ΔG = ΔE + ΔEZPE − TΔS − ΔGU (2)
strate their enhanced photocatalytic performances. Despite these efforts,
few previous reports have revealed that a single system can exhibit both where ΔE,ΔEZPE ,TΔS represent the change in total energies, the zero-
excellent performance for overall water splitting reaction and potential point energies and entropic contributions. EZPE could be obtained from
applications in solar cell. the frequency calculation by
In this paper, we construct the MoSSe/g-GeC heterostructure by ∑
vertically stacking the MoSSe and g-GeC monolayers, and achieve the EZPE = 1/2 hν (3)
above-mentioned multifunctionality in the newly designed hetero­
structure. According to the first-principles calculations, a type-II band where ν represents the vibrational frequency.
alignment is distinguished in MoSSe/g-GeC heterostructure, which can Meanwhile, TS is given by
separate the photo-excited electrons and holes. The band edge positions [ )]
∑ ( ) ∑ (
of MoSSe/g-GeC heterostructure are suitable for water splitting and the TS = kb T ln
1
+
hν 1
+ 1 (4)
free energy changes (ΔG) for HER and OER are calculated to further K
1 − e− hν/kb T K
kb T e− hν/kb T − 1
confirm the feasibility of water splitting reaction. In addition, the
introduction of external strain on MoSSe/g-GeC heterostructure not only where e represents the electron charge, h represents Planck’s constant
greatly decreases the ΔG of HER/OER, but also leads to an enhanced and kb is Boltzmann’s constant. Here, T is set to be 298.15 K.
visible-light absorption and the power conversion efficiency. Our pre­
sent works suggest that MoSSe/g-GeC heterostructure have a potential 3. Results and discussions
application for high-efficiency photovoltaic devices and photocatalysis.
3.1. Geometrical structures and stability of MoSSe/g-GeC
2. Computational methods heterostructures

The first-principles calculations are carried out by employing the The crystal structures of Janus MoSSe, g-GeC monolayers are dis­
Vienna ab initio simulation package (VASP) [39] with the projected played in Fig. 1(a) and (b). The MoSSe monolayer exhibits an asym­
augmented wave (PAW) pseudopotentials method [40]. During struc­ metric structure with three atomic layers, in which the top-layer Se and
tural optimization, the generalized gradient approximation (GGA) bottom-layer S atoms are bonded with the middle-layer Mo atoms,
[41,42] in Perdew–Burke–Ernzerhof (PBE) form was adopted for respectively, whereas the 2D g-GeC are planar honeycomb structures
exchange-correlation potential. The convergence tolerances for the connected by Ge and C atoms. The optimized lattice parameters of
forces and energy are set to 0.01 eV/Å and 10− 6 eV, respectively. A MoSSe and g-GeC monolayers are 3.25 and 3.24 Å, respectively, which
Γ-centered Monkhorst-Pack k-point grid of 10 × 10 × 1 is chosen to in accordance with their experimental values and previous theoretical
sample the Brillouin zone and the cutoff energy is set to 500 eV. To results [24,31,33]. The lattice mismatch between MoSSe and g-GeC
better evaluating the vdW heterostructures, semi-empirical DFT-D3 monolayers is only 0.31%, which guarantees the feasibility of the
correction method is adopted for the long-range vdW interaction [43]. experimental stacking. Fig. 1(c) and (d) present the band structures of
The thickness of vacuum space was larger than 20 Å, which is enough to two structures calculated by PBE and HSE06 functionals. The results
avoid the interaction of adjacent layers caused by periodicity. The Heyd- from PBE functional indicate that MoSSe and g-GeC monolayers both are
Scuseria-Ernzerhof (HSE06) hybrid functional [44] is used to further semiconductors with band gap values of 1.56 and 2.11 eV, respectively,
accurately calculate the electronic properties because the PBE functional while HSE06 functional enlarge their band gaps to 2.04 and 2.85 eV,
underestimates bandgaps. Ab initio molecular dynamics (AIMD) simu­ respectively. Our results are in agreement with the previous studies
lations were carried out to examine the thermal stability of MoSSe/g- [37,46,47].
GeC heterostructures. To identify the most possible configuration of MoSSe/g-GeC heter­
The interfacial binding energy (Eb) between the MoSSe and g-GeC is ostructures, based on the relative positions of contacted atoms, we
defined as Eb = EMoSSe/g− GeC − EMoSSe − Eg− GeC , where EMoSSe/g− GeC consider six typical stacking modes, namely AA-stacking, AA1-stacking,
represent the total energies of MoSSe/g-GeC heterostructure, while AB-stacking, AB1-stacking, AC-stacking, AC1-stacking, respectively, as
EMoSSe , Eg− GeC are the total energies of individual MoSSe and g-GeC shown in Fig. 2. The calculated equilibrium interlayer distances and Eb
monolayer, respectively.In order to explore the charge redistribution of all the constructed heterostructures are summarized in Table 1, and
between the g-GeC and MoSSe layer, the plane-averaged charge density the results demonstrate that the most stable pattern of MoSSe/g-GeC
difference Δρ(z) is calculated by Δρ(z) = heterostructure is AB1-stacking. Moreover, the Eb of − 245 meV per
∫ ∫ ∫
ρMoSSe/g− GeC (x, y, z)dxdy − ρMoSSe (x, y, z)dxdy − ρg− GeC (x, y, z)dxdy, unit is more negative than that of previous reported MoSSe/BP (− 130
where the ρMoSSe/g− GeC (x, y, z)dxdy, ρMoSSe (x, y, z)dxdy, ρg− GeC (x, y, z)dxdy meV) [37], MoSSe/graphene (− 83 meV) [48] and g-GeC/BP (− 93.4
meV) [49], implying that the present AB1-stacking structure is favorable
are the charge density at (x, y, z) points of MoSSe/g-GeC heterostructure,
in energy. Therefore, only the most stable pattern of MoSSe/g-GeC
MoSSe monolayer, and g-GeC monolayer, respectively.
heterostructure is discussed in the subsequent calculations. The AIMD
The power conversion efficiency is calculated using the method re­
simulations displayed in Fig. 3(a) reveal that energy and temperature
ported by Scharber et al. [45], in which can be expressed by
have slight oscillation with the increasing time and no significant
( )∫
d ∞ structural change occurs in the end, which further confirms that MoSSe/
βFF VOC JSC 0.65 Eg − ΔEC − 0.3 Egd P(ℏω)d(ℏω)
η= = ∫∞ (1) g-GeC heterostructures are stable thermally.
Psolar 0
P(ℏω)d(ℏω)
3.2. The electronic properties of MoSSe/g-GeC heterostructure
where the fill factor βFF is set to 0.65, and VOC is the maximum open
circuit voltage estimated by Edg − ΔEC − 0.3, where Edg and ΔEC are the
To better investigate the electronic properties of MoSSe/g-GeC

2
Y.-L. Liu et al. Applied Surface Science 545 (2021) 148952

Fig. 1. Top and side views of (a) MoSSe and (b) g-GeC. Band structures of (c) MoSSe and (d) g-GeC with the PBE and HSE06 functional, respectively.

heterostructure, we calculated the projected band structures of the demonstrates a significant charge redistribution in MoSSe/g-GeC het­
MoSSe/g-GeC heterostructure by HSE06 functional. As shown in Fig. 3 erostructure, where charges mainly accumulate at the interfacial region
(b), the MoSSe/g-GeC heterostructure is a direct band gap semi­ close to the MoSSe monolayer and deplete near the g-GeC monolayer,
conductor with valence band maximum (VBM) and conduction band indicating that electrons transfer from g-GeC layer to MoSSe layer. The
minimum (CBM) both locating at K point. The calculated band gaps of charge transfer between the MoSSe and g-GeC layer can introduce an
MoSSe/g-GeC heterostructure is 1.83 eV, which is smaller than their effective build-in electric field, which is important for the photoelec­
individual monolayers. It is worth noting that the CBM of MoSSe/g-GeC tronic applications of MoSSe/g-GeC heterostructure. Similar charge
heterostructure is dominated by the MoSSe monolayer, while the VBM transfer modes are also reported in the previous excellent photocatalytic
originate from the g-GeC monolayer, resulting in a staggered band systems, such as g-GeC/GaN [47], BP/β-AsP [50] and InSe/g-C3N4 [51]
structure. The projected density of states (PDOS) allows us to see more heterostructures.
clearly the contribution of MoSSe and g-GeC to the electronic properties.
As presented in Fig. 3 (c), the VBM of the MoSSe/g-GeC heterostructure
is contributed by the electronic states of the g-GeC monolayer, while 3.3. The photovoltaic and photocatalytic performance of MoSSe/g-GeC
CBM is composed of that of the MoSSe monolayer. Moreover, the charge heterojunction
densities at VBM and CBM for the MoSSe/g-GeC heterostructure are also
in accordance with the results from PDOS calculations. As a result, an The optical absorption coefficients of MoSSe/g-GeC heterostructures
obvious type-II band alignment is demonstrated in the MoSSe/g-GeC are calculated to evaluate their optical response to the solar light. For
heterostructure, which can effectively separate photogenerated elec­ comparison, we also plotted the optical absorption coefficients of MoSSe
trons and holes pairs and prolong carrier lifetimes, enhancing the pho­ and g-GeC monolayers, depicted in Fig. 4(a). One can noted that MoSSe
tocatalytic and photovoltaic performance. monolayer exhibits a larger visible-light absorption coefficient around at
The work functions and charge density differences are calculated to 3.0 eV compared with that of g-GeC monolayers. After they stacked, the
further explore the interfacial properties of the MoSSe/g-GeC hetero­ absorption peaks of the MoSSe/g-GeC heterostructure still can reach 6 ×
structure. The calculated work functions of MoSSe and g-GeC mono­ 104 cm− 1 in the visible light region, and overlaps a wide energy region
layers are 6.00 and 5.21 eV, respectively (Fig. S1). The work function (around 2.0–4.5 eV) with incident Air Mass 1.5G solar flux. This suggests
difference between MoSSe and g-GeC monolayers will induce the charge that MoSSe/g-GeC heterostructures can respond well to the visible and
redistribution at the interfacial region of the MoSSe/g-GeC hetero­ near UV lights. Furthermore, we calculated the power conversion effi­
structure. Fig. 3(d) and (e) present the electrostatic potentials and the ciency of the MoSSe/g-GeC heterostructure as a solar cell device. The
charge density difference of the MoSSe/g-GeC heterostructure. The band edges and band offsets of the heterostructure are shown in Fig. S2.
work function of the MoSSe/g-GeC heterostructure becomes 5.86 eV. Here, the g-GeC layer is the donor and the MoSSe layer is the receptor,
Moreover, the result from the charge density difference indeed and their band gaps are 2.40 and 2.00 eV, respectively. The PCE contour
plots in Fig. 4(b) show that the PCE of the MoSSe/g-GeC heterostructure

3
Y.-L. Liu et al. Applied Surface Science 545 (2021) 148952

Fig. 2. Top and side views of the MoSSe/g-GeC heterostructure with different stacking configurations: (a) AA-stacking, (b) AA1-stacking, (c) AB-stacking, (d) AB1-
stacking, (e) AC-stacking, (f) AC1-stacking.

heterostructure. The changes of Gibbs free energy are calculated to

Table 1
confirm the thermodynamic feasibility of HER and OER in MoSSe/g-GeC
The calculated properties of MoSSe/g-GeC heterostructures with different
heterostructure. The process of HER is demonstrated by
stacking configurations: interlayer distance (dil), binding energy (Eb).
Stacking models AA AA1 AB AB1 AC AC1 * + H+ + e− →H* (5)
dil (Å) 3.60 3.67 3.27 3.39 3.28 3.47
Eb (meV/unit) − 180 − 189 − 232 − 245 − 222 − 216 and that of OER is divided into four steps as follow:

* + H2 O→OH* + H+ + e− (6)
is 7.6%, which is comparable to reported AsP/CdSe heterostructure
(13%) [52] and the organic solar cells (11.7%) [53]. Therefore, the OH* →O* + H+ + e− (7)
MoSSe/g-GeC heterostructure should be a promising candidate material
for solar cells. O* + H2 O→OOH* + H+ + e− (8)
To explore the applications of MoSSe/g-GeC heterostructures in
water splitting, we firstly calculated the band alignments of MoSSe and OOH* →* + O2 + H+ + e− (9)
g-GeC monolayers and their heterostructures at pH = 0. As displayed in
where the * represent the active site on the MoSSe/g-GeC hetero­
Fig. 4(c), the absolute band edges of the MoSSe monolayer both straddle
structure. It is clearly shown that the intermediates in the HER is H* and
the water redox potential, while monolayer g-GeC only can act as a
reduction photocatalyst due to its higher VBMs than the oxidation po­ in the OER are OH* , O* , and OOH* , respectively. Detailed configurations
tential of O2/H2O, which are in accordance with previous works[46]. and parameters of MoSSe/g-GeC heterostructure in the calculation of
Interestingly, MoSSe/g-GeC heterostructure can keep a suitable band free energy are displayed in Fig. S4 and Table S1-S2. Ultimately, the
edge positions for the water-splitting reaction, implying it is promising calculated ΔG of HER for MoSSe/g-GeC heterostructure is 0.69 eV,
for photocatalytic water splitting. which is shown in Fig. 4(d). For OER, the rate limiting step is that O*
It is known that the adsorption of water molecule on the surface of reacts with one H2O molecule to produce OOH*, which resulting in an
photocatalyst is one crucial step for water splitting reaction. To explore ΔG of 2.58 eV. While under the equilibrium potential of 1.23 V, as
the possible water splitting process, we firstly calculated the adsorption shown in Fig. 5(a), the ΔG in rate limiting step is decreased to 1.35 eV.
energy of water molecule on the two surfaces of MoSSe/g-GeC hetero­ The present ΔGs of HER and OER for the MoSSe/g-GeC heterostructure
structure. Three possible adsorption sites were considered, including top are lower than that of previous reported photocatalysts, such as g-GaN/
of Ge (Getop), top of C (Ctop) and hollow sites, as shown in Fig. S3. The Mg(OH)2 heterostructure[54] (2.915 eV for OER) and SiI2 monolayer
results demonstrate that the water adsorption energies of three sites on [55] (0.75 eV for HER), suggesting the MoSSe/g-GeC heterostructure is
the g-GeC surface all are more negative than that of the MoSSe surface, potential structure for water splitting to produce hydrogen and oxygen.
indicating that the water splitting reaction could prefer to occur on the
g-GeC surface. Therefore, we next discuss in detail water splitting pro­
cess, including HER and OER, on the g-GeC surface of MoSSe/g-GeC

4
Y.-L. Liu et al. Applied Surface Science 545 (2021) 148952

Fig. 3. (a) Variations of energy and temperature for MoSSe/g-GeC heterostructure during AIMD simulation lasting for 5 ps at 500 K. The insets represent the top
views of initial and final structures in AIMD simulation, respectively. The projected (b) band structures and (c) density of states of MoSSe/g-GeC. The insets in (c) are
the charge densities of CBM and VBM. (d) The electrostatic potential and (e) the plane-averaged charge density difference of the MoSSe/g-GeC. 3D isosurface of the
charge density differences also plots in inset of (e), where the yellow and blue represent the charge accumulation and depletion, respectively. (For interpretation of
the references to colour in this figure legend, the reader is referred to the web version of this article.)

Fig. 4. (a) The absorption coefficients of MoSSe, g-GeC monolayer and the MoSSe/g-GeC heterostructure, respectively. (b) Calculated power conversion efficiency
contour as a function of the donor bandgap and conduction band offset. (c) The band alignment of MoSSe, g-GeC monolayer and the MoSSe/g-GeC heterostructure at
HSE06 level, respectively. (d) The change of Gibbs free energy for HER on pristine and strained MoSSe/g-GeC heterostructures at pH = 0.

5
Y.-L. Liu et al. Applied Surface Science 545 (2021) 148952

Fig. 5. (a) The change of Gibbs free energy for OER paths on the MoSSe/g-GeC heterostructures. (b) The effects of strains on band gaps and band edge alignments of
MoSSe/g-GeC heterostructure. The free energy profile for OER on − 4% strained MoSSe/g-GeC heterostructures at (c) U = 0 V and (d) U = 1.91 V, respectively. (e)
The absorption coefficients of MoSSe/g-GeC heterostructure under different strains.

3.4. The effect of strain on MoSSe/g-GeC heterostructures excellent HER activity with ΔG of 0.01 eV, which is lower than that of Pt
(− 0.09 eV) [58]. To further understand such catalytic performance of
Strain engineering has been considered as an effective means to MoSSe/g-GeC heterostructure, we calculated the bader charge variation
regulate the electronic properties of two-dimensional (2D) materials of individual layers at different strains, which is plotted in Fig. S6. From
without introducing dopants and defects. The previous reports have the figure we can find that the introduction of compressive strain can
revealed that the photocatalytic performances of MoSSe and g-GeC promote charge transfer from the MoSSe monolayer to g-GeC, and hence
monolayers can be significantly improved by applying appropriate induce the charge redistribution on the surfaces of MoSSe/g-GeC het­
strain [29,56,57]. Here, we calculated the effect of stain on the elec­ erostructure. Such charge redistribution makes the g-GeC surface more
tronic and optical properties of the MoSSe/g-GeC heterostructure (The charged under compressive strain, which is beneficial for the adsorption
negative and positive value represent the compressive and tensile stain, of hydrogen atom, leading to the enhancement of HER activities. Similar
respectively.). The variations in band energy gap and band edge align­ strain behaviors also are revealed in previous reports [59,60]. Mean­
ments of the MoSSe/g-GeC heterostructure as a function of strain are while, the OER performance of MoSSe/g-GeC heterostructure also can
plotted in Fig. 5(b). From the figure we can find that the band energy be effectively regulated by strain engineering (see Fig. S7). It should be
gaps of the MoSSe/g-GeC heterostructure exhibit a rapid decrease with noted that 4% compressive strain still shows a better OER activity. In
the increase of tensile strain, while it increases slowly under the this case, the second step, where the OH* decompose to form O*, be­
compressive strain. The change of band gap can be attributed to the shift comes the rate limiting step and the ΔG in this step is only 1.91 eV (Fig. 5
of their CBMs, and strain have no obvious influence on their VBMs. More (c)). Accordingly, when the external potential of 1.91 V is satisfied, all
interestingly, an indirect to direct bandgap transition occurs in the reactions of OER are downhill in free energy (see in Fig. 5(d)), implying
MoSSe/g-GeC heterostructure under certain strain. The chosen band the OER in water splitting is thermodynamically favorable at this con­
structures plotted in Fig. S5 (a)–(d) demonstrate that the CBM moves dition. Fortunately, the band edge positions of MoSSe/g-GeC hetero­
from the K point to one point between Γ and K leading to this transition. structure still straddle water redox potential under 4% compressive
In addition, we can see that the CBM and VBM in MoSSe/g-GeC heter­ strain, indicating that this heterostructure can more effectively achieve
ostructures still originate the contribution of MoSSe layer and g-GeC overall water splitting reaction by applying appropriate compressive
layer, respectively, thus MoSSe/g-GeC heterostructures can remain strains.
type-II band alignment under the entire strain. Fig. 5(e) show the changes in the optical absorptions of MoSSe/g-
Next, the OER and HER performances of strained structures are GeC heterostructure as a function of strain. We noted that the optical
further investigated to evaluate their photocatalytic activities. The absorptions of MoSSe/g-GeC heterostructures within the visible light
relaxed structures and relative parameters of intermediates during free region are enhanced by the tensile strain, which improves the response
energy calculation are presented in Fig. S4 and Table S1-S2. For tensile to solar energy. Especially, the 2% tensile strain can significantly reduce
strain, the obtained ΔGs of HER for MoSSe/g-GeC heterostructure in­ the donor bandgap and conduction band offset of MoSSe/g-GeC heter­
crease (see Fig. 4(d)), which is not conducive for the hydrogen evolu­ ostructure (see Fig. S2), then PCE is improved to 10.3%, which is dis­
tion. While compressive strain can reduce the ΔGs of HER. Especially, played in Fig. 4(b). Consequently, the photocatalytic and photovoltaic
4% compressive strain makes MoSSe/g-GeC heterostructure exhibit an performance of MoSSe/g-GeC heterostructure can be further enhanced

6
Y.-L. Liu et al. Applied Surface Science 545 (2021) 148952

under strain engineering. [10] X. Zhang, C. Cao, A. Bieberle-Hütter, Enhanced electrochemical water oxidation:
the impact of nanoclusters and nanocavities, Phys. Chem. Chem. Phys. 19 (2017)
31300–31305.
4. Conclusions [11] Z. Li, J. Li, C. He, T. Ouyang, C. Zhang, S. Zhang, C. Tang, R.A. Römer, J. Zhong,
Few-layerβ-SnSe with strong visible light absorbance and ultrahigh carrier
mobility, Phys. Rev. Appl. 13 (2020), 014042.
In summary, using first-principles calculations, we propose the
[12] Y. Mao, C. Xu, J. Yuan, H. Zhao, A two-dimensional GeSe/SnSe heterostructure for
MoSSe/g-GeC heterostructure as a promising multifunctional candidate high performance thin-film solar cells, J. Mater. Chem. A 7 (2019) 11265–11271.
for achieving overall water splitting reaction and photovoltaic applica­ [13] X. Niu, Y. Li, Q. Zhou, H. Shu, J. Wang, Arsenene-based heterostructures: highly
efficient bifunctional materials for photovoltaics and photocatalytics, ACS Appl.
tion. Our results demonstrate that the MoSSe/g-GeC heterostructure is a
Mater. Interfaces 9 (2017) 42856–42861.
type-II semiconductor and possess a noticeable visible-light adsorption [14] A. Mahmood, G. Shi, X. Wang, X. Xie, J. Sun, Photocatalytic properties of novel
intensity. The positions of valence and conduction-band edges met the two-dimensional B4C3/g-C3N4 van der Waals heterojunction with moderate
requirement of water splitting reaction. More importantly, we found bandgap and high carrier mobility: a theoretical study, Appl. Catal. B: Environ. 278
(2020) 119310.
that strain engineering can further regulate the catalytic activities of [15] Z. Zhang, Q. Qian, B. Li, K.J. Chen, Interface engineering of monolayer MoS2/GaN
MoSSe/g-GeC heterostructure by changing interfacial charge transfer. hybrid heterostructure: modified band alignment for photocatalytic water splitting
Under 4% compressive strain, the MoSSe/g-GeC heterostructure ex­ application by nitridation treatment, ACS Appl. Mater. Interfaces 10 (2018)
17419–17426.
hibits superior catalytic activities with the ΔG of HER/OER being just [16] K. Cheng, Y.u. Guo, N. Han, X. Jiang, J. Zhang, R. Ahuja, Y. Su, J. Zhao, 2D lateral
0.01/1.91 eV. Besides, the tensile strain can enhance the optical heterostructures of group-III monochalcogenide: potential photovoltaic
adsorption of MoSSe/g-GeC heterostructure and the PCE is promoted to applications, Appl. Phys. Lett. 112 (2018) 143902.
[17] S. Arra, R. Babar, M. Kabir, van der Waals heterostructure for photocatalysis:
10.3% at 2% tensile strain. Therefore, the present MoSSe/g-GeC heter­ graphitic carbon nitride and Janus transition-metal dichalcogenides, Phys. Rev.
ostructure can simultaneously be considered as an efficient visible-light Mater. 3 (2019), 095402.
photocatalyst and a promising photovoltaic material. [18] B. Wang, H. Yuan, J. Chang, X. Chen, H. Chen, Two dimensional InSe/C2N van der
Waals heterojunction as enhanced visible-light-responsible photocatalyst for water
splitting, Appl. Surf. Sci. 485 (2019) 375–380.
CRediT authorship contribution statement [19] L. Zhang, X. Hao, Y. Li, Z. Jin, Performance of WO3/g-C3N4 heterojunction
composite boosting with NiS for photocatalytic hydrogen evolution, Appl. Surf. Sci.
499 (2020), 143862.
Yu-Liang Liu: Data curation, Investigation, Writing - original draft.
[20] H. Fan, H. Zhou, W. Li, S. Gu, G. Zhou, Facile fabrication of 2D/2D step-scheme
Ying Shi: Conceptualization, Methodology, Supervision, Writing - re­ In2S3/Bi2O2CO3 heterojunction towards enhanced photocatalytic activity, Appl.
view & editing. Chuan-Lu Yang: Visualization, Software. Surf. Sci. 504 (2020), 144351.
[21] L. Dong, J. Lou, V.B. Shenoy, Large in-plane and vertical piezoelectricity in Janus
transition metal dichalchogenides, ACS Nano 11 (2017) 8242–8248.
Declaration of Competing Interest [22] H. Jin, T. Wang, Z.-R. Gong, C. Long, Y. Dai, Prediction of an extremely long
exciton lifetime in a Janus-MoSTe monolayer, Nanoscale 10 (2018) 19310–19315.
[23] C. Xia, W. Xiong, J. Du, T. Wang, Y. Peng, J. Li, Universality of electronic
The authors declare that they have no known competing financial characteristics and photocatalyst applications in the two-dimensional Janus
interests or personal relationships that could have appeared to influence transition metal dichalcogenides, Phys. Rev. B 98 (2018), 165424.
the work reported in this paper. [24] 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, Y. Wang, D. Sokaras, D. Nordlund, P. Yang, D.A. Muller, M.-
Y. Chou, X. Zhang, L.-J. Li, Janus monolayers of transition metal dichalcogenides,
Acknowledgments Nature Nanotech. 12 (2017) 744–749.
[25] J. Zhang, S. Jia, I. Kholmanov, L. Dong, D. Er, W. Chen, H. Guo, Z. Jin, V.B. Shenoy,
L.i. Shi, J. Lou, Janus monolayer transition-metal dichalcogenides, ACS Nano 11
This work was supported by the National Basic Research Program of (2017) 8192–8198.
China (Grant No. 2019YFA0307701) and the National Natural Science [26] W.-J. Yin, B.o. Wen, G.-Z. Nie, X.-L. Wei, L.-M. Liu, Tunable dipole and carrier
Foundation of China (No. 11874180), Young and Middle-aged Scientific mobility for a few layer Janus MoSSe structure, J. Mater. Chem. C 6 (2018)
1693–1700.
and Technological Innovation leaders and Team Projects in Jilin Prov­ [27] Z. Guan, S. Ni, S. Hu, Tunable electronic and optical properties of monolayer and
ince (20200301020RQ). multilayer Janus MoSSe as a photocatalyst for solar water splitting: a first-
principles study, J. Phys. Chem. C 122 (2018) 6209–6216.
[28] F. Ersan, A.G. Gökçe, E. Aktürk, Point defects in hexagonal germanium carbide
Appendix A. Supplementary material monolayer: A first-principles calculation, Appl. Surf. Sci. 389 (2016) 1–6.
[29] X. Gao, Y. Shen, Y. Ma, S. Wu, Z. Zhou, Graphene/g-GeC bilayer heterostructure:
Supplementary data to this article can be found online at https://doi. Modulated electronic properties and interface contact via external vertical strains
and electric fileds, Carbon 146 (2019) 337–347.
org/10.1016/j.apsusc.2021.148952. [30] H. Şahin, S. Cahangirov, M. Topsakal, E. Bekaroglu, E. Akturk, R.T. Senger,
S. Ciraci, Monolayer honeycomb structures of group-IV elements and III-V binary
References compounds: First-principles calculations, Phys. Rev. B 80 (2009).
[31] H. Yuan, R.S. Williams, Synthesis by laser ablation and characterization of pure
germanium-carbon alloy thin films, Chem. Mater. 5 (1993) 479–485.
[1] J. Liu, Y. Liu, N. Liu, Y. Han, X. Zhang, H. Huang, Y. Lifshitz, S.-T. Lee, J. Zhong,
[32] X. Wu, W. Zhang, L. Yan, R. Luo, The deposition and optical properties of Ge1− xCx
Z. Kang, Metal-free efficient photocatalyst for stable visible water splitting via a
thin film and infrared multilayer antireflection coatings, Thin Solid Films 516
two-electron pathway, Science 347 (2015) 970–974.
(2008) 3189–3195.
[2] H.B. Gray, Powering the planet with solar fuel, Nature Chem. 1 (2009) 7.
[33] H.U. Din, M. Idrees, A. Albar, M. Shafiq, I. Ahmad, C.V. Nguyen, B. Amin, Rashba
[3] F. Gao, G.-L. Zhao, S. Yang, J.J. Spivey, Nitrogen-doped fullerene as a potential
spin splitting and photocatalytic properties of GeC-MSSe(M=Mo, W) van der Waals
catalyst for hydrogen fuel cells, J. Am. Chem. Soc. 135 (2013) 3315–3318.
heterostructures, Phys. Rev. B 100 (2019), 165425.
[4] K.S. Novoselov, A.K. Geim, S.V. Morozov, D. Jiang, Y. Zhang, S.V. Dubonos, I.
[34] F. Li, W. Wei, P. Zhao, B. Huang, Y. Dai, Electronic and optical properties of
V. Grigorieva, A.A. Firsov, Electric field effect in atomically thin carbon films,
pristine and vertical and lateral heterostructures of Janus MoSSe and WSSe,
Science 306 (2004) 666–669.
J. Phys. Chem. Lett. 8 (2017) 5959–5965.
[5] H.Y. Liu, C.L. Yang, M.S. Wang, X.G. Ma, Two-dimensional BiP3 with high carrier
[35] W. Guo, X. Ge, S. Sun, Y. Xie, X. Ye, The strain effect on the electronic properties of
mobility and moderate band gap for hydrogen generation from water splitting,
the MoSSe/WSSe van der Waals heterostructure: a first-principles study, Phys.
Appl. Surf. Sci. 501 (2020), 144263.
Chem. Chem. Phys. 22 (2020) 4946–4956.
[6] X. Lv, W. Wei, Q. Sun, F. Li, B. Huang, Y. Dai, Two-dimensional germanium
[36] Z. Zhou, X. Niu, Y. Zhang, J. Wang, Janus MoSSe/WSeTe heterostructures: a direct
monochalcogenides for photocatalytic water splitting with high carrier mobility,
Z-scheme photocatalyst for hydrogen evolution, J. Mater. Chem. A 7 (2019)
Appl. Catal. B: Environ. 217 (2017) 275–284.
21835–21842.
[7] H.-C. Huang, Y. Zhao, J. Wang, J. Li, J. Chen, Q. Fu, Y.-X. Bu, S.-B. Cheng, Rational
[37] D. Chen, X. Lei, Y. Wang, S. Zhong, G. Liu, B. Xu, C. Ouyang, Tunable electronic
design of an efficient descriptor for single-atom catalysts in the hydrogen evolution
structures in BP/MoSSe van der Waals heterostructures by external electric field
reaction, J. Mater. Chem. A 8 (2020) 9202–9208.
and strain, Appl. Surf. Sci. 497 (2019), 143809.
[8] P. Cheng, T. Wu, J. Liu, W.-Q. Deng, K. Han, Lead-free, two-dimensional mixed
[38] K. Ren, S. Wang, Y. Luo, J.-P. Chou, J. Yu, W. Tang, M. Sun, High-efficiency
germanium and tin perovskites, J. Phys. Chem. Lett. 9 (2018) 2518–2522.
photocatalyst for water splitting: a Janus MoSSe/XN (X = Ga, Al) van der Waals
[9] Q. Liang, G. Brocks, X. Zhang, A. Bieberle-Hütter, Monolayer nitrides doped with
heterostructure, J. Phys. D: Appl. Phys. 53 (2020), 185504.
transition metals as efficient catalysts for water oxidation: the singular role of
nickel, J. Phys. Chem. C 123 (2019) 26289–26298.

7
Y.-L. Liu et al. Applied Surface Science 545 (2021) 148952

[39] G. Kresse, J. Furthmüller, Efficient iterative schemes for ab initio total-energy [51] C. He, J.H. Zhang, W.X. Zhang, T.T. Li, Type-II InSe/g-C3N4 heterostructure as a
calculations using a plane-wave basis set, Phys. Rev. B 54 (1996) 11169–11186. high-efficiency oxygen evolution reaction catalyst for photoelectrochemical water
[40] P.E. Blöchl, Projector augmented-wave method, Phys. Rev. B 50 (1994) splitting, J. Phys. Chem. Lett. 10 (2019) 3122–3128.
17953–17979. [52] X. Cai, Y. Chen, B. Sun, J. Chen, H. Wang, Y. Ni, L.i. Tao, H. Wang, S. Zhu, X. Li,
[41] J.P. Perdew, K. Burke, M. Ernzerhof, Generalized gradient approximation made Y. Wang, J. Lv, X. Feng, S.A.T. Redfern, Z. Chen, Two-dimensional Blue-AsP
simple, Phys. Rev. Lett. 77 (1996) 3865–3868. monolayers with tunable direct band gap and ultrahigh carrier mobility show
[42] J.P. Perdew, Y. Wang, Accurate and simple analytic representation of the electron- promising high-performance photovoltaic properties, Nanoscale 11 (2019)
gas correlation energy, Phys. Rev. B 45 (1992) 13244–13249. 8260–8269.
[43] S. Grimme, J. Antony, S. Ehrlich, H. Krieg, A consistent and accurate ab initio [53] J. Zhao, Y. Li, G. Yang, K. Jiang, H. Lin, H. Ade, W. Ma, H. Yan, Efficient organic
parametrization of density functional dispersion correction (DFT-D) for the 94 solar cells processed from hydrocarbon solvents, Nat. Energy 1 (2016) 15027.
elements H-Pu, J. Chem. Phys. 132 (2010), 154104. [54] K. Ren, J. Yu, W. Tang, A two-dimensional vertical van der Waals heterostructure
[44] J. Heyd, G.E. Scuseria, M. Ernzerhof, Hybrid functionals based on a screened based on g-GaN and Mg(OH)2 used as a promising photocatalyst for water splitting:
Coulomb potential, J. Chem. Phys. 118 (2003) 8207–8215. a first-principles calculation, J. Appl. Phys. 126 (2019), 065701.
[45] M.C. Scharber, D. Mühlbacher, M. Koppe, P. Denk, C. Waldauf, A.J. Heeger, C. [55] Z.-H. Liu, C.-L. Yang, M.-S. Wang, X.-G. Ma, SiI2 monolayer as a promising
J. Brabec, Design rules for donors in bulk-heterojunction solar cells—towards 10 % photocatalyst for water splitting hydrogen production under the irradiation of solar
energy-conversion efficiency, Adv. Mater. 18 (2006) 789–794. light, Int. J. Hydrogen Energy 45 (2020) 17517–17524.
[46] K. Ren, C. Ren, Y.i. Luo, Y. Xu, J. Yu, W. Tang, M. Sun, Using van der Waals [56] T.Y. Lü, X.X. Liao, H.Q. Wang, J.C. Zheng, Tuning the indirect–direct band gap
heterostructures based on two-dimensional blue phosphorus and XC (X = Ge, Si) transition of SiC, GeC and SnC monolayer in a graphene-like honeycomb structure
for water-splitting photocatalysis: a first-principles study, Phys. Chem. Chem. Phys. by strain engineering: a quasiparticle GW study, J. Mater. Chem. 22 (2012)
21 (2019) 9949–9956. 10062–10068.
[47] P. Lou, J.Y. Lee, GeC/GaN vdW heterojunctions: a promising photocatalyst for [57] C. Jin, X. Tang, X. Tan, S.C. Smith, Y. Dai, L. Kou, A Janus MoSSe monolayer: a
overall water splitting and solar energy conversion, ACS Appl. Mater. Interfaces 12 superior and strain-sensitive gas sensing material, J. Mater. Chem. A 7 (2019)
(2020) 14289–14297. 1099–1106.
[48] Y.i. Li, J. Wang, B. Zhou, F. Wang, Y. Miao, J. Wei, B. Zhang, K. Zhang, Tunable [58] T. He, S.K. Matta, G. Will, A. Du, Transition-metal single atoms anchored on
interlayer coupling and Schottky barrier in graphene and Janus MoSSe graphdiyne as high-efficiency electrocatalysts for water splitting and oxygen
heterostructures by applying an external field, Phys. Chem. Chem. Phys. 20 (2018) reduction, Small Methods 3 (2019) 1800419.
24109–24116. [59] H. Li, C. Tsai, A.L. Koh, L. Cai, A.W. Contryman, A.H. Fragapane, J. Zhao, H.S. Han,
[49] X. Gao, Y. Shen, Y. Ma, S. Wu, Z. Zhou, A water splitting photocatalysis: blue H.C. Manoharan, F. Abild-Pedersen, J.K. Nørskov, X. Zheng, Activating and
phosphorus/g-GeC van der Waals heterostructure, Appl. Phys. Lett. 114 (2019), optimizing MoS2 basal planes for hydrogen evolution through the formation of
093902. strained sulphur vacancies, Nat. Mater. 15 (2016) 48–53.
[50] Y.L. Liu, Y. Shi, H. Yin, C.L. Yang, Two-dimensional BP/β-AsP van der Waals [60] C. Ling, L. Shi, Y. Ouyang, Q. Chen, J. Wang, Transition metal-promoted V2CO2
heterostructures as promising photocatalyst for water splitting, Appl. Phys. Lett. (MXenes): a new and highly active catalyst for hydrogen evolution reaction, Adv.
117 (2020), 063901. Sci. 3 (2016) 1600180.