Solar Energy 182 (2019) 453–461

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Solar Energy
journal homepage: www.elsevier.com/locate/solener

Numerical simulation of graphene/GaAs heterojunction solar cells T

a,b a,b a,b,⁎ c
Meng Yu , Yanqiu Li , Qijin Cheng , Shuai Li
a
College of Energy, Xiamen University, Xiamen 361102, PR China
b
Shenzhen Research Institute of Xiamen University, Shenzhen 518000, PR China
c
College of Physics & Information Engineering, Quanzhou Normal University, Quanzhou 362000, PR China

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

Keywords: For a thorough understanding of graphene/GaAs heterojunction solar cells, the effect of the graphene work
Numerical simulation function, absorption loss, density of interface states, as well as the incorporation of an AlxGa1−xAs (0 ≤ x ≤ 1)
Graphene buffer layer on the performance of graphene/GaAs heterojunction solar cells was investigated via AFORS-HET
GaAs simulation software. It is demonstrated that graphene with a work function of approximately 5 eV favors the
Buffer layer
efficiency improvement. The absorption loss is also an unnegligible factor for the optimization of the graphene
Solar cell
work function. The density of interface states can significantly affect the carrier recombination at the hetero-
junction interface between graphene and GaAs and the corresponding photovoltaic performance. In addition, the
work function of a back electrode should also be taken into account for selecting a back electrode material due to
its significant influence on the carrier transportation and collection. Furthermore, when an AlxGa1−xAs (x = 0.2)
buffer layer was introduced to this heterojunction interface, an enhanced photovoltaic conversion efficiency of
24.78% can be achieved. Finally, a comparison among simulation and experimental data for the graphene/GaAs
heterojunction solar cells is presented. This study indicates the great potential of graphene/GaAs heterojunction
for the application in high-efficiency solar cells.

1. Introduction graphene doping, application of graphene nanowires, antireflection

Due to their excellent characteristics such as environmental
friendliness, easy access and renewability, solar cells are considered as
an ideal candidate for future energy resources. Considerable attention
has been paid to the fabrication of high-efficiency and low-cost solar
cells in the past few decades, represented by traditional crystalline si-
licon, Cu(In, Ga)Se2 and perovskite solar cells (Lewis, 2007; Pillai et al.,
2007; Panthani et al., 2008; Sum and Mathews, 2014). Recently, as a
two-dimensional material, graphene has attracted tremendous research
attention because it possesses outstanding photovoltaic properties: high
optical transmittance of 97.7% within the visible light region, high
carrier mobility of 15,000 cm2 V−1 s−1 at room temperature, excellent
chemical and physical stability (Geim and Novoselov, 2007; Berger
et al., 2006; Kim et al., 2009). These unique properties make graphene
promising for potential applications in transparent electrodes, displays,
solar cells, etc.
Recently, heterojunction solar cells based on the combination of
graphene and semiconductors have attracted tremendous research in-
terest. Li et al. (2010) firstly reported the graphene/Si solar cell with a
photovoltaic conversion efficiency (PCE) of 1.5%. Subsequently, var-
ious methods for performance enhancement have been applied such as
layer and interface passivation (Miao et al., 2012; Fan et al., 2011;
Zhang et al., 2013; Shi et al., 2013). To date, a PCE of 15.6% has been
achieved for graphene/Si heterojunction solar cells (Song et al., 2015),
which is close to the commercial crystalline silicon solar cells. More-
over, graphene/Si heterojunction solar cells have a lower cost and
simpler fabrication process compared with crystalline silicon solar cells.
In comparison with the widely used Si, GaAs possesses a series of ex-
traordinary characteristics, including a higher carrier mobility
(8500 cm2 V−1 s−1), higher absorption coefficient (104 cm−1), better
radiation resistance, more compatible bandgap (1.42 eV) within the
visible light spectrum, and only several hundreds of nanometers of
GaAs is sufficient for carriers’ generation due to its direct bandgap
nature (Blakemore, 1982; Gunn and Elliott, 1966). These characteristics
make GaAs a more promising material for heterojunction optoelec-
tronic devices such as solar cells and photodetectors (Yoon et al., 2010;
Cotal et al., 2009; Luo et al., 2015). However, research on graphene/
GaAs heterojunction solar cells is scarce. Jie et al. (2013) firstly fabri-
cated this type of heterojunction solar cells by utilizing graphene and n-
GaAs. The reported efficiency of the bilayer graphene/GaAs hetero-
junction solar cell was 1.95%, which was much lower than our ex-
pectation. He et al. (2015) reported the graphene/GaAs solar cell with a

⁎
Corresponding author at: College of Energy, Xiamen University, Xiamen 361102, PR China.
E-mail address: Qijin.Cheng@xmu.edu.cn (Q. Cheng).

https://doi.org/10.1016/j.solener.2019.02.061
Received 19 January 2019; Received in revised form 22 February 2019; Accepted 24 February 2019
0038-092X/ © 2019 International Solar Energy Society. Published by Elsevier Ltd. All rights reserved.
M. Yu, et al. Solar Energy 182 (2019) 453–461

PCE of 13.7% using TFSA as a doping material, TiO2 as an anti-reflec- Table 1

tion film and P3HT as a hole transport layer. The obtained PCE in- Input parameters for functional layers in simulation (Messei and Aida, 2015;
dicates that the graphene/GaAs heterojunction solar cell has a great New Semiconductor Materials (NSMs) Archive – Aluminium Gallium Arsenide).
potential for research and application. Parameters n-GaAs AlxGa1−xAs
Numerical simulation provides a pre-evaluation of various para- (x = 0.2)
meters’ influence on the performance of solar cells, such as work
Layer thickness (cm) 1.5 × 10−3 5 × 10−7
function, layer thickness, bandgap and density of interface states. In
Bandgap (eV) 1.42 1.84
addition, it provides guidance for actual experiments to promote the Optical bandgap (eV) 1.42 1.84
exploration process (Sen, 2009; Oppong-Antwi et al., 2017). Electron affinity (eV) 4.07 3.7
In our previous work (Li et al., 2019), we discussed the impact of the Dielectric constant 12.9 10.6
incorporation of an electron-blocking/hole-transporting layer on the Effective conduction band density (cm−3) 4.7 × 1017 1.6 × 1019
performance of graphene/GaAs solar cells via AFORS-HET software. In Effective valence band density (cm−3) 9 × 1018 4 × 1018
Electron mobility (cm2 V−1 s−1) 4000 212
this simulation work, we systematically investigate the effect of various
Hole mobility (cm2 V−1 s−1) 200 126
factors (including the graphene work function, absorption loss, density Acceptor concentration (cm−3) 0 0
of interface states as well as the work function of the back electrode) on Donor concentration (cm−3) 1 × 1017 0
the cell performance for a comprehensive and thorough understanding Characteristic energy for acceptors (eV) 0.01 0.01
of graphene/GaAs heterojunction solar cells. Importantly, during the Characteristic energy for donors (eV) 0.01 0.01
Prefactor for donor-like Urbach tail states 1 × 1014 1 × 1014
analysis of various factors on the cell performance, we have in-
GDO (cm−3 eV−1)
vestigated the change of the electric field distribution and the energy Prefactor for acceptor-like Urbach tail states 1 × 1014 1 × 1014
band diagram in detail. This helps us to shed light on the underlying GAO (cm−3 eV−1)
physical mechanism affecting the performance of the graphene/GaAs Thermal velocity of electrons (cms−1) 4.4 × 107 1.98 × 105
heterojunction solar cells. Moreover, an AlxGa1−xAs (0 ≤ x ≤ 1) layer Thermal velocity of holes (cm s−1) 1 × 107 1.7 × 105
has been introduced into the graphene/GaAs heterojunction Schottky Layer density (g cm−3) 5.32 5.0
Auger recombination coefficient for 1 × 10−30 0.7 × 10−31
solar cells for interface optimiztion. A high photovoltaic conversion
electrons (cm6 s−1)
efficiency of 24.78% has been achieved through the introduction of an Auger recombination coefficient for holes 1 × 10−30 6.1 × 10−31
AlxGa1−xAs ( x = 0.2) buffer layer. Finally, a comparison among simu- (cm6 s−1)
lation and experimental data for the graphene/GaAs heterojunction Direct band to band recombination 7.2 × 10−10 0
solar cells is presented. coefficient (cm3 s−1)

2. Structure of solar cells and simulation details

Fig. 1 shows the schematic diagrams of Ag/graphene/n-GaAs/Ag
Schottky heterojunction solar cells with and without a buffer layer. The
simulation work was carried out by AFORS-HET software. This software
is widely used for modeling of heterojunction (HJ) and heterojunction
with intrinsic thin-layer (HIT) solar cells. In fact, AFORS-HET software
analyzes the properties of heterojunction solar cells through solving the
one-dimensional Poisson equation and the continuity equations based
on Shockley–Read–Hall recombination statistics.
In this simulation work, we firstly investigate the effect of graphene
work function on the performance of graphene/GaAs heterojunction
solar cells. Subsequently, the influence of several factors (such as gra-
phene absorption loss, density of interface states and work function of
the back electrode) on the performance of graphene/GaAs solar cells is
also investigated in detail. For further performance improvement, a
thickness of 5 nm AlxGa1−xAs (x = 0.2) layer is employed into the in-
terface between graphene and GaAs. The basic parameters for the
graphene/n-GaAs heterojunction solar cells are listed in Table 1.
Optical parameters of front and back Ag electrodes are set as default
values in the AFORS-HET software. The operation temperature was set
at 300 K, and the solar illumination was set at AM 1.5 with a power
density of 100 mW/cm2.
3. Result and discussion
3.1. Influence of graphene work function
In the graphene/GaAs Schottky heterojunction solar cells, graphene
not only plays a role as a transparent electrode for light transmission,
but also serves as a layer for carriers’ separation and collection.
Therefore, it has a significant impact on the performance of graphene/
GaAs heterojunction solar cells. Some early studies have revealed that
the work function of graphene is variable through applying an electric
field or chemical doping and ranges from 4.3 to 5.0 eV (Hibino et al.,
2009; Garg et al., 2014).
Herein, we firstly investigated the photovoltaic parameters of

Fig. 1. Schematics of (a) graphene/GaAs and (b) graphene/AlxGa1−xAs (x = 0.2)/GaAs heterojunction solar cells in this simulation.

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M. Yu, et al.
Fig. 2. (a) Effect of graphene work function on photovoltaic properties of graphene/GaAs solar cells. (b) Conduction band diagrams of graphene/GaAs solar cells in
the GaAs side. Inset of (b) shows the conduction band diagram at the position of back contact.
graphene/GaAs heterojunction solar cells with different work functions
of graphene. As shown in Fig. 2(a), when the work function of graphene
increases from 4.3 to 5.0 eV, the short-circuit current density (Jsc ) in-
itially increases from 44.12 to 47.92 mA cm−2, and then decreases
slightly to 46.8 mA cm−2. The open circuit voltage (Voc ), fill factor (FF)
and photovoltaic conversion efficiency (PCE) increase greatly, and the
PCE reaches 17.84% at a graphene work function of 5.0 eV.
In a metal-semiconductor contact, the relationship between the
built-in potential (Vbi ) and Schottky barrier height (ΦBo) can be de-
scribed as Eq. (1):
Vbi = (ΦBo − Φn)/ q
where Φn is the difference between the bottom of the conduction band
and Fermi level of semiconductor; q is the charge of an electron. One
can note that Φn is a constant at a fixed doping concentration. The
Schottky barrier height ΦBo at the interface of metal-semiconductor
contact can be expressed as follow:
ΦBo = Φm − χ
where Φm is the work function of graphene; χ is the electronic affinity
of GaAs. One can notice that the increasing Φm means a higher corre-
sponding ΦBo , leading to the increase of Vbi . Due to the positive re-
lationship between Vbi and Voc , Voc is enhanced as well.
To illustrate the effect of graphene work function on the perfor-
mance of the graphene/GaAs heterojunction solar cells more visually,
Fig. 2(b) depicts the energy band diagrams of graphene/GaAs solar cells
in the GaAs side with various work functions of graphene. When the
work function of graphene increases from 4.3 to 5.0 eV, the conduction
band in the GaAs side shows a larger bending degree, together with a
wider depletion region. In addition, the inset of Fig. 2(b) depicts the
energy band diagrams of graphene/GaAs heterojunction solar cells at
the position of the back contact for graphene with work functions of 4.3
and 5.0 eV, respectively. It indicates that the work function of graphene
can hardly influence the energy band diagram at the position of the
back contact. This is because the width of the built-in electric field is
much smaller than the thickness of the GaAs layer, the energy band
diagram at the position of back contact is almost unaffected.
It is noteworthy that the photo-excited carriers are mainly generated
in the GaAs layer, and then they are separated by built-in electric field.
Subsequently, the photo-excited electrons and holes are collected in the
GaAs layer and the graphene layer, respectively. When the work
Solar Energy 182 (2019) 453–461
function of graphene is small (4.3 eV), the heterojunction solar cell
almost shows no efficiency. Herein, the calculated ΦBo and Vbi are
0.19 eV and 0.08 V, respectively. This suggests that electrons can easily
move forward to graphene from GaAs owing to such a low Schottky
barrier height, which causes a large leakage current and degrades
voltage output.
As for the short-circuit current density (Jsc ), it shows a trend of
increasing first and then decreasing slightly. Eqs. (3) and (4) give the
expressions of the width of the depletion region x n and the maximum
electric field intensity Emax formed by the Schottky junction, respec-
tively.
(1)
1
2ε V 2
x n = ⎜⎛ s bi ⎟⎞
⎝ qNd ⎠ (3)
qNd x n
|Emax| =
εs (4)
(2)
where εs and Nd represent the dielectric constant and the doping con-
centration of GaAs, respectively. Based on Eqs. (1)–(4), one can obtain
that a small work function of graphene means a lower x n and |Emax|,
resulting in an inefficient separation and collection for photo-generated
carriers, and it would be reflected in the small Jsc . With the increase of
graphene work function, the collection efficiency of photo-generated
carriers is enhanced to a large extent, so Jsc increases. However, when
the work function of graphene is too large, it may aggravate the dis-
continuity of the energy band, leading to an increase in series re-
sistance, so Jsc decreases slightly.
The overall trend is that a larger graphene work function can fa-
cilitate the enhancement in the photovoltaic performance. Therefore,
the optimization in the graphene work function is essential and effec-
tive for fabricating high-performance graphene/GaAs heterojunction
solar cells. In Lin et al.’s research work (Lin et al., 2013), they in-
vestigated different graphene work functions on the performance of
graphene/Si solar cells and revealed that a high graphene work func-
tion (∼5.1 eV) significantly improves the photovoltaic performance of
graphene/Si solar cells, which further confirms our simulation result.
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M. Yu, et al.
Table 2
Absorption coefficient and light transmittance for different number of graphene
layers.
Layer number Absorption coefficient (cm−1) Light transmittance (%)
1 6.8 × 105 97.7
2 4.3 × 106 95.4
3 6.4 × 106 93.1
4 8.5 × 106 90.8
5 1.06 × 107 88.5
6 1.28 × 107 85.3
3.2. Effect of graphene absorption loss on the cell’s photovoltaic
performance
Despite a high light transmittance of 97.7% for single-layer gra-
phene, absorption loss of graphene is also a factor which cannot be
ignored when graphene serves as a transparent electrode.
According to the discussion above, a higher graphene work function
favors efficiency improvement in the graphene/GaAs solar cells.
Recently, different methods have been proposed for optimizing the
work function of graphene, such as chemical doping or application of
electric fields (Denis, 2010; Yu et al., 2009). In addition, increasing the
number of graphene layers is adopted as a simple and effective method
to meet the requirement of the optimization of the graphene work
function (Li et al., 2014). Unfortunately, increasing the number of
graphene layers will encounter a decline in the light transmittance.
Table 2 shows the absorption coefficient and light transmittance of
graphene with different number of graphene layers (Nair et al., 2008).
It can be seen from Table 2 that single-layer graphene has an excep-
tional light transmission performance and hardly produces light ab-
sorption loss. However, the light transmittance drops drastically to
85.3% for graphene with six layers, which means a serious absorption
loss of graphene. Herein, we concentrate on investigating the effect of
the number of graphene layers on the graphene/GaAs Schottky junction
solar cells for a balance between work function and absorption loss.
Fig. 3 shows the photovoltaic parameters of graphene/GaAs solar
cells with various number of graphene layers. When the number of
graphene layers increases, Voc and Jsc of graphene/GaAs solar cells
show a downward trend while FF shows an upward trend. PCE has an
optimal value for graphene with two layers. The relationship between
Voc and Fermi level is expressed in Eq. (5):
Fig. 3. Photovoltaic parameters of graphene/GaAs solar cells with various number of graphene layers: (a) open-circuit voltage, (b) short-circuit current density, (c)
fill factor, and (d) photovoltaic conversion efficiency. (e) Absorption spectra of graphene/GaAs heterojunction solar cells with various number of graphene layers.
456
Solar Energy 182 (2019) 453–461
1 n
Voc = (EF − EF )
q (5)
where EFn represents the electron quasi-Fermi level of GaAs under il-
lumination, and EF represents the thermal-equilibrium Fermi level for
graphene in contact with GaAs. Here, EF is a constant and EFn depends
on the number of photo-generated carriers in the GaAs layer. An in-
crease in the number of graphene layers can result in a decrease in light
transmittance. When there is less photo-generated carriers, EFn is closer
to EF , and the difference between EFn and EF becomes smaller, giving
rise to the decrease of Voc. At a small absorption loss, there are a large
number of photo-generated carriers in the GaAs layer due to the suffi-
cient incident light. Jsc depends on the amount of collected photo-
generated carriers, so the solar cell shows better performance at a small
number of graphene layers. Eq. (6) (Kitai, 2011) shows the dependence
of Voc on the photo-generated current (IL ) in a solar cell:
kT I
Voc = ln( L + 1)
q I0 (6)
where IL and I0 are the photo-generated current and the reverse sa-
turation current, respectively; k is Boltzmann constant; and T is the
temperature. The increase in IL can favor the enhancement in Voc . It is
worthy of noting that Jsc is more susceptible to light absorption than
Voc . This can be explained from Eq. (6), which indicates that Voc is
proportional to the logarithm of IL , while Jsc is proportional to IL .
Fig. 3(e) illustrates the absorption spectra with different number of
graphene layers. One can notice that light absorption decreases with the
increase of the number of graphene layers. At a high number of gra-
phene layers, the absorption loss causes a significant drop in the
amount of photo-generated carriers, giving rise to a low Jsc . This fur-
ther confirms the above analysis.
Lin et al. measured the sheet resistance of graphene as a function of
the number of graphene layers and found that the sheet resistance de-
creased with the increase in the number of graphene layers, which may
account for the upward trend of FF with the increased number of gra-
phene layers (Lin et al., 2013). Therefore, the light absorption loss
should also be taken into account in the process of achieving graphene
with a high work function by increasing the number of graphene layers.
It would be better to combine the layer adjustment with other physical
and chemical methods for optimization in graphene properties, instead
of relying on solely increasing the number of graphene layers.
M. Yu, et al. Solar Energy 182 (2019) 453–461

Fig. 4. J-V curves of the solar cells obtained with different densities of interface Fig. 5. Electric field distributions and corresponding energy band diagrams
states. (inset) of graphene/n-GaAs Schottky heterojunction solar cells at different
densities of interface states.

3.3. Influence of the density of interface states

In addition to the property of each functional layer, the density of
interface states (Dit ) is also a critical factor for photovoltaic perfor-
mance of solar cells. Due to the lattice mismatch and the existence of a
large number of dangling bonds on the surface, there would be nu-
merous interface states between graphene and GaAs. It can cause a
serious carrier recombination, which degrades the performance of solar
cells. The intrinsic graphene has few defects, but the defect states as-
sociated with wrinkles and impurities are inevitable during the process
of graphene transfer and physical and chemical operation in the actual
experiments. In the simulation, a GaAs layer with a thickness of 5 nm
containing a bulk defect density of 1 × 1015 to 1 × 1019 cm−3 eV−1 was
incorporated into the interface between graphene and GaAs. This cor-
responds to the interfacial defect layer with an interface defect density
of 1 × 109 to 1 × 1013 cm−2 eV−1. The obtained J-V curves of the solar
cells with different densities of interface states are shown in Fig. 4. It is
clear that the increased Dit will cause a considerable decline in Voc . The
specific photovoltaic parameters are listed in Table 3. The Voc limit
imposed by interface recombination can be expressed as the following
formula (Jensen et al., 2002):
1⎧ qN S
Voc = Φc − AkT ln ⎛ v it ⎞ ⎫
⎜ ⎟
Dit = 1 × 109 cm−2 eV−1. It can be seen from Fig. 5 that graphene/GaAs
heterojunction solar cells show a strong intensity of electric field near
the interface for a high Dit . However, the intensity of electric field de-
creases gradually in the side of GaAs layer. When GaAs is in contact
with intrinsic graphene, the majority carriers (electrons) travel across
the interface from GaAs to graphene due to the alignment of their Fermi
levels. Under a high density of interface states, the electrons flowing out
from the GaAs layer are trapped due to the capture effect of interface
states. These acceptor-like interface states with electrons will become
negative charged. With the accumulation of trapped electrons, there
will form an intense electric field at the interface between graphene and
GaAs. As shown in Fig. 5, one can notice that the electric field becomes
much weaker in the GaAs side, and it means that photo-excited holes
generated in the GaAs bulk have a less possibility to reach the graphene
side. Thus, Jsc decreases as a result of deterioration in the collection
efficiency for carrier.
For a supplementary explanation, the simulated energy band dia-
grams at corresponding densities of interface states are shown in the
inset of Fig. 5. It can be seen that the energy band of GaAs with a high
density of interface states is flattened. This tendency is consistent with
the variation of the intensity of electric field. Generally, a flat energy
band accelerates the carrier recombination, leading to a decrease in

q⎨
⎩ ⎝ Jsc ⎠ ⎬⎭ (7) Voc . Therefore, it is necessary to control the density of interface states
for achieving better performance. This result indicates that a Dit lower
where Nv and Sit are the effective density of states of the valence band than 1 × 1011 cm−2 eV−1 favors the efficiency enhancement.
and the interface recombination rates, respectively; Φc is the effective Recently, several approaches have been proposed for interface op-
barrier height; and A is the ideality factor. It implies that the high timization (Jiao et al., 2014; Rehman et al., 2018; Song et al., 2015).
density of interface states can cause high interface recombination rates, For example, Rehman et al. utilized an Al2O3 layer to serve as an
leading to an exponentially decrease inVoc. electron blocking layer at the graphene/Si heterojunction interface
For further illustration of the influence of interfacial defects, Fig. 5 (Rehman et al., 2018). This approach helps to minimize the surface
exhibits the electric field distributions and energy band diagrams of recombination at the heterojunction interface for performance en-
graphene/GaAs heterojunction solar cells with two different densities of hancement. Through a further optimization of thickness of Al2O3 layer,
interface states: high Dit = 1 × 1013 cm−2 eV−1 and low a PCE of 8.4% for graphene/Si Schottky junction solar cells was
achieved (neither with graphene doping nor with top layer passiva-
Table 3 tion). The proposed modified Schottky barrier height for the thermionic
Photovoltaic parameters of graphene/GaAs heterojunction solar cells with dif- model in the Rehman et al.’s work is shown in Eq. (8):
ferent densities of interface states.
Density of interface states Voc (mV) Jsc (mA/ FF (%) PCE (%) A ∗ T2⎞
(cm−2 eV−1) cm2)
ΦBo = k T ∗ ln ⎛
⎜ ⎟

⎝ J0 ⎠ (8)
1× 109 500.2 44.93 79.58 17.89
500.2 44.86 79.55 17.85 where A* is the Richardson constant; J0 is the reverse saturation current
1 × 1010
1 × 1011 499.8 44.16 79.33 17.51 density. The introduction of Al2O3 layer decreases the tunneling prob-
1 × 1012 496.8 39.95 77.88 15.46 ability of electrons from Si to graphene, and J0 decreases significantly.
1 × 1013 485.8 27.56 75.06 10.05 Thus, according to Eq. (8), ΦBo increases, giving rise to a high Voc .

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Fig. 6. Influence of the work function of the back contact on the performance of the graphene/GaAs solar cells: (a) obtained J-V curves; (b) change trend of fill factor;
(c) conduction band diagram at the position of the back contact; (d) electric field distributions at the position of the back contact.
3.4. Work function of the back electrode
Herein, Eq. (9) expresses the relationship between Jsc and collection
efficiency:
∞
Jsc = ∫0 ηc (E )[1 − R (E )] α (E ) bs (E , Ts ) dE
where bs (E , Ts ) is the photon flux; α (E ) is the quantum efficiency; R (E )
is the reflectance; ηc (E ) is the collection efficiency of carriers; and E is
the incident photon energy. It indicates that the collection efficiency of
carriers can significantly affect the photovoltaic performance.
Generally speaking, the back electrode affects the collection effi-
ciency of carriers by exerting influence on the energy band distribution
at the back contact. Therefore, it is also necessary to explore the effect
of work function of the back electrode on the performance of graphene/
GaAs heterojunction solar cells. It helps us to select an appropriate back
electrode for graphene/GaAs solar cells in actual experiments.
Fig. 6(a) depicts the simulated J-V curves with different work
functions of the back electrode. It can be seen that a work function in
the range of 3.8–4.4 eV can hardly change the photovoltaic perfor-
mance of the solar cells. However, a further increase of work function to
4.6–4.8 eV leads to an obvious decrease in Voc , accompanied with a
distinctive s-shaped kink in J-V curves. The appearance of S-shaped
kink has been reported in several past works (Wadhwa et al., 2010; An
et al., 2013), but the mechanism of the S-shaped kink is still unclear and
needs further study. The curve of fill factor versus work function of the
back electrode shown in Fig. 6(b) confirms the considerable decline of
the FF reflected in Fig. 6(a).
Solar Energy 182 (2019) 453–461
The simulated conduction band diagrams with different work
functions at the position of the back electrode are shown in Fig. 6(c).
Based on the theory of metal-semiconductor Schottky contact, one can
notice that an Ohmic contact is formed between GaAs and the back
electrode when the work function of the back electrode ranges from 3.8
(9) to 4.0 eV. Under this condition, photo-generated electrons can be col-
lected effectively. Furthermore, when the work function of the back
electrode increases to 4.2 eV, the conduction band of GaAs bends up-
wards. It means the formation of Schottky contact on the back contact,
and the carrier collection will be hindered slightly. With a further in-
crease of work function to about 4.6–4.8 eV, the Schottky barrier height
is large enough to block the collection of electrons. As shown in Eq. (6),
a decrease inIL causes a decrease of VOC . Eq. (10) indicates that FF is
mainly affected by series resistance (RS ) and parallel resistance (Rsh )
(Rand et al., 2007):
I R V
FF(Rsh , Rs ) ≈ FF(0, ∞) ⎡ ⎛1 − SC S ⎞ − ⎛ OC ⎞ ⎤
⎜ ⎟ ⎜ ⎟
⎢⎝ VOC ⎠ ⎝ ISC Rsh ⎠ ⎥ (10)
⎣ ⎦
The back electrode with a large work function will hinder the carrier
collection severely resulting in an increased RS and therefore a con-
siderable decrease in FF.
Fig. 6(d) shows the distributions of the electric field of graphene/
GaAs solar cells with different work functions of the back electrode. It
indicates that the work function of the back electrode significantly in-
fluences the electric field at the back contact. Furthermore, an increase
in the work function of the back electrode will strengthen the electric
field at the back side. Specifically, the built-in potentials between GaAs
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and the back electrode are calculated to be 0.09 and 0.69 V, respec-
tively, when the work functions of the back electrode are 4.2 and
4.8 eV, respectively. A high built-in potential shows much stronger
hindrance to the transportation and collection of photo-generated
electrons, which verifies our explanation as aforementioned. There are
generally a variety of electrode materials, such as Au, Ag, Al, etc. This
simulation result helps us to evaluate the performance of electrode
candidate before the actual fabrication process.

3.5. AlxGa1−xAs (x = 0.2) buffer layer for performance improvement

In the discussion above, the density of interface states is confirmed

to be a crucial factor for photovoltaic performance. Reducing the carrier
recombination through the interface optimization is considered as a
feasible approach. Under illumination, the photo-generated carriers are
mainly generated in the GaAs layer, and the carrier recombination
mainly occurs at the interface between the graphene and the GaAs
absorption layer. The recombination of carriers is regarded as a loss of
photo-generated carriers, so it is necessary to suppress the recombina-
tion for effective carrier collection. AlxGa1−xAs (0 ≤ x ≤ 1) compound
is applicable for serving as the interface buffer layer in the graphene/
GaAs solar cells. Firstly, AlxGa1−xAs (0 ≤ x ≤ 1) is structurally similar
to GaAs (both of them belong to direct bandgap semiconductors with a
similar bandgap). In addition, AlxGa1−xAs (0 ≤ x ≤ 1) is typically lat-
tice matched with GaAs owing to their small difference in the lattice
constant (αAlx Ga1 − x As = αGaAs + 0.0078x, 0 ≤ x ≤ 1) (Singh, 2013).
Furthermore, it has been demonstrated that the combination of GaAs
and AlxGa1−xAs (x = 0.2) exhibits excellent performance in quantum
well solar cells and multiple-junction solar cells (Lam et al., 2016;
Abolghasemi and Kohandani, 2018).
Herein, an AlxGa1−xAs (x = 0.2) buffer layer was employed to the
interface between graphene and GaAs for interface optimization. The
layer parameters of AlxGa1−xAs (x = 0.2) used in this simulation are
shown in Table 1. The J-V curves of graphene/GaAs heterojunction
solar cells with and without an AlxGa1−xAs (x = 0.2) buffer layer under
illumination are shown in Fig. 7(a). With the insertion of AlxGa1−xAs Fig. 7. J-V curves (a) and energy band diagrams (b) of graphene/GaAs het-
(x = 0.2) buffer layer, one can notice that: (I) Voc increases by 32% erojunction solar cells with and without an AlxGa1−xAs (x = 0.2) buffer layer
from 0.50 to 0.66 V; (II) Jsc increases slightly from 44.93 to 45.61 mA/ under illumination, respectively.
cm2; (III) PCE increases by 38.5% from 17.89% to 24.78%.
For an investigation of this dramatic improvement in the photo-
3.6. Comparison among simulation and experimental data
voltaic performance, the energy band diagram obtained in the simula-
tion is shown in Fig. 7(b). Generally speaking, due to the difference in
Since the graphene/GaAs heterojunction solar cells were firstly re-
the Fermi level between graphene and GaAs, electrons flow from GaAs
ported in 2013, great efforts have been devoted to improving their
to graphene when GaAs is in contact with graphene by van der Waals
photovoltaic performance. Herein, we summarize the recent progress in
force. However, the band discontinuity usually occurs in the interface
the graphene/GaAs heterojunction solar cells and compare these ex-
of a heterojunction, the conduction band offset (ΔEC ) and the valence
perimental data with our simulation result as shown in Table 4.
band offset (ΔEV ) can be expressed as Eqs. (11) and (12), respectively.
It can be seen that Voc is higher in experimental works than that in
ΔEC = χ2 − χ1 (11) this simulation, which can be mainly attributed to the optimization of
graphene and the presence of interface layer. In Jie et al.’s work (Jie
ΔEV = ΔEg − (χ2 − χ1 ) (12) et al., 2013), the possible reason for higher Voc is that the graphene
work function of their work is higher than 5.0 eV used in our simulation
where χ2 and χ1 are the electron affinities of GaAs and AlxGa1−xAs
work, and that a higher graphene work function favors the improve-
(x = 0.2), respectively; ΔEg is the bandgap difference between GaAs
ment in Voc. Further adjustment in the number of graphene layers leads
and AlxGa1−xAs (x = 0.2).
to a higher Schottky-barrier height and lower series resistance, and a
Under illumination, photo-generated excess holes and electrons are
PCE of 1.95% is obtained. Recently, it has been reported that Si atom
separated by the built-in electric field, subsequently, they are trans-
doping can open the bandgap of graphene (Zhang et al., 2016). This
ported to the front electrode and the back electrode, respectively. For
approach can increase the work function of graphene and improve the
the graphene/GaAs heterojunction solar cells with an AlxGa1−xAs
quality of interface, resulting in a higher barrier height ΦBo and Voc . In
(x = 0.2) buffer layer, the calculated ΔEC is 0.37 eV, whereas the cal-
addition, bis(trifluoromethanesulfonyl)amide [((CF3SO2)2NH)] (TFSA)
culated ΔEV has a lower value of 0.05 eV. A higher ΔEC increases the
doping is adopted as an effective method for the optimization of gra-
barrier height of electrons, and it can hinder the transportation of
phene. The Fermi level of graphene moves downward through TFSA
electrons from the interface to the front electrode, so the recombination
doping, and then p-type graphene favors the enhancement in Voc . It is
decreases. On the other hand, a smaller ΔEv almost has no impact of the
also reported that TFSA doping can reduce the series resistance, which
transportation on photo-generated holes (Wen et al., 2013; Rawat et al.,
contributes to the increase in Jsc and FF. The other reason for the higher
2014). As a result, Voc is significantly improved, and the overall per-
Voc in the experimental works is associated with the incorporation of
formance of graphene/GaAs solar cells is improved.

459
M. Yu, et al.
Table 4
Comparison of recent experimental works together with our simulation work for the graphene/GaAs heterojunction solar cells under illumination.
Method Structure Voc (mV)
Graphene optimization (Single layer) Gr/GaAs 620
(Bilayer) Gr/GaAs 650
(Si doped) Gr/GaAs 650
Interface engineering (Si QDs)/Gr/h-BN/GaAs 690
TiO2/TFSA-Gr/P3HT/GaAs 760.9
Light absorption Au NPs/Al2O3/TFSA-Gr/GaAs 820
Others Gated-Gr/Al2O3/TFSA-Gr/GaAs 960
This simulation work Gr/GaAs 500
This simulation work Gr/AlxGa1−xAs/GaAs 660
interface layer. In Li et al.’s work, hexagonal boron nitride layer was
inserted into the interface between graphene and GaAs for suppressing
electron transfer from GaAs to graphene. Furthermore, photo-induced
doping through Si quantum dots is applied in this device for adjusting
carrier transportation. The Schottky barrier height ΦBo is enhanced ef-
fectively, and a high Voc of 690 mV is obtained (Li et al., 2016).
Through an introduction of P3HT as an interface layer, accompanied
with a TiO2 antireflective film and TFSA doping, He et al. achieved a
high Voc of 760.9 mV and a PCE of 13.7%. This significant improve-
ment is because the P3HT layer serves as an electron-blocking/hole-
transporting layer and thus suppresses carrier recombination, giving
rise to the improvement of the overall cell performance (He et al.,
2015). Our previous simulation result has also confirmed that the P3HT
interface layer can favor the enhancement in Voc effectively (Li et al.,
2019). In Li et al.’s work (Li et al., 2015), they creatively designed a
gating structure of graphene/Al2O3/graphene. Through the use of an
external voltage, a tunable Fermi level for graphene was obtained, and
an increased ΦBo induced higher Voc for the graphene/GaAs hetero-
junction solar cells. With the introduction of an AlxGa1−xAs layer, the
obtained Voc in this simulation work is comparable with that obtained
in the experimental works.
It is noteworthy that this simulation work shows a higher Jsc than
that in the experimental works. This discrepancy can be attributed to
the following two factors: (i) Under simulated conditions, the absorp-
tion and reflection of the incident light, layer contact, as well as elec-
trode contact are regarded as an ideal case. In fact, these factors can
strongly affect Jsc . For instance, in Lin et al.'s work, through the use of
Au nanoparticles for suppressing the interfacial recombination and
Al2O3 coating for reducing the reflection of incident light, Jsc increases
from 19.1 to 28.6 mA cm−2 (Lin et al., 2016).
Jsc increases from 19.1 to 28.6 mA cm−2 (Lin et al., 2016). (ii) In
this simulation, defects and density of interface states are controlled at
a lower level. However, these factors are important for photovoltaic
performance in the actual experiments because they can cause leakage
current and carrier recombination, which can lead to the decrease in
Jsc .
This comparison demonstrates that a comprehensive and specific
simulation work is essential for evaluating the performance of solar
cells. Moreover, in view of the difference in the photovoltaic perfor-
mance between simulation and experimental works, it will encourage
the researchers’ effort for improving photovoltaic performance via
further optimization approaches. In addition, these continuous efforts
will also stimulate graphene/GaAs heterojunction solar cells to be a
competitive option for high-performance photovoltaic devices.
4. Conclusion
In this work, the graphene/GaAs heterojunction solar cells were
simulated by AFORS-HET software. Various factors such as graphene
work function, absorption loss, interface states and work function of the
back electrode on the performance of graphene/GaAs heterojunction
solar cells are investigated in detail. The work function and absorption
460
Solar Energy 182 (2019) 453–461
Jsc (mA/cm2) FF (%) PCE (%)
6.43 27 1.09
10.03 30 1.95
13.6 51 4.5
18 59.7 10.18
26.18 68 13.7
28.6 69.2 16.2
27.1 71.1 18.5
44.93 79.58 17.89
45.61 82.42 24.78
loss should be considered comprehensively in the graphene optimiza-
tion. Bilayer graphene with a work function of 5.0 eV favors the pho-
tovoltaic performance. A back electrode material with a work function
similar to GaAs is an appropriate selection. Furthermore, the insertion
of AlxGa1−xAs (x = 0.2) buffer layer can significantly improve the
photovoltaic performance, attributed to its prominent contribution in
decreasing the carrier recombination. This study helps to understand
various factors that can affect the performance of graphene/GaAs het-
erojunction solar cells and provides guidance for actual experiments in
fabricating high-efficiency solar cells.
Acknowledgements
This work was supported by Shenzhen Science and Technology
Innovation Committee (Grant No. JCYJ20170306141238532; Project
name: Research on the fabrication of graphene nanowalls and relevant
application in the Si-based heterojunction solar cells), China.
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