Solar Energy 201 (2020) 227–246

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

A review of Sb2Se3 photovoltaic absorber materials and thin-film solar cells T

a,b,⁎ b a a c
Abdurashid Mavlonov , Takhir Razykov , Fazal Raziq , Jiantuo Gan , Jakapan Chantana ,
Yu Kawanoc, Takahito Nishimurad, Haoming Weie, Andriy Zakutayevf, Takashi Minemotoc,
Xiaotao Zua, Sean Lig, Liang Qiaoa
a
School of Physics, University of Electronic Science and Technology of China, Chengdu 610054, China
b
Physical-Technical Institute, Uzbekistan Academy of Sciences, Bodomzor Yoli 2“B”, Tashkent 100084, Uzbekistan
c
Department of Electrical and Electronic Engineering, Ritsumeikan University, 1-1-1 Nojihigashi, Kusatsu, Shiga 525-8577, Japan
d
Ritsumeikan Global Innovation Research Organization, Ritsumeikan University, 1-1-1 Nojihigashi, Kusatsu, Shiga 525-8577, Japan
e
School of Physics and Physical Engineering, Shandong Provincial Key Laboratory of Laser Polarization and Information Technology, Qufu Normal University, Qufu
273165, China
f
National Renewable Energy Laboratory, Golden, CO 80401, USA
g
School of Materials, University of New South Wales, Sydney 2052, NSW, Australia

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

Keywords: Energy generated from environmentally friendly, cost-effective solar cells is a key aspect for developing a clean
Sb2Se3 renewable-energy economy. Non-toxic and Earth-abundant materials with high absorption coefficient (> 105
Thin-film solar cells cm−1) and optimal bandgap (1–1.5 eV) have received great attention as photovoltaic (PV) absorber layers
Photovoltaics during the last few decades. Among them, antimony selenide (Sb2Se3) has been a promising PV absorber, with
Open-circuit voltage deficit
steadily increasing power-conversion efficiency (PCE) compared to other emerging compounds. Very recent
Carrier management
studies showed that high-quality ZnO:Al/ZnO/CdS/TiO2/Sb2Se3/MoSe2/Mo devices with PCE of 9.2% can be
fabricated using cost-effective novel compounds. Considering these recent advances, this article provides an
overview of the material properties of Sb2Se3 thin films and the recent progress made with Sb2Se3-based solar
cells. Analysis of Sb2Se3-based thin-film solar cells has also shown that the devices have relatively good light
management due to their suitable bandgap and high absorption coefficient, whereas carrier management, i.e.
collection efficiency of photo-generated carriers, needs significant improvement. Overall, this study provides
background knowledge on material properties and device performance and suggests main research directions to
overcome the limiting factors of solar cell performance.

1. Introduction absorber materials including metal sulfides and selenides—such as

Photovoltaic (PV) technologies offer a clean, sustainable solution to
meet the increasing global energy demand via direct conversion of solar
radiation (or other sources of radiation) into electricity (Green, 2019;
Ramanujam et al., 2016). According to the Shockley-Queisser (S-Q)
detailed-balance model, a single-junction solar cell with an optimum
bandgap of Eg ≈ 1.14 eV of the absorber layer can yield a maximum
power-conversion efficiency (PCE) of 33.3% (Alharbi and Kais, 2015).
In reality, Cu(In,Ga)Se2- and CdTe-based PV technologies, which are
the most common thin-film solar cells, have PCEs of 22.6% and 22.1%
at the laboratory scale and 19.2% and 18.6% at module level, respec-
tively (Green et al., 2018; Jackson et al., 2016). However, the high price
of In and Ga as well as the toxicity of Cd may limit their very large-scale
(multi-terawatt) use (Zakutayev, 2017). Hence, many Earth-abundant
Cu2SnS3 (Baranowski et al., 2015; Chantana et al., 2017d; Hossain
et al., 2018), CuSbS2 (Dittrich et al., 2007; Xue et al., 2015), FeS2 (Luo
et al., 2015), Cu2ZnSnSe4 (Hartnauer et al., 2016), CuSbSe2 (Xue et al.,
2015), Sb2(S,Se)3 (Wang, W. et al., 2018), Sb2Se3 (Wen et al., 2017) and
SnSe (Razykov et al., 2018a)—have been investigated as alternatives
for the highly efficient, environmentally friendly, stable, and cost-ef-
fective thin-film solar cells.
Antimony selenide (Sb2Se3) belongs to a family of inorganic binary
V2-VI3 compounds (e.g., Bi2S3, Bi2Se3, Bi2Te3, Sb2S3, Sb2Se3, Sb2Te3)
(Zeng et al., 2016). The Sb2Se3 material and related compounds exist
naturally in the form of the mineral stibnite and have orthorhombic
structure, which is formed by (Sb4Se6)n ribbons stacked in parallel in
the [0 0 1] direction (Kondrotas et al., 2018; Zhou et al., 2015). Despite
the similar structure of these materials, only a few of them—e.g., Sb2S3,

⁎
Corresponding author at: School of Physics, University of Electronic Science and Technology of China, Chengdu 610054, China.
E-mail addresses: mavlonov@uestc.edu.cn (A. Mavlonov), andriy.zakutayev@nrel.gov (A. Zakutayev), liang.qiao@uestc.edu.cn (L. Qiao).

https://doi.org/10.1016/j.solener.2020.03.009
Received 19 February 2020; Received in revised form 3 March 2020; Accepted 3 March 2020
Available online 08 March 2020
0038-092X/ © 2020 International Solar Energy Society. Published by Elsevier Ltd. All rights reserved.
A. Mavlonov, et al.
Bi2S3, and Sb2Se3—have been reported for PV applications (Kondrotas
et al., 2018). In the case of Sb2S3, its higher bandgap (about 1.7 eV) is
the main limiting factor for use in single-junction solar cells; never-
theless, it can be a suitable candidate for multijunction tandem solar
cells. As for Bi2S3, its lowest unoccupied molecular orbital (LUMO or
conduction band) has been found to be lower in energy compared to
those in Sb2S3 and Sb2Se3, which is unfavorable for electron injection
from the absorber into the buffer layer (Patrick and Giustino, 2011).
Overall, atomistic calculations have shown that Sb2Se3-based solar cells
hold higher potential among V2-VI3 compounds (Patrick and Giustino,
2011). Although this work focuses on Sb2Se3-based thin-film solar cells,
we note that they share many similarities with those based on other V2-
VI3 compounds, e.g. Sb2S3 and Sb2(S,Se)3, hence the readers are re-
ferred to recent comparative study by Lei et al. on these materials for
more details (Lei et al., 2019).
Among these V2-VI3 materials, Sb2Se3 has recently attracted tre-
mendous interest for use as a PV light absorber as well as battery (Ou
et al., 2017; Tian et al., 2019) and photochemical applications (Liang
et al., 2017; Wu et al., 2019), because of its promising optoelectronic
properties and favorable environmental characteristics. Sb2Se3 is not on
the lists of highly toxic materials by American, European Union, or
Chinese regulation authorities, nor in the lethal dose LD50 or lethal
concentration LCt50 data. The abundance of Sb and Se elements in the
Earth’s crust is 0.2 and 0.05 ppm, respectively (Zeng et al., 2016; Zhou
et al., 2014), and Sb2Se3 has good physiochemical stability (Koc et al.,
2012). Fig. 1 highlights the recent research advances as well as future
research areas of Sb2Se3-based thin-film solar cells. As shown in Fig. 1,
thin films with preferential (221) crystal orientation and low defect
density are desired to increase the PCE. Furthermore, proper band
alignment between constituent layers and the thin-film absorber mor-
phology must be considered. Another important research direction is
the defect physics of Sb2Se3, including the effects of Se vacancies (VSe)
on PV performance. It is clearly shown from current density–voltage (J-
V) curves that future research challenges are related primarily to re-
ducing open-circuit voltage (VOC) deficit via carrier management.
Overall, Sb2Se3 is receiving growing research interest within the PV
community because of its favorable material properties and rapidly
improving PCE. Although more than 100 papers have been published
on Sb2Se3-based thin-film solar cells in the last decade, no recent
comprehensive review exists on this PV technology. We note that re-
cently, Wang et al. and Lei et al. discussed, in part, the development of
Sb2Se3 thin-film solar cells in their 2018 and 2019 studies dedicated to
Sb2(S,Se)3-based thin-film solar cells (Lei et al., 2019; Wang, X. et al.,
2018). In 2016, Tang et al. briefly reviewed the material and optoe-
lectronic properties and device performance of Sb2Se3 (Zeng et al.,
2016), but many works have been reported on Sb2Se3 material and
device performance since that time and therefore, an up-to-date review
is necessary.
Here, we review recent research advances and remaining challenges
of Sb2Se3 thin-film absorber materials and PV solar cells on the path
toward high efficiency. Following this introduction (Section 1), we
briefly summarize the history of research on Sb2Se3–based thin-film
solar cells (Section 2) so as to put the recent advances in perspective.
Next, we introduce the Sb2Se3 properties (Section 3)—including crystal
structure, electronic structure, electrical properties, point defects, de-
fect chemistry and optical properties—for both crystalline and amor-
phous Sb2Se3 materials. Then, we discuss the fabrication and perfor-
mance of Sb2Se3 devices (Section 4), including absorber deposition
methods, buffer layer, hole-transport layer and back contacts, and
transparent electrode layers. We also discuss the effect of shunt re-
sistance (RSh) and series resistance (RS) on device performance and
summarize the resulting device stability. Finally, we highlight current
status, challenges as well as future research directions in Sb2Se3
(Section 5).
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Solar Energy 201 (2020) 227–246
2. History of Sb2Se3 research
In 1950, Dögnes synthesized Sb2Se3 and showed that it was iso-
structural with Sb2S3. Because Sb2S3 had a longer research history, this
finding was beneficial to understand the physical properties of the
material via comparative studies (Dönges, 1950; Hofmann, 1933). In
1957, Tideswell et al. confirmed that these two compounds had similar
features (Tideswell et al., 1957). Furthermore, they precisely calculated
the Sb2Se3 lattice parameters (a = 11.62 ± 0.01 Å,
b = 3.962 ± 0.007 Å, c = 11.77 ± 0.01 Å), which are almost iden-
tical with recent data (Chandrasekharan and Kunjomana, 2009; Voutsas
et al., 1985). In the 1960s, several Sb2Se3 physical properties were in-
vestigated. Uphoff et al. studied the thermoelectric properties of
amorphous and crystalline Sb2Se3 films (Uphoff and Healy, 1963) and
found that the material parameters depended on structure. Between the
1970s and 1990s, the number of reports on physical properties of
Sb2Se3 thin films gradually increased. As a result, knowledge expanded
significantly on the optical, electrical, structural, electronic, and mag-
netic properties of the material. In the 1990s and 2000s, Sb2Se3 was
used as a supporting material (or passive element) in solar cells.
Although synthesis and characterization of Sb2Se3 thin films had
been carried our since 1950s, early studies on Sb2Se3-based solar cells
reported the PCE below 1% in 1982 (Bhattacharya and Pramanik,
1982), 2002 (Rajpure and Bhosale, 2002), and 2009 (Messina et al.,
2009). However, active research on Sb2Se3 solar cells began in 2014,
probably after reports on TiO2-sensitized inorganic–organic solar cells
(PCE of 3.2%), TiO2/Sb2Se3 and CdS/Sb2Se3 thin film solar cells (PCE of
2.26% and 1.9%) by Seok et al. (Choi et al., 2014c) and Tang et al. (Luo
et al., 2014; Zhou et al., 2014), respectively. Hence, the role of this
material changed from being a passive component to being the active
component in PV. Afterwards, Tang and co-workers put significant ef-
fort into developing the Sb2Se3 thin-film PV architecture, reaching PCEs
of 3.7% at the end of 2014 (Leng et al., 2014), 5.6% in 2015 (Zhou
et al., 2015), 6.5% in 2017 (Chen et al., 2017b), and 7.6% in 2018 (Wen
et al., 2018). Most of these champion cells were prepared by using rapid
thermal evaporation (RTE), except the one with 7.6%, which was pre-
pared by vapor transport deposition (VTD) (Wen et al., 2018). They
have claimed that one-dimensional Sb2Se3 ribbons are beneficially
aligned vertically to maintain high carrier transport throughout the
Sb2Se3 layer. Very recently, Li et al. reported on Sb2Se3 solar cells
fabricated by closed-space sublimation with a PCE of 9.2%, i.e., the
highest efficiency to date (Li et al., 2019). Fig. 2A depicts the PCE of
Sb2Se3 and other Sb-containing thin-film solar cells. As shown,
Sb2(S,Se)3 and Sb2S3 have reached the PCE of 6.6% and 7.5%, respec-
tively. In contrast, CuSbS2 and CuSbSe2 have only yielded PCE of 3.2%
and 5%, respectively. Overall, these achievements have proven the fact
that Sb-containing thin-film absorbers are suitable for PV application,
whereas the current highest efficiency has placed the Sb2Se3 solar cell
in a visible position (cf. Fig. 2B).
Recently, Sb2Se3 has received growing research interest as observed
based on several literature reports (Fig. 2C). In the literature, Sb2Se3
has been successfully prepared by chemical growth methods, such as
spin coating (Choi et al., 2014c; Wang et al., 2019; Zhou et al., 2014)
and electrodeposition (ED) (Ngo et al., 2014), atomic layer deposition
(Mahuli et al., 2019), as well as physical growth methods, such as VTD
(Hu, X. et al., 2018a; Hu, X. et al., 2018b; Wen et al., 2018), RTE (Chen,
C. et al., 2018; Chen et al., 2017b; Wang et al., 2017), magnetron
sputtering (MS) (Liang et al., 2018; Tang et al., 2019a; Yuan et al.,
2016a; Yuan et al., 2016b), and close-spaced sublimation (CSS) (Li, D.-
B. et al., 2018; Li et al., 2019; Shen et al., 2018). To date, the physical
deposition methods have yielded higher device performance than the
chemical deposition methods. It has been demonstrated that Sb2Se3
solar cells can be prepared using both substrate and superstrate con-
figurations. The superstrate configuration has been used more widely
and resulted in most of the champion cells (Chen et al., 2017b; Leng
et al., 2014; Li, D.-B. et al., 2018; Wang et al., 2017; Wen et al., 2018;
A. Mavlonov, et al. Solar Energy 201 (2020) 227–246

Fig. 1. Important features studied and future research areas of Sb2Se3-based thin-film solar cells. Counter-clockwise from top: schematics of the device in planar
architecture; the crystal structure with preferred (right side) and non-preferred (left side) orientations (Zhou et al., 2015); defect control in the case of VSe; electronic
band structure; the scanning electron microscopy image of the device cross-section(Wang et al., 2019). In the middle: comparison between absorption efficiency of
the incident light (“light management”) and collection efficiency of photo-generated carriers (“carrier management”).

Zhou et al., 2015)—except for the latest 9.2% champion device
(Fig. 2D), which was fabricated in substrate configuration (Li et al.,
2019). Several publications have reported on the buffer/absorber in-
terface, with an attempt to improve the heterojunction and interface
quality (Chen et al., 2017c; Li et al., 2019; Wang et al., 2017). In par-
ticular, wide-bandgap compounds such as ZnO, TiO2, and SnO2 have
been used as an alternative to conventional CdS, aiming to enhance the
transparency of the buffer layer in the short-wavelength region and to
improve the heterojunction quality via proper band alignment, reduced
lattice mismatch and minimized inter-diffusion of Cd. Moreover, recent
studies showed fabrication possibility of semi-transparent Sb2Se3 based
thin-film solar cells (Chen et al., 2019), which can potentially be used in
many areas, e.g. energy saving window application (Dalapati et al.,
2018).
3. Material properties
3.1. Summary of materials properties
In general, the absorber layer of the solar cell must meet three
important requirements: 1) high absorption coefficient within the
useful spectral range to effectively absorb photons and generate the
electron-hole pairs; 2) good charge-carrier transport properties to
harvest the photo-generated carriers before their recombination; and 3)
achievable high and uniform internal electric field in the p-n junction,
which ensures the separation of electron-hole pairs. Note that the band-
tail states and/or dangling bonds, e.g., charged defects, may cause
nonuniformity of the field. Hence, the selection of a suitable absorber
layer relies not only on optimal bandgap values, but also, on other
properties of the material, such as readily attainable p-type or n-type
conductivity, high charge-carrier mobility, long charge-carrier lifetime,
long diffusion length of charge carriers, large dielectric constant, and
low exciton binding energy.
Several important properties of Sb2Se3 are summarized in Table 1.
The low melting point of Sb2Se3 (885 K) and its high vapor pressure
(Liu, X. et al., 2014) allow the deposition of high-quality thin films
using low-temperature vacuum-based deposition methods that were
established for CdTe thin-film solar cells (Romeo et al., 2018). Experi-
mental measurements show that polycrystalline Sb2Se3 with stoichio-
metric ratio has a bandgap (Eg) of about 1.03 eV indirect and 1.17 eV
direct (Chen et al., 2015), which is suitable for using Sb2Se3 as a PV
absorber layer. Theoretical calculations indicate strong light absorption
in Sb2Se3 due to high density of states (DOS) present in the valence
band (VB) and conduction band (CB) (Yu et al., 2013). Experimental
data have confirmed that Sb2Se3 films have a high absorption coeffi-
cient α > 105 cm−1 for photon energies larger than the bandgap

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A. Mavlonov, et al. Solar Energy 201 (2020) 227–246

Fig. 2. (A) The record PCEs for Sb-related

thin-film solar cells: Sb2Se3 (Chen et al.,
2017b; Choi et al., 2014c; Leng et al.,
2014; Li, D.-B. et al., 2018; Li et al., 2019;
Liu et al., 2015; Messina et al., 2009; Wang
et al., 2017; Wen et al., 2018; Zhou et al.,
2015), CuSbS2 (Banu et al., 2016; Banu
et al., 2019; Hutter et al., 2018c) CuSbSe2
(Welch et al., 2017; Welch et al., 2015),
Sb2(S,Se)3 (Choi et al., 2014b; Ishaq et al.,
2018), and Sb2S3 (Choi et al., 2014a;
Kondrotas et al., 2018). (B) Optimal
bandgap range (1.0–1.5 eV) with higher
Shockley–Queisser limit values (green line)
under the AM1.5 solar spectrum (orange
line). (C) Number of publications as a
function of year for Sb2Se3-based PV ab-
sorber technologies. (D) J-V curve of the
current champion cell adopted from (Li
et al., 2019).

Table 1 efficiently collect charge carriers after photo-generation. In general,

Physical properties of Sb2Se3. The label a indicates that the optical bandgap carrier lifetime can be prolonged by reducing the density of defects that
values were calculated using density functional theory. act as recombination centers. For example, Chen et al. determined τe of
Property of the Material Symbol Value Reference 67 ± 7 ns for Sb2Se3 using time-resolved transient absorption spec-
troscopy, as shown in Table 1. Further, the internal quantum efficiency
Lattice parameters (Å) a 11.6330 (Zhou et al., 2014) measurements were performed to estimate the diffusion length of
b 11.7800
electrons. The results revealed a long diffusion length of 1.7 ± 0.2 µm
c 3.9850
Space group Pnma 62 (Zhou et al., 2014) along the preferential c-direction (Chen et al., 2017a). In the following
Density (g cm−3) Ρ 5.84 (Zeng et al., 2016) subsections, we present detailed description of the structural, elec-
Melting point (K) Tm 885 (Zeng et al., 2016) tronic, electrical, defect, and optical properties of crystalline Sb2Se3, as
Bandgap (eV) Eg,d (direct) 1.17, 1.07a (Chen et al., 2015; well as amorphous Sb2Se3.
Eg,i (indirect) (300 K) Koc et al., 2012)
1.03, 0.99a
(300 K)
Absorption coefficient Α > 105 (Chen et al., 2015) 3.2. Crystal structure
(cm−1)
Relative dielectric εr 14.3–19.8 (Zeng et al., 2016)
Sb2Se3 crystalizes into an orthorhombic structure (Fig. 3), which
constant (ε0)
Exciton binding energy Eexc 1.28 (Lawal et al., 2018) belongs to the Pnma (62) space group (Zeng et al., 2016; Zhou et al.,
(eV) 2014). The crystal structure parameters of Sb2Se3 were calculated and
Minority-carrier lifetime τe 60 (Chen et al., 2017a) measured by several research groups. Sb2Se3 has lattice constants of
(ns) a = 11.62 ± 0.01 Å, b = 3.962 ± 0.007 Å, and c = 11.77 ± 0.01 Å,
Mobility (cm2 · V−1 · µe 15 (Zeng et al., 2016)
with a primitive cell volume of 0.524 nm−3 and density of 5810 kg/m3
s−1) µh 42
Diffusion length (µm) Le,c 1.7 (Chen et al., 2017a) (Caracas and Gonze, 2005; Tideswell et al., 1957; Zeng et al., 2016).
The distances of the “bonded” Sb-Se range from 2.576 Å to 2.777 Å,
whereas the separations of the “non-bonded” Sb-Se begin at 2.98 Å. The
(hν > Eg). As a result, Sb2Se3 films with only 800 nm thickness are Se-Sb-Se and Sb-Se-Sb angles range between 86.6° and 96.0° and be-
sufficient to absorb photons within the wavelength range of tween 91.0° and 98.9°, respectively. The Sb2Se3 structure consists of Se-
400–1000 nm (Chen et al., 2015), which is an optimal spectral range for Sb-Se chains (ribbons) along the c-axis, or the so-called needle axis.
PV conversion (cf. Fig. 2B) (Chen et al., 2015). Hence, Sb2Se3 has a crystal structure consisting of one-dimensional
High charge-carrier transport properties are also very important for (1D) ribbons formed from Sb4Se6 units, where the ribbons themselves
improving device efficiency. As shown in Table 1, high electron and are bound by weak Se–Se interactions (Ganose et al., 2017). A stereo-
hole mobilities of 15 and 42 cm2V−1s−1, respectively, have been ob- chemically active Sb s2 lone pair leads to a square pyramidal co-
tained for Sb2Se3 thin films grown with preferential crystallographic ordination around the Sb; thus, this lone pair occupies space in between
orientation, despite its anisotropic nature. the ribbons (Kyono et al., 2002; Tideswell et al., 1957).
Solar cells are minority-carrier devices (i.e., electrons in a p-type Overall, the stereochemically active lone pair leads to 1D crystal
absorber), so a long carrier lifetime of electrons (τe) is favorable to topology, which is one of the major advantages of Sb2Se3 for high-
performance PV. In other words, the bonds within the ribbons are

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A. Mavlonov, et al.
Fig. 3. (A) Partial and total density of states (DOS) and projected density of states and (B) energy band structure of Sb2Se3. (C) Crystal structure of Sb2Se3 with (1 2 0)
and preferred (2 2 1) orientations. (D) Raman spectra of Sb2Se3 thin films grown at 25° and 290 °C. The peaks at 190 and 253 cm−1 belong to Sb2Se3, where peaks at
373 and 451 cm−1 belong to Sb2O3. (A, B), (C), and (D) reproduced with permission from (Koc et al., 2012), (Zhou et al., 2015), and (Liu, X. et al., 2014),
respectively.
stronger compared to the bonds between the ribbons, which is also the
main reason for anisotropic carrier transport. Due to the 1D structure,
the grain boundaries (GBs) that form parallel to the ribbons would be
inherently benign to charge-carrier recombination. This is particularly
beneficial to reduce a major source of losses at GBs, which may exist in
three-dimensional (3D)-bonded polycrystalline thin-film solar cells. As
discussed above, the crystalline structure of Sb2Se3 is formed by the
packing of the [Sb4Se6]n ribbons, which have a quasi-1-dimensional
character (Caracas and Gonze, 2005). Within the [Sb4Se6]n ribbons, the
atoms are covalently bonded, whereas there are weak van der Waals
interactions between ribbons. Investigations by local density approx-
imation (LDA) from density functional theory (DFT) revealed that the
electron density is concentrated within the ribbons (Tan et al., 2017)
and that grain boundaries in Sb2Se3 are electrically benign (Zhou et al.,
2015). It was calculated that surfaces orthogonal to the (0 0 1) pla-
ne—e.g., (0 1 0), (1 1 0), and (1 2 0) surfaces—are the most prevalent
due to the lowest surface energies as well as absence of covalent bond
breakage and no dangling bonds. In addition, the average surface po-
tential of Sb2Se3 films has been found to be 9.1 mV, which is drastically
lower than that in CIGS or CZTS (> 100 mV) (Zhou et al., 2015). Thus,
it can be hypothesized that in Sb2Se3, recombination loss by defects can
be minimized if the surfaces are terminated by the suitably orientated
[Sb4Se6]n ribbons—namely, (1 0 0), (0 1 0), (1 1 0), and (1 2 0) planes.
This is different from the best-known PV light absorbers with 3D
structures, where the breakage of covalent bonds introduces defect
states at the GBs (Schmidt et al., 2008; Yin et al., 2014). In 3D poly-
crystalline thin-film solar cells, carrier recombination at the GBs can be
suppressed by passivation—e.g., via carefully engineering the Cu-defi-
cient GBs in CIGS thin-film solar cells (Ramanujam and Singh, 2017) or
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Solar Energy 201 (2020) 227–246
a high-temperature CdCl2 or Cd-free halogen treatment in CdTe solar
cells (Bosio et al., 2016). In comparison, such passivation may not be
required in Sb2Se3, yet controlling the film orientation is one of the key
factors to achieve high efficiency solar cell due to the anisotropic
physical properties (Zhou et al., 2015).
3.3. Electronic structure
The electronic structure of Sb2Se3 has been investigated in detail by
several research groups (Caracas and Gonze, 2005; Deringer et al.,
2015; Hurych et al., 1974; Koc et al., 2012; Sajid-ur-Rehman et al.,
2018). Research studies using LDA and generalized gradient approx-
imation (GGA) within DFT framework showed that Sb2Se3 is an in-
direct-bandgap semiconductor (Koc et al., 2012; Vadapoo et al., 2011).
Fig. 3A illustrates the partial and total DOS of Sb2Se3. As shown, the
lowest VB appears between −14 and −12 eV, which is generated by
Se-4s states. The VB located between −10 and −7 eV is mainly
dominated by Sb-5s states. The highest-occupied VB between about
−5.5 eV and 0 eV is dominated by Se-4p states and Sb-5p states; yet,
values of Sb-5p density are lower compared to that of Se-4p. However,
Sb-5p states have a larger contribution to the CB compared to the Se-4p
states. Overall, for the formation of a Sb2Se3 band structure, the 5s and
5p orbitals of Sb atoms are more dominant compared to 4s and 4p
orbitals of Se atoms.
Fig. 3B shows that the valence band maximum (VBM) of Sb2Se3 is
located between the Γ and S points in the first Brillouin zone (BZ),
whereas the conduction band minimum (CBM) is located between the Γ
and Y points of the BZ. From this calculation, the direct- and indirect-
bandgap values were found to be 1.07 and 0.99 eV, respectively, which
A. Mavlonov, et al.
Fig. 4. (A, C, D) Magnified X-ray photoelectron spectroscopy (XPS) spectra of as-deposited Sb2Se3 film. (B) Magnified XPS spectra of the plasma-etched Sb2Se3 film.
Reproduced with permission from (Liu, X. et al., 2014).
are in reasonable agreement with experimental results (cf. Table 1).
Note that these optical bandgap values are underestimated compared to
experimental data. This is mainly caused by the exchange correlation
approximation used for the DFT calculation.
In addition to electronic band structure, another important material
property is vibrational response, which can be evaluated using Raman
spectroscopy. Fig. 3D depicts the Raman spectra of Sb2Se3 thin films
grown at 25 °C and 290 °C, respectively (Liu, X. et al., 2014). At both
temperatures, two Raman peaks were observed at 190 and 253 cm−1,
corresponding to the heteropolar Sb-Se and nonpolar Sb-Sb vibrations
that are characteristics of Sb2Se3 (Liu, Y.-Q. et al., 2014,). However, two
more Raman bands were depicted at 373 and 451 cm−1, which are
characteristics of Sb2O3 and indicate the presence of Sb2O3 in Sb2Se3
(Cebriano et al., 2012). Thus, in addition to Sb2Se3 phases, experi-
mental works showed the presence of secondary phases such as Sb2O3
in the measured samples.
The chemical states of Sb2Se3 thin films are typically studied by X-
ray photoelectron spectroscopy (XPS) measurements. Fig. 4 shows the
magnified XPS spectra for as-deposited (A, C, D) and plasma-etched (B)
Sb2Se3 films (Liu, X. et al., 2014). As shown, along with the binding
energies of Sb-4d, Sb-3d, and Se-3d, the binding energy of O-1s peak
was also observed in as-deposited films (Fig. 4A), which is consistent
with the existence of Sb2O3 observed in Raman studies and other re-
ports (Honma et al., 2000). In comparison, the O-1s peak of Sb2O3 was
not observed in the plasma-treated sample (surface etching down to
∼10 nm by Ar+ source (Fig. 4B), indicating that Sb2O3 is only pre-
sented on the surface of the Sb2Se3 thin film. Shongalova et al. showed
that oxidation can also be possible reason for Sb2O3 formation
(Shongalova et al., 2018b). Recent studies also confirmed that the
Sb2O3 can be removed by chemical treatments, e.g., using (NH4)2S
aqueous solution, which can dissolve Sb2O3, Se, and Sb2Se3 (Chen et al.,
2017c; Xia et al., 2015).
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Solar Energy 201 (2020) 227–246
3.4. Electrical properties
As discussed earlier, 1D ribbon-like morphology of Sb2Se3 results in
anisotropic charge-transport properties. In general, the Sb2Se3 films are
p-type (Lai et al., 2012a; Lai et al., 2012b). However, some Sb2Se3
samples show n-type conductivity when the extrinsic dopants of Te (Wu
et al., 2015), Bi (Li et al., 2011; Sankapal et al., 2001), or intrinsically
higher Sb content (> 60%) (Mustafa et al., 2011) are introduced.
Moreover, selenium vacancy (VSe) can be also an n-type defect or a
donor. Because the p-type conductivity of the Sb2Se3 absorber has been
used for solar cells, discussions presented in this work focus on p-type
Sb2Se3 unless otherwise mentioned.
In the past, Rodriguez-Lazcano et al. studied the photosensitivity of
Sb2Se3 thin films, where the dark and illuminated conductivity values
were found to be 2 × 10−8 and 1 × 10−6 (Ω cm)−1, respectively
(Rodriguez-Lazcano et al., 2005). Yuan et al. reported the high hole
mobility of 22 cm2V−1s−1 in Sb2Se3 films (Yuan et al., 2016b), which is
even higher than in CZTS (10 cm2V−1s−1) (Huang et al., 2014) or PbSe
(< 1 cm2V−1s−1) (Liu et al., 2010). Yet, orientating the crystal grains
important to increase the solar cell efficiency by maintain the maximal
mobility and minimal recombination (Phillips et al., 2017). However,
reported free charge-carrier density (∼1013 cm−3) is much lower than
the optimal value of 1016 cm−3 for solar cells (Chen et al., 2017a), and
it may be difficult to measure accurately. Hence, several works have
been dedicated to increase the free charge-carrier density in Sb2Se3,
which will be discussed in the next section.
In early work on Sb2Se3, large 0.2–1.0 eV variation of activation
energy (Ea) of crystalline Sb2Se3 was found. This variation was attrib-
uted to the difference in the Fermi level that is pinned at a different
position in the energy gap in the range of 0.54–0.66 eV (Gilbert et al.,
1974), or to the thickness dependence of Ea in Sb2Se3 films (El-Salam
et al., 1993). The activation energy was also correlated with chemical
composition, with Ea decreasing from 1.0 eV to 0.2 eV in SbxSe1-x films
A. Mavlonov, et al.
with x from 0.0 to 0.9 (Zayed et al., 1995). The reported high activation
energies strongly suggest the presence of deep traps (Iovu et al., 2007).
Wen et al. also found that the bulk defect density in VTD-grown Sb2Se3
films is about 1014 cm−3 (interface defect density 2.8 × 1010 cm−3)
(Wen et al., 2018), which is higher than that in CdTe-based solar cells
(1011 to 1013 cm−3) (Versluys et al., 2004). Hence, the density of these
deep traps should be reduced to enhance the VOC and solar cell per-
formance.
3.5. Defects
Defects have a crucial influence on device performance by causing
degradation of optical and electrical properties (Möller, 1991), so sev-
eral researchers have investigated intrinsic defects in Sb2Se3 using ad-
mittance spectroscopy measurements (Hu, X. et al., 2018b), First-
principles Calculations (Huang et al., 2019), and hybrid Density Func-
tional Theory (Savory and Scanlon, 2019). Hu et al. found three elec-
trically active defects located at 0.3–0.4 eV, 0.2–0.6 eV, and 0.5–0.6 eV
above the VBM, which were denoted D1, D2, and D3, respectively. The
D1 and D2 defects were found to be bulk defects, and their activation
energy increased with increasing cell efficiency. The D3 defect was
found to be an interface or near-interface defect and had no obvious
relationship with efficiency of the solar cells. However, the nature of
these defects, e.g., electron or hole traps, was not stated. Wen et al.
reported that Sb2Se3 solar cells have one electron-trap (E1) and two
hole-trap states (H1 and H2). The E1 was argued to be associated with
the formation of antimony antisite (SbSe) defects, whereas H1 and H2
defects were attributed to antimony vacancy (VSb) and selenium antisite
(SeSb) defects, respectively (Wen et al., 2018). Interestingly, E1 and H2
defects have similar densities; hence, authors correlated this with the
formation of defect pairs, presumably a [SbSe + SeSb] complex.
Note that VSb and SeSb are found theoretically to be the dominant
acceptor defects in Sb2Se3 films (Liu et al., 2017). On the other hand,
VSe was reported to act not only as an n-type donor that competes with
the p-type conductivity, but also, it reduces the solar cell performance
by acting as a recombination center for the photo-generated charge
carriers (Zeng et al., 2016). In other words, the formation of VSe should
be avoided. To reduce the VSe-related recombination loss. Leng et al.
performed post-selenization treatment (Leng et al., 2014). Li et al. (Li,
Z. et al., 2016) also showed that the carrier concentration of the Sb2Se3
absorber layer can be increased as a result of the additional evaporation
of Se, which is probably due to the passivation the hole trap centers
caused by VSe. In addition to increased free charge-carrier density, they
observed lower recombination loss, which was attributed to improved
heterojunction quality. This could also be due to prolonged Se eva-
poration suppressed the formation of a Sb2O3 layer on the surface of the
as-deposited Sb2Se3 thin films.
In previous studies, the properties of intrinsic defects in binary
Sb2Se3 were expected to be simple (Liu et al., 2017). However, very
recently, Huang et al. (Huang et al., 2019) and Savory et al. (Savory and
Scanlon, 2019) have reported that the defect chemistry of quasi-one-
dimensional (Q1D) Sb2Se3 is rather complicated compared to conven-
tional semiconductors, e.g. CdTe. With other words, it has been argued
that the identical defects located on non-equivalent atomic sites might
have different properties, e.g. formation energy, because of the low
symmetry of the Q1D structure (Fig. 5A). Although these two studies
have general similarity on expectations and results, we note various
results. For instance, Huang et al. reported that VSe1, VSe2, VSe3, SbSe1,
SbSe2 and SbSe3 are donor defects, whereas VSb1, VSb2, SeSb1, and SeSb2
are acceptor defects. Furthermore, it has been predicted that 2SeSb1,
and 2SeSb2 (two Se anions take the place of one Sb cation site) may also
form, which are expected to be acceptor defects. In contrast, Savory
et al. have reported for the first time that SbSe1, SbSe2 SbSe3 SeSb1 and
SeSb2 are amphoteric defects, which can be possible trap states for both
electrons and holes. They showed that under Sb-rich conditions, several
defects, e.g. VSe (all sites), SbSe (all sites) and the Sb interstitial (Sbi),
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Solar Energy 201 (2020) 227–246
have formation energy below 1.5 eV, which are expected to be present
in the film in reasonable concentrations (Fig. 5B). However, under Se-
rich condition, the formation energies of several problematic defects are
moved to higher energy positions (See Fig. 5C). Overall, studies have
shown that intrinsic defects have lower concentration under Se-rich
condition compared to Sb-rich condition, which can clarify to some
extent why higher device performances have depicted for the samples
grown under Se-rich condition. Furthermore, VOC deficit, i.e. ∼0.42 V
for most of the champion solar cells, has been correlated with Fermi
level pinning at about 0.4 eV (Huang et al., 2019) or at 0.58 eV (Savory
and Scanlon, 2019) above the VBM under Se-rich condition, approx-
imating a maximum achievable VOC to be around 0.47 V. However,
recent experimental studies have shown that solar cells with VOC of
0.57 V (Zhao et al., 2018b) or even 0.64 V (Zhao et al., 2018a) can be
fabricated.
In addition to intrinsic defects, several effects are also expected from
extrinsic doping, including bandgap modulation (Asaduzzaman et al.,
2016; Mohamed and Rohani, 2011), grain-size enhancement (Yang
et al., 2012), defect passivation (Altamura et al., 2016; Liu et al., 2015),
conductivity increase (Grundmann, 2015; Hu, L. et al., 2018; Li et al.,
2013), and photoactivity improvement (Altamura et al., 2016; Liu
et al., 2015). Li et al. (Li, Y. et al., 2016b) reported that Mg was found to
be inert to the electric properties of Sb2Se3, whereas Fe introduced n-
type doping. However, free charge-carrier concentration remained low
(about 1013 cm−3), i.e., similar to those of the undoped Sb2Se3, perhaps
due to problems with incorporating dopant into the Sb2Se3 crystal. In
contrast, Costa et al. (Costa et al., 2018) reported that Fe-doped Sb2Se3
films grown by co-electrodeposition are p-type with high carrier density
ranging from 3.7 × 1016 cm−3 (undoped) to 1.0 × 1019 cm−3. The
highest free charge-carrier density was reported for a 5% concentration
of Fe ions relative to Sb content in the solvent. The free charge-carrier
density was found to decrease with further increase in the Fe con-
centrations up to 20% and 50%, arguably due to donor defects that
partially compensate acceptor defects and/or due to formation of Sb2O3
secondary phases.
Furthermore, Alemi and coworkers reported on Sb2Se3 films doped
with several transition metals and lanthanides, namely, Lu3+, Ho3+,
Nd3+, Sm3+, and Gd3+, and co-doped with Lu3+/Yb3+ and Lu3+/Er3+
(Alemi et al., 2011a, b; Alemi et al., 2012; Hanifehpour et al., 2013).
The electrical conductivity of the doped Sb2Se3 films was slightly im-
proved compared to that of undoped films, which further increased
with increasing temperature. Chen et al. reported on Sn-doped Sb2Se3
films (Chen, S. et al., 2018). They found that Sn-doping also enhanced
the electrical conductivity of the films, which yielded free charge-car-
rier density of about 2 × 1016 cm−3. In addition to aforementioned
dopants, alkaline doping (Na) has also been investigated on RTE-grown
Sb2Se3 films, inspired by its success in Cu2SnS3 (Chantana et al.,
2017c), Cu2ZnSnSe4 (López-Marino et al., 2016) and CIGS (Pianezzi
et al., 2014) solar cells. However, Na doping was found to degrade the
performance of the Sb2Se3-based solar cells, and it showed negligible
influence on the conductivity of the film (Li, Y. et al., 2016a). The
authors argued that Na diffuses in the film and remains inert between
(Sb4Se6)n ribbons.
Overall, more systematic and quantitative investigations on doped
Sb2Se3 films are needed to clarify the doping effects toward efficient
electrical properties in the Sb2Se3 films. In addition, a comparative
study on various growth methods could probably be beneficial to se-
parate the effective influence of the dopants from side effects, e.g., poor
crystal quality or formation of unintentional defects during the de-
position process.
3.6. Optical properties
The optical properties of Sb-Se compounds strongly depend on both
crystal structure and chemical composition. Polycrystalline Sb2Se3 films
with stoichiometric composition exhibit Eg within the range of
A. Mavlonov, et al. Solar Energy 201 (2020) 227–246

Fig. 5. (A) Crystal structure of Sb2Se3 with labeled individual sites and calculated formation energy of intrinsic defects versus Fermi level above the VBM for Sb2Se3
under (B) Sb-rich and (C) Se-rich chemical potential conditions. Defect labels are given in the legend, whereas transition levels are shown by the filled dots, charge
states are given by labels next to lines, where the lines with the same slope represent the same charge state. Adopted from (Savory and Scanlon, 2019).

Fig. 6. (A) The incident light intensity decay

versus wavelength for c-Sb2Se3. The dashed
line is the absorption coefficient versus wa-
velength (top x-axis; right y-axis). (B) The
calculated normal-incidence reflectivity from
air to a-Sb2Se3 (black line) and c-Sb2Se3 (red
line), and from CdS to c-Sb2Se3 film (green
line). The solid blue line is the experimen-
tally measured reflectance at the air/c-
Sb2Se3 interface. Adopted from (Chen et al.,
2015).

1.0–1.3 eV in most of the reports (Chen et al., 2015; Costa et al., 2018;
Lai et al., 2012a; Ma et al., 2011; Mehta et al., 2010; Park et al., 2019;
Rajpure and Bhosale, 2000; Shen et al., 2018), but larger variations of
the bandgap values have been reported in literature (Fernandez and
Merino, 2000; Hanifehpour et al., 2013). This Eg variation in poly-
crystalline films was attributed to the fact that Sb2Se3 thin films pre-
pared by various methods and growth conditions could have different
Sb/Se ratios and/or different crystalline quality (Kosek et al., 1978). In
addition to these experimental data, DFT calculations also showed
different optical bandgap values in the range of 0.99–1.32 eV (Koc
et al., 2012; Lawal et al., 2018; Vadapoo et al., 2011). Systematic in-
vestigation on optical properties of Sb2Se3 by Chen et al. (Chen et al.,
2015) showed that polycrystalline Sb2Se3 has an indirect bandgap of
1.03 eV and a direct bandgap of 1.17 eV at 300 K. This was confirmed
by temperature-dependent transmission and photoluminescence mea-
surements, and it was similar with other recently reported experimental
data (Black, 1957; Haque et al., 2018; Lai et al., 2012a). These ex-
perimental as well as theoretical results indicate that the Eg of Sb2Se3
lies within the optimal range shown in the S-Q model to achieve high
PCE (Fig. 2B) (Shockley and Queisser, 1961). In addition to an optimal

234
A. Mavlonov, et al.
Eg, the absorber layer should have a high absorption coefficient
(α > 104 cm−1) to effectively generate the electron-hole pairs. Flat
electronic bands of Sb2Se3 are suggested to yield enhanced light ab-
sorption due to the high DOS present in the valence and conduction
band extremes (Yu et al., 2013). This is also reflected by experimental
data, where Sb2Se3 films have a high absorption coefficient in the range
of 105 cm−1 for hν > Eg (Lai et al., 2012a; Lai et al., 2012b; Li, D.-B.
et al., 2018; Liang et al., 2017; Liu et al., 2015; Steinmann et al., 2015).
This value is very beneficial for PV applications and much higher than
that of other novel PV absorber layers (Fernandes et al., 2010;
Kazmerski et al., 1983; Lakhdar et al., 2014; Sun et al., 2011). Thick-
ness-dependent studies showed that photons with wavelengths
λ > 800 nm are completely absorbed within 400-nm-thick Sb2Se3 film
(cf. Fig. 6A) (Chen et al., 2015), which is lower than the thickness of
conventional thin-film solar cell absorbers. Moreover, high dielectric
constant (εr) values are favorable for the absorber layer because they
lead to better screening of the photo-generated charge carriers from
electrically charged defects. Investigations show that Sb2Se3 has higher
εr values (> 18 ε0) compared to those of CdTe (10.0 ε0) and CuInSe2
(14.3 ε0) (Chen et al., 2017a; Madelung, 2012). This higher εr leads to
lower exciton binding energy (Eexc), which is required for effective
dissociation of excitons into free electrons and holes upon light illu-
mination (Lawal et al., 2018).
Reflection loss is one of the limitations in PV technology which can
be minimized by antireflective coating (Yao and He, 2014). As shown in
Fig. 6B, the Sb2Se3 reflection loss of direct illumination was found to be
40%, which further dropped to 10% for a CdS/Sb2Se3 heterojunction
within the wavelength range of 500–1,700 nm (Chen et al., 2015).
Hence, it is necessary to use an antireflection layer to improve the
photocurrent in the Sb2Se3 solar cells. Compared to the crystalline
Sb2Se3 (c-Sb2Se3), amorphous Sb2Se3 (a-Sb2Se3) showed suppression of
reflectivity (Fig. 6B) in the visible and near-ultraviolet. This suppression
was argued to be due to the sensitivity of the resonant p-bonds transi-
tions to the absence of long-range order and/or due to influence of the
disorder on the CB DOS resulting from reduced Sb-5d band-overlap
contributions (Shaffer et al., 1972). This CB DOS argument was sup-
ported by XPS data, showing that c-Sb2Se3 and a-Sb2Se3 showed similar
magnitude of the VB DOS (Wood et al., 1972).
3.7. Amorphous Sb2Se3
A literature survey shows that the room-temperature and/or low-
temperature (< 150 °C) grown Sb2Se3 thin films are amorphous, in-
dependent of the deposition process. The optical bandgap of a-Sb2Se3
was found to be 1.39 ± 0.02 eV using ellipsometry measurement
(Chen et al., 2015), which is higher compared to those of the poly-
crystalline films (Haque et al., 2018). This difference is mainly due to
the amorphous nature of the material. Moreover, the bandgap of
Sb1-xSex compound increases monotonically from 0.15 eV (for x = 0) to
1.95 eV (for x = 1) (Shimakawa, 1981).
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Solar Energy 201 (2020) 227–246
Fig. 7. (A) The variation of the optical
bandgap in the amorphous Sb-Se system as a
function of Sb concentration. Dashed lines
show the bandgap of Se (1.95 eV) and Sb
(0.15 eV) elements. Solid line represents the
linear function of alloy composition given in
Eq. (1). The circles are the experimental Eg
values. Adopted from (Shimakawa, 1981).
(B) The lattice constant versus bandgap en-
ergy of absorber layers (blue circles) and
buffer layers (red triangles) used in thin-film
solar cells. Data taken from (Burst et al.,
2016).
Mustafa et al. investigated the temperature- and composition-de-
pendent optical parameters of a-Sb2Se3 grown by thermal evaporation.
The bandgap of a-Sb2Se3 decreases with increasing Sb content and with
increasing temperature. For different composition ratios, Eg values were
obtained using linear, nonlinear, Varshni, and Bose-Einstein equations.
Among them, the Varshni equation yielded the best fitting with Eg and
the rate of Eg change values of 1.43 eV and 9.30 × 10−4 eV/K, re-
spectively. Furthermore, they found that optical absorption of a-Sb2Se3
obeys the indirect-transition process. The composition-dependent var-
iation of the Eg was also observed in other publications, which mono-
tonically decreases with increasing Sb/Se ratio (Fouad et al., 1997;
Mueller and Wood, 1972; Rajpure et al., 1997; Torane et al., 1999;
Wood et al., 1973). This composition-dependent Eg was explained by
the chemical-bond approach (Shaaban et al., 2007): (a) atoms of dif-
ferent kinds (Sb-Se) combine more favorably than with the same kind
(Sb-Sb). Consequently, bonds between atoms of the same kind will only
occur if there is an excess of a certain type of atom. (b) The sequence of
bond formation depends on decreasing bond energy and goes until all
the available valences of the atoms are saturated. And (c) each atom is
coordinated by 8-N atoms, where N is the number of outer shell elec-
trons. Based on this theory, increasing the antinomy content leads to a
decrease of low-probability Se-Se bonds. Thus, by adding Sb to SbxSe1-x,
the average bond energy of the compound decreases, and the bandgap
decreases.
On the other hand, Shimakawa showed that the optical bandgap of
the a-Sb2Se3 films can be explained using the following equation
(Shimakawa, 1981):
Eg (Sb, Se) (Y ) = YEg (Sb) + (1 − Y ) Eg (Se), (1)
where Y, Eg(Sb), and Eg(Se) are the volume fraction of Sb element,
bandgap of Sb (0.15 eV), and bandgap of Se (1.95 eV), respectively
(Shimakawa, 1981). As shown in Fig. 7A, this calculation is in good
agreement with experimental data. Also, El-Sayad et al. (El-Sayad et al.,
2009) reported on structural and optical properties of nearly stoichio-
metric a-Sb2Se3 thin films grown by thermal evaporation, as a function
of heat-treatment temperature, where annealing was performed in a
vacuum under a pressure of ∼1.5 × 10−4 Pa. An amorphous-to-crys-
talline phase transition was found to occur at 423 K (150 °C). Further-
more, post-annealing at different conditions also confirmed the phase
transition from amorphous to crystalline at higher temperatures (Costa
et al., 2017; Kamruzzaman et al., 2017). In contrast to polycrystalline
Sb2Se3 films, which exhibit both indirect- and direct-bandgap optical
transitions, a-Sb2Se3 films show only indirect bandgap with a relatively
high 0.49-eV Urbach’s tail, compared to 0.32 eV for polycrystalline
films annealed at 473 K.
A. Mavlonov, et al.
4. Solar cell fabrication
4.1. Summary of solar cell fabrication
Unlike silicon-based solar cells, thin-film solar cells have two typical
configurations: substrate and superstrate configurations (cf. Fig. S1). In
a substrate configuration, the layers are deposited with a bottom-up
approach, i.e., deposition starts with the back contact and ends with the
top transparent electrode (TE) layer, which is on the light-exposed side.
Hence, this configuration allows the use of opaque substrates such as
commercially available rigid and/or flexible thin metallic foils, cera-
mics, and polymers. In a superstrate configuration, the layers are de-
posited with a top-down approach, where the deposition starts with the
top TE layer, i.e., the light-exposed side, and the process ends with the
deposition of metallic back-contact. Consequently, only highly trans-
parent substrates are required for this configuration because light has to
pass through the substrate and reach the absorber layer. In the case of
the superstrate configuration, which is more common for Sb2Se3, the
solar cells work as follows: the n-type TE and CdS layers transmit the
photons to the Sb2Se3 layer, which can contribute for electron-hole pair
generation. The photons with higher energy (> 2.4 eV) do not con-
tribute for this process due to their absorption in the TE (Eg > 3 eV)
and/or CdS (Eg = 2.4 eV) layers (Hamri et al., 2019). Photo-generated
minority-charge carriers (electrons) move from p-type Sb2Se3 to n-type
CdS due to the creation of a built-in electric field at the p-n hetero-
junction between the Sb2Se3/CdS interface, then these electrons move
into the TE layer. On the other hand, holes are attracted by the p-type
hole-transport layer and collected by the back contact. In the conven-
tional high-efficiency solar cells, each component layer of the solar cell
contributes in its own way to enhance the PCE of the device. Fig. 8
shows the common Sb2Se3–based thin-film solar cell with substrate
configuration, which consists of glass/BC/HTL/Absorber/CdS/
window/TE/Anti-reflective coating/Grid layers. As shown, the thin-
film device structure is made of several layers and interfaces. As a re-
sult, not only the quality of the absorber layer, but also properties of
other layers and interfaces, e.g. absorber/BC, buffer/absorber, and TE/
buffer, affect the PV performance (Minemoto et al., 2001b; Minemoto
and Murata, 2015). Fig. 8 depicts the technical issues that have an ef-
fect on the device performance. In particular, the influence of the
crystal orientation (in Sb2Se3 bulk), sputtering damage and the rollover
effects (at the interface and surface of Sb2Se3) needs further detailed
investigations in nanoscale, since materials with nanoscale structure
(nanomaterials or nanosctucrures) mostly have unique physical prop-
erties (Hübler and Osuagwu, 2010).
To understand the status of the Sb2Se3 solar cells, it is instructive to
compare them with CdTe solar cells. CdTe is one of the most successful
Fig. 8. The typical (substrate) structure of thin-film solar cells and technical issues related to each layers and/or interfaces. TE, HTL, and BC denote the ‘transparent
electrode’, ‘hole transport layer’, and ‘back contact’, respectively. Note that the sputtering damage at the absorber surface is caused during the deposition of window
and/or TE layers by sputtering method.
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Solar Energy 201 (2020) 227–246
thin-film solar cells and has the second-largest share (5%) in the world
PV market after silicon (Si)-based solar cells (∼92%) (Ramanujam and
Singh, 2017). CdTe has an almost ideal bandgap of 1.45 eV and high
absorption coefficient (104–105 cm−1) for use as a PV absorber material
with a thickness of only about 1–4 µm (Bosio et al., 2018). CdTe has a
cubic zincblende crystal structure with a high melting point of 1,092 °C
(Belas et al., 2003). Unlike ternary and quaternary compounds, the
physical and chemical properties of the CdTe films—e.g., stoichiometry,
morphology, phase, and defect density—can be controlled more di-
rectly (Steinmann et al., 2015). Despite its high melting point, recent
advances of deposition techniques allowed deposition of CdTe at rela-
tively low temperature (< 450 °C) (Romeo et al., 2018) using various
growth methods (Ojo and Dharmadasa, 2016; Paudel et al., 2014;
Rimmaudo et al., 2017). However, CdTe thin-film solar cells deposited
at low temperatures have showed relatively low PCE (16%) compared
to those deposited at high temperature (22.1%) (Green et al., 2018;
Romeo et al., 2018). Over some 40 years, CdTe research achievements
have yielded a PCE of 22.1% at lab scale and 18.6% at the module level,
which are commercially available from the U.S. PV supplier, First Solar
(Bosio et al., 2018; Green et al., 2018). The champion CdTe thin-film
solar cells with the VOC of 887.2 mV, JSC of 31.69 mA/cm2, and fill
factor (FF) of 78.5% have yielded the record cell efficiency of 22.1%
(Green et al., 2018). If these parameters are compared with the values
from the S-Q limit, JSC/JS-Q ≈ 0.96, which is an indication of good
carrier collection resulting from high absorption coefficient. However, a
voltage deficit of VOC/VS-Q ≈ 0.75 is suggested to be due to the re-
combination losses at the interface and/or crystal grains of the poly-
crystalline CdTe (Polman et al., 2016). However, concerns regarding
toxicity of Cd and scarcity of Te necessitate the development of alter-
native solar cell materials to further increase the production capacity
and reduce the cost—e.g., via omitting the additional recycling systems
that are required for commercial CdTe modules.
In contrast to CdTe, Sb2Se3 is a low-toxicity, cost-effective com-
pound that also has excellent optoelectric properties such as an optimal
bandgap of 1.1 eV and high absorption coefficient of 105 cm−1.
Interestingly, Sb2Se3 has also been investigated for more than 40 years,
but its use as a solar cell absorber has only been seen recently. Sb2Se3
possesses a smaller bandgap than CdTe, so a theoretical JSC of 44.23
mAcm−2 is expected, which is higher compared to 32.88 mAcm−2 for
CdTe due to extended photon absorption in the infrared (IR) spectral
region (Rühle, 2016). Due to its simple binary structure and lower
melting point of 611 °C compared to CdTe (1092 °C), it has been pos-
sible to deposit Sb2Se3 in the form of high-quality microcrystals at re-
latively low temperatures (300–400 °C) without the complexity of
phase and composition control. Such low temperatures allow the use of
flexible polymer substrates as well as more cost-effective TEs, e.g., Al-
A. Mavlonov, et al.
doped ZnO (AZO), with wider bandgap and better optoelectric prop-
erties. Furthermore, unlike the 3D cubic crystal structure of CdTe,
Sb2Se3 consists of pseudo-1D ribbons that make this material scientifi-
cally interesting. Such low-dimensional features can be beneficial to
obtain electronically passive GBs due to fewer dangling bonds, com-
pared to 3D bonded absorber materials that have strong (covalent)
bonds in all dimensions (Steinmann et al., 2015; Zakutayev, 2017). To
date, a Sb2Se3 record efficiency of 9.2% has been obtained with JSC of
32.58 mAcm−2, VOC of 0.4 V, and FF of 70.3% (Li et al., 2019). Recent
advances in the PCE of Sb2Se3-based solar cells are summarized in Table
S1. In the following section, we introduce the growth methods used for
solar cell fabrication, then analyze the limitations of device perfor-
mance.
4.2. Absorber deposition methods
Preparation of high-quality materials with good surface morphology
as well as low defect and pinhole density is required to reduce the re-
combination losses and device shunting to obtain high-performance
solar cells. However, high-quality absorber growth is a very complex
task that involves optimizing deposition conditions and heat-treatment
procedures as well as selecting partner compounds with suitable lattice
parameters and electronic properties. Moreover, apart from conven-
tional inorganic solar cells with cubic crystal structure, the pseudo-1D
structure of Sb2Se3 offers unique opportunities for efficient charge
transport and low recombination behavior, but also adds new chal-
lenges for material preparation. Controlled nucleation is required
during the growth of anisotropic materials because the transport
properties of the device depend on anisotropic physical properties.
Thus, optimization of growth parameters to prepare the film without
(or with fewer) pinholes, desired surface roughness, and with alignment
of grains with proper direction is required to maintain good transport
properties.
So far, the deposition of Sb2Se3 thin films has been explored by
several growth methods. Physical deposition methods for preparing
Sb2Se3 include physical vapor deposition (Bibin and Kunjomana, 2019),
thermal evaporation (Butt et al., 2018), vacuum evaporation (Mustafa
et al., 2009), rapid thermal evaporation (Wang et al., 2017), vapor
transport deposition (Liu et al., 2017), magnetron sputtering (Liang
et al., 2017; Liang et al., 2018; Shongalova et al., 2018a; Tang et al.,
2019b), close-spaced sublimation (Hutter et al., 2018b; Li, D.-B. et al.,
2018; Li, G. et al., 2018) chemical molecular beam deposition (CMBD)
(Razykov et al., 2018b), and pulsed laser deposition (PLD) (Yu et al.,
2010). Chemical methods for Sb2Se3 growth include electrodeposition
(Kwon et al., 2017), chemical-bath deposition (Rodriguez-Lazcano
et al., 2005), successive ionic-layer adsorption and reaction (SILAR)
(Pathan and Lokhande, 2004), solvothermal synthesis (Ma et al., 2011),
spin coating (Kim et al., 2017; Wang et al., 2019), and vapor–liquid-
solid (VLS) growth (Yang et al., 2009). Among them, physical deposi-
tion methods—namely RTE, CSS, and VTD—have yielded higher PCE
compared to chemical methods, whereas spin coating has been pro-
mising among the chemical methods. Hence, we briefly introduce these
four growth methods for Sb2Se3 preparation in the following section. In
addition to growth methods, several post-treatment processes—namely,
heat treatment (Wen et al., 2017), chemical treatment (Chen et al.,
2017c; Leng et al., 2014; Li, Z. et al., 2016), and doping (Chen, S. et al.,
2018; Li, Y. et al., 2016a)—have been applied to enhance the material
properties and device performance, as is also discussed below.
Close-Spaced Sublimation. Relatively low cost and high growth rate
are the main advantages of CSS. This method has been widely used to
deposit semiconductor compounds such as CdTe (Alamri, 2003) for PV
applications. Recently, this method was also used to fabricate Sb2Se3
solar cells (Hutter et al., 2018a; Li, D.-B. et al., 2018). Sb2Se3 source
(powder) and substrate are placed in the bottom and top of the graphite
box, respectively. Most CSS-deposited Sb2Se3 solar cells have been
fabricated with a superstrate configuration. However, the highest
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Solar Energy 201 (2020) 227–246
efficiency of 9.2% with JSC = 32.58 mAcm−2, VOC = 400 mV, and
FF = 70.3% was obtained from a ZnO:Al/ZnO/CdS/TiO2/Sb2Se3/
MoSe2/Mo substrate configuration (Li et al., 2019).
Rapid Thermal Evaporation. The deposition principle of RTE is very
similar to the CSS method. Hence, the source-to-substrate distance is
about < 10 mm. Unlike CSS, RTE uses a very short growth time of a
few tens of seconds that may further lower the processing costs.
Although deposition time is short, RTE has been found to be sufficient
for nucleation of crystals and morphology control (Zhou et al., 2015).
Most RTE-deposited Sb2Se3 films have not required additional heat
treatment, so this method has been very productive for preparing sev-
eral champion solar cells over the past 4–5 years with PCEs in the range
of 2%–7%. To date, RTE-deposited Sb2Se3 thin-film solar cells have
reached the highest PCE of 7% with JSC ≈ 29 mAcm−2, VOC ≈ 410 mV,
and FF = 59.3% for a simple ITO/CdS/Sb2Se3/Au structure (Chen, C.
et al., 2018). However, the main drawbacks of this method are: 1) the
need for further improvement of crystalline quality by reducing the
defect density, which is mainly caused by the small distance between
source and the substrate, as well as very short deposition time, which
makes it difficult to mix the vapors of elements. 2) Because RTE is a
vacuum-based method, deposition cost can be higher compared to non-
vacuum chemical growth methods. Despite the existence of these pro-
blems, RTE has been one of the best methods to fabricate Sb2Se3 solar
cells in laboratory scale.
Vapor Transport Deposition. In the VTD method, the most important
deposition parameters that can influence the growth kinetics and ma-
terial quality are source-to-substrate distance, source and substrate
temperatures, and partial pressure of ambient gases. VTD-grown sam-
ples have shown higher crystalline quality and lower defect density
compared to RTE-grown samples. Hence, VTD-deposited Sb2Se3 thin-
film solar cells yielded the highest efficiency of 7.6% with JSC = 29.9
mAcm−2, VOC = 420 mV, and FF = 60.4% for a simple ITO/CdS/
Sb2Se3/Au solar cell structure (Wen et al., 2018).
Spin Coating. Spin coating is a non-vacuum chemical deposition
method. Several parameters such as solution pH, ion concentrations,
complexing agents, temperature, rotation speed, and number of coating
layers can be adjusted to control kinetics and thermodynamics of the
spin-coating growth process. This method is not only simple and cost
effective, but also has several advantages such as easy dopability. For
example, introducing the extrinsic dopants into the films can easily be
achieved by adding respective solute of dopants in the precursor solu-
tion, which is important for optimizing the physical properties of the
solar cells. Using this method (Choi et al., 2014c), Sb2Se3-sensitized
inorganic–organic heterojunction solar cells with single-source Sb2Se3
precursor (Se-SPP) achieved the PCE of 3.9% with JSC = 27.2 mA/cm2,
VOC = 340 mV, and FF = 41.9% for a FTO/TiO2/CdS/Sb2Se3/HTL/Au
device structure (Wang et al., 2019).
To summarize these different methods, Fig. 9 shows the J-V curve
and external quantum efficiency (EQE) spectra of Sb2Se3 devices fab-
ricated by the aforementioned growth techniques. In general, the de-
vice parameters, e.g. PCE, JSC and FF, exhibit a strong correlation with
series resistance of the solar cell which is discussed in details in Section
4.6. As expected, the CSS-grown champion cell has the highest FF,
whereas the cell prepared by spin coating had the lowest FF. Because
VTD and RTE devices were prepared by the same research group using
an identical device structure of ITO/CdS/Sb2Se3/Au, the devices have a
similar J-V curve; however, the former cell has a slightly higher current
density compared to the latter. This difference is mainly due to the
improved crystalline quality of the VTD Sb2Se3 film. On the other hand,
the CSS cell has a higher EQE in the long-wavelength spectral region
compared to other counterparts. Since the EQE of the solar cell at the
infrared spectral range is strongly related to rear surface recombination,
the diffusion lengths as well as the absorption of the photons, the higher
red response of the CSS cell might be due to improved device structure.
However, this champion device showed a low EQE in the low-wave-
length region. This is probably correlated with the reduced
A. Mavlonov, et al.
Fig. 9. (A) J-V curves and (B) EQE spectra of Sb2Se3 solar cells fabricated using different growth methods. Adopted from (Chen, C. et al., 2018; Li et al., 2019; Wang
et al., 2019; Wen et al., 2018).
transmittance of the ZnO:Al/ZnO/CdS/TiO2/Sb2Se3/MoSe2/Mo struc-
ture. Interestingly, similar double buffer layers of CdS/TiO2 were used
in VTD and spin-coated devices, but the latter cell showed a higher EQE
in the short-wavelength region compared to the former cell. The reason
for this performance difference is still unclear.
Post-deposition annealing is an efficient approach to passivate
electrically active defects. As discussed, the oxidation of the Sb2Se3
surface with a 1.15-nm-thick oxide was observed in some studies where
Sb2Se3 was annealed in air. To avoid forming this oxide layer during the
heat treatment, post-annealing under an air-free environment (e.g.,
under N2 or Se(vapor)/N2 flow) has been suggested (Costa et al., 2017;
Kamruzzaman et al., 2017). These studies found that as-grown Sb2Se3
films were amorphous and that after thermal treatment, all films
showed a pure orthorhombic Sb2Se3 phase. It was also found that
300 °C is optimal for PV application, whereas at higher annealing
temperatures (400 and 500 °C), heat treatment caused the crystal-
lographic texturing of films in the (1 2 0) direction, which is detrimental
for PV performance. In addition to these studies, Chen et al. demon-
strated that recombination losses at GBs can be reduced by introducing
n-type Cu interstitial doping at GBs using low-temperature CuCl2 heat
treatment (Chen, C. et al., 2018).
4.3. Buffer layer
The buffer layer is usually an n-type material that is used to form a
p-n heterojunction with a p-type absorber layer. The bandgap of the
buffer layer should be wide enough to transmit light into the absorber
layer. From an electrical perspective, photo-generated electrons in the
absorber layer move toward the TE layer through the buffer layer. To
avoid energy losses in these regions, lattice matching and proper band
alignment (in energy) must be considered. Fig. 7B shows the lattice
constant versus bandgap of buffer (red color) and absorber (blue color)
used in thin-film solar cells. Lattice mismatch at the interface may lead
to interfacial defects, Fermi-level pinning, and band alignment issues
that can limit device performance.
One of the most commonly used buffer layers in thin-film solar cells
is CdS (Al-Douri et al., 2014; Al-Douri et al., 2013; Ibraheam et al.,
2016), even though it has different lattice matching with different ab-
sorber layers. For example, the interface of the CdS/Cu(In,Ga)Se2 het-
erojunction has a very small lattice mismatch of < 1% (Furlong et al.,
1998; Lindahl et al., 2013). However, the lattice mismatch was found to
be 10% for the CdS/CdTe interface (Terheggen et al., 2004), where
nanocrystalline CdS grains were suggested to reduce the strain (Burst
et al., 2016). For CdS/Cu2ZnSnS4, a lattice mismatch of 7% is reported,
whereas the substitution of a CdS buffer layer with ZnS yielded a
smaller value of 1% (Kaur et al., 2017). As shown in Fig. 7B, a large
lattice mismatch (> 10%) is expected between CdS and Sb2Se3; how-
ever, it has been widely used in the Sb2Se3 solar cell structure. On the
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Solar Energy 201 (2020) 227–246
other hand, novel buffer layers, i.e., SnO2, TiO2, and ZnO, have similar
lattice parameters with Sb2Se3 film.
In Sb2Se3 solar cells, the importance of minimizing lattice mismatch
was realized as early as 1982 (Bhattacharya and Pramanik, 1982); yet,
most studies on this issue have been qualitative. Phillips et al. observed
that Sb2Se3 thin films grown on TiO2 exhibited voids, which were at-
tributed to contamination of the surface and/or strain relief due to
lattice mismatch (Phillips et al., 2017). Similarities between SnO2
buffer layer and commonly used TEs of ITO (In2O3:Sn) and FTO
(SnO2:F) are expected to produce less lattice mismatch. Lu et al. re-
ported that for SnO2/Sb2Se3 solar cells, the lowest interfacial defects
density was for SnO2 film annealed at 480 °C (Lu et al., 2018). Liu et al.
reported that the lattice mismatch and dangling bonds at the CdS/
Sb2Se3 interface were the main causes for increased defect states (Liu
et al., 2015). When they deposited the Sb2Se3 under an oxygen en-
vironment, the device performance was significantly enhanced com-
pared to that of the reference device; the improvement was correlated
with reduced lattice mismatch or passivated dangling bonds at the CdS/
Sb2Se3 interface. Wang et al. showed that the ZnO/Sb2Se3 interface had
lower defects density when randomly oriented ZnO was used, compared
to [0 0 1]-oriented ZnO (Wang et al., 2017). First-principles calculations
of nitrogen-doped Sb2Se3 also showed that lattice parameters of the
host material can be altered by doping due to the large difference in
electronic polarizability between the cations and dopants, and an
elasto-optic effect triggered by the lattice expansion or contraction
(Sajid-ur-Rehman et al., 2018). Overall, both experimental and theo-
retical works have shown that the lattice matching at the buffer/Sb2Se3
interface can be further improved by using novel buffer layers (Fig. 7B)
and/or by controlling the lattice parameters of Sb2Se3.
In addition to lattice matching, electronic band alignment at the
interface should be optimized to avoid unintentional energy losses at
the interfaces. As shown in Fig. S2, if the CBM of the buffer layer is
higher than that of the absorber layer, the interface is defined as a
“spike,” where a barrier is formed against photo-generated electrons
leading to a decrease in JSC and FF. In contrast, when the CBM of the
buffer layer is lower than that of the absorber, this interface is defined
as a “cliff,” which leads to an increase of JSC; yet, VOC decreases due to
the increased carrier recombination rate. Hence, proper band alignment
with a minimization of CB mismatch is required in solar cells. In the
case of CIGS-based solar cells, excellent device performance was sug-
gested when CB position of the buffer layer higher by 0–0.4 eV com-
pared to that of the absorber layer (Minemoto et al., 2001b). It has been
observed that when buffer layers with tunable bandgap were used in
thin-film solar cell structures— e.g., in Cu(In,Ga)Se2 (Minemoto et al.,
2011), Cu(In,Ga)(Se,S)2 (Chantana et al., 2017b), Cu2ZnSn(S,Se)4
(Hironiwa et al., 2015) and CH3NH3Pb3-xClx perovskite heterojunctions
(Minemoto and Murata, 2015)—the PCE of these thin-film solar cells
was enhanced.
A. Mavlonov, et al.
Engineering of the buffer/absorber interface in solar cells has been
demonstrated to improve device performance due to improved carrier-
transport properties and reduced recombination losses. In particular,
recombination losses through trap states might be minimized by
avoiding the misalignment between the CBM of the buffer and absorber
layers (Kaur et al., 2017). However, not only the buffer/absorber in-
terface, but also the TE/buffer interfaces have to be band-aligned for
effective collection of photo-generated carriers (i.e., electrons in the
case of Sb2Se3). To date, CdS is the most commonly used buffer layer in
Sb2Se3 solar cells mainly because of its easy preparation via well-es-
tablished chemical-bath deposition and acceptable CB alignment
(Fig. 10). However, CdS has some drawbacks, namely: 1) unintentional
absorption of photons in the CdS layer at higher photon energies due to
its low bandgap of 2.4 eV (Matsuo et al., 2015), 2) detrimental effects
on the device performance via diffusion of Cd into Sb2Se3 (Zhou et al.,
2017), 3) high lattice mismatch (cf. Fig. 7B), and 4) toxicity (Zhou
et al., 2014). Hence, several alternative buffer layers have been in-
vestigated for Sb2Se3 solar cells.
Recently, Sb2Se3/buffer heterojunctions have been prepared using
various buffer layers such as ZnO, TiO2, SnO2, and CdSe. Wen et al.
investigated ZnO/Sb2Se3 solar cells and found that not only crystalline
orientation of the absorber layer but also the defects in ZnO are im-
portant for improving device performance (Wen et al., 2017). Tang and
co-workers (Li, K. et al., 2018) showed that PCE of Sb2Se3-based thin-
film solar cells can be improved by using tunable-bandgap Zn1-xMgxO
as a buffer layer, which was initially used in CIGS-based solar cells in
order to decrease the majority carrier recombination via the buffer/
CIGS interface defects (Minemoto et al., 2001a; Minemoto et al., 2003).
In addition to aforementioned single buffer-layer structures, double
buffer-layer strategies have also been considered in order to reduce the
shunting path between absorber and TE layers by utilizing a highly
resistive second buffer layer, e.g. i-ZnO (Ishizuka et al., 2005) or
Zn1-xMgxO (Chantana et al., 2017b). In Sb2(S,Se)3 solar cells, a TiO2/
CdS double buffer layer has been used to achieve a high VOC of 792 mV
by increasing the RSh (Wang, W. et al., 2018), where TiO2 has been used
as a window layer. For ZnO/Zn1-xMgxO/Sb2Se3 devices with a double
buffer, improved device performance (4.45%) has been reported com-
pared to the control device with single ZnO buffer layer (Li, K. et al.,
2018). In this report, ZnO/Zn1-xMgxO layers were grown by the spin-
coating sol–gel method, whereas other growth methods may be used to
further improve this device structure. Furthermore, a highly resistive
buffer layer was also found to be beneficial to reduce the recombination
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Solar Energy 201 (2020) 227–246
Fig. 10. Schematics of efficient band align-
ment in a heterojunction solar cell. TE, HTL
and BC denote the, transparent electrode‘,
,hole-transport layer‘ and ,back contact‘,
respectively. (*) Eg values of TEs may vary
depending on the dopant concentation. Data
taken from the following references,
namely: ITO and Niox (Liu et al., 2016); FTO
and Au (Faheem et al., 2019); AZO (Lahmar
et al., 2016); SnO2 (Kulkarni et al., 2015);
ZnO and Zn0.85Mg0.15O (Li, K. et al., 2018);
TiO2, CdS and Sb2Se3 (Wang et al., 2019);
Spiro-OmeTAD (Poplavskyy and Nelson,
2003); CuI and P3HT(Zardetto et al., 2017);
Ni, Ag, Al and Mo (Grundmann, 2015; Raziq
et al., 2018).
and increase the VOC and RSh (Chantana et al., 2018a; Li et al., 2015).
Overall, optimization of buffer layer properties may lead to further
improvement of device performance.
4.4. Hole-transport layer and back contact
Collection efficiency of photo-generated carriers can be improved
by using a hole-transport layer (HTL) between the absorber/back-con-
tact by reducing the resistance of the back contact (Choi et al., 2014a).
Li and co-authors reported that the HTL of 4,4′,4″,4″′-(9-octylcarbazole-
1,3,6,8-tetrayl)tetrakis(N,N-bis(4-methox-yphenyl) aniline) (CZ-TA)
reduced the back-contact resistance in Sb2Se3 solar cells and led to
increased photo-generated carrier collection (Fig. 11A), whereas the
PCE of the device significantly improved (6.84%) (Li, D.-B. et al., 2018).
As shown in Fig. 11B, the EQE(-1 V)/EQE(0 V) ratio deviated from unity
for the Sb2Se3 solar cells without a HTL at long wavelengths > 600 nm,
which indicates a poor carrier-collection efficiency near the back con-
tact that has been improved for devices with a HTL. Chen et al. (Chen
et al., 2017b) showed that when a PbS quantum dot film was used as a
HTL, it minimized carrier recombination loss at the back contact, but
also contributed to photocurrent by its own near-infrared absorption. In
addition to HTL strategy to achieve ohmic behavior at absorber/BC
interface, Zhang et al. (Zhang et al., 2019) showed that expensive Au
contacts can be substituted with cost-effective materials such as NiOx
HTL and Ni back contact, whereas optimal thickness of NiOx layer is
found to be 7 nm. Furthermore, the Mo back-contact selenization in
substrate device configuration led to enhanced (2 2 1)-orientation of the
Sb2Se3 absorber layer and improved quality of the heterojunction, re-
sulting to an increase in the VOC and FF (Li et al., 2017). However, the
rollover effect was observed in CIGS-based solar cells due to the for-
mation of MoSe2 layer between the absorber/BC interface (Kato et al.,
2016). In other words, this effect can be explained by the presence of a
barrier, i.e. likely at the BC interface, which prevents the carrier
transport in the cell by acting as Schottky diode. In Sb2Se3-based solar
cells, this effect has also been observed occasionally from temperature
dependent J-V curve at low temperatures (Chen et al., 2017b; Kumar
et al., 2019; Li, D.-B. et al., 2018), yet detailed investigation is needed
for clarification.
4.5. Transparent electrode layer
The TE has a direct influence on device performance. In general, TE
A. Mavlonov, et al.
Fig. 11. (A) J-V and (B) EQE curves for Sb2Se3 solar cells with and without HTL. Inset in (B) shows the EQE(-1 V)/EQE(0 V) ratio. Represented with permission from
(Li, D.-B. et al., 2018).
layer should fulfill three main requirements to achieve high efficiency.
First, the conduction band offset between TE/buffer interface is needed
to be optimized, where TE layers with tunable bandgap, e.g. Al-doped
Zn1-xMgxO, are preferred (Chantana et al., 2017a; Murata et al., 2015;
Nishimura et al., 2019). Second, TE layer should have both high optical
transparency and high electrical transport properties. Increasing the
free charge carrier density in TE layer may reduce the electrical re-
sistivity, yet optical transparency suffers from increased free carrier
absorption. This existing trade-off between the optoelectric parameters
can only be optimized via maintaining the high mobility of free charge
carriers (Chantana et al., 2019a; Chantana et al., 2019b). Third, de-
position temperature of TE layer should be lower than 150 °C, i.e.
especially in substrate structure, where the physical properties of
Sb2Se3 tend to change above this temperature range (cf. Section 3.7).
To date, the most commonly used TEs are wide-bandgap (> 3 eV)
In2O3:Sn (ITO), ZnO:Al (AZO), and SnO2:F (FTO). ITO is widely used as
a TE in many optoelectronic applications, e.g., flat-panel display, light-
emitting diodes, and solar cells. Hence, ITO-coated substrates are
commercially available or can easily be prepared using well-established
techniques. However, scarcity and high price of In is the main issue for
finding an alternative for ITO electrodes (Mallick and Basak, 2018). On
the other hand, FTO has better thermal stability (> 500 °C) than ITO,
which has been the reason for its wide use in high-temperature-pro-
cessed CdTe-based solar cells. However, the high processing tempera-
ture of FTO makes it more challenging to obtain in-house compared to
ITO.
Recent studies showed that Earth-abundant, non-toxic, and low-cost
AZO films can be fabricated with comparable physical properties. From
the stability perspective, AZO films have good thermal stability up to
400–450 °C, which makes it possible to deposit high-quality Sb2Se3
films (at < 450 °C) on AZO-coated substrates by considering the
proper band alignment. However, in the literature, FTO (Kulkarni et al.,
2015; Leng et al., 2014; Li, K. et al., 2018; Li, Z. et al., 2016; Liu, X.
et al., 2014; Lu et al., 2018; Ngo et al., 2014; Wang et al., 2017; Wang
et al., 2015; Wen et al., 2017; Zhou et al., 2014; Zhou et al., 2015) and
ITO (Liu et al., 2015; Wen et al., 2018; Zhou et al., 2017) have been
widely used, whereas reports on AZO (Li et al., 2019; Yuan et al.,
2016a; Yuan et al., 2016b) are rare. Hence, detailed investigations on
TEs can be a new opportunity for further improving the device per-
formance and ensuring low-cost manufacturing.
In thin-film solar cells, the window layer is often used next to the TE
layer and has an essential role to minimize recombination losses and
enhance the PCE. In particular, the window layer minimizes uninten-
tional shunt-current carrier recombination via pinholes of the buffer
and/or absorber layer (Akari et al., 2018; Kamaruddin et al., 2017). In
conventional thin-film solar cells, ZnO has been widely used as a
window layer between the TE and buffer layers to enhance the shunt
resistance (RSh) of the device, whereas reports on Sb2Se3-based solar
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Solar Energy 201 (2020) 227–246
cells with a window layer (ZnO (Yuan et al., 2016a; Yuan et al., 2016b))
are rare. On the other hand, most of the window and TE layers have
been prepared by sputtering method due to its several advantages, e.g.
scalability to large areas, reproducibility and low-cost (Ellmer, 2000).
In literature, low-surface carrier recombination at the CIGS/buffer in-
terface was achieved by preventing the absorber surface from sput-
tering damage during the subsequent layer growth (Chantana et al.,
2018b). However, to the best of our knowledge the influence of sput-
tering damage has not been addressed for Sb2Se3-based thin-film solar
cells.
4.6. Effect of shunt and series resistances on device performance
Both shunt and series resistances also influence the device perfor-
mance. Overall, high shunt resistance (RSh) is beneficial to maintain
high VOC, whereas low series resistance (RS) is beneficial to increase the
JSC values. Also, high FF can be maintained if RSh values are increased
and RS values are decreased. Low RSh affects the performance of the
solar cell by reducing the FF and VOC (Hutter et al., 2018b). Usually,
high RSh enables device reproducibility via high VOC and good junction
quality (Zhou et al., 2015). In contrast, low RSh may result from existing
pinholes in the absorber and/or a current pathway through the device
edges (Bosio et al., 2018).
As shown in Fig. 12A, Sb2Se3-based solar cells showed an increased
PCE at higher RSh values, which was more obvious for CdS than for
other single buffer layers. Solar cells with double buffer layers (e.g.,
SnO2/CdS and CdS/ZnO and TiO2/CdS) have higher RSh, but there was
no obvious correlation between RSh and PCE. One can see from Table S1
that the devices with double buffers layers have higher VOC but lower
JSC compared to the ones with a single buffer layer. Thus, it seems that
the double buffer layers limit the current flow through the device.
However, we note that in recent works, e.g., Wang et al. (Wang et al.,
2019), Shen et al. (Shen et al., 2018), and Liang et al. (Liang et al.,
2018), the authors successfully used respective TiO2/CdS, SnO2/CdS
and ZnO/CdS double buffer layers to maintain not only high RSh and
VOC, but also, high JSC. Unlike RSh—and independent of growth
methods and materials used—RS has a direct influence on PCE. As
shown in Fig. 12B, the PCE systematically increases with decreasing RS.
Fig. 12C shows the influence of RS and RSh in the J-V curve of the solar
cell. According to the equivalent circle, RS is inversly proportional to
JSC. In other words, high RS acts as a blocking layer in the solar cell;
hence, it limits the current flow (Fig. 12D).
In solar cells, crystalline quality and optoelectrical properties of the
absorber layer and proper band alignment between layers are important
to reduce the RS. As discussed above, Zhou et al. found that there is a
correlation between the device performance and orientation of Sb2Se3
films (Zhou et al., 2015), where the PCE tends to decrease with in-
creasing the peak intensity of (1 2 0) orientation. When RSh and RS
A. Mavlonov, et al.
Fig. 12. PCE versus illuminated (A) RSh and (B) Rs for Sb2Se3-based solar cells listed in Table S1. (C) Comparison between the current–voltage characteristics of solar
cells with (red curve) and without (blue curve) RSh and RS issues. (D) shows the equivalent circuit of a real solar cell.
values of those solar cells were analyzed, RSh remained constant at
∼1,600 Ω, i.e., confirming a similar junction quality, whereas RS in-
creased with increasing value of the (1 2 0) peak. The authors suggested
that the [1 2 0]-oriented grain consists of (Sb4Se6)n ribbons aligned
horizontally, i.e., in parallel with the substrate; hence, grains with this
orientation limit the transport properties due to the anisotropic nature
of the film. On the other hand, Sb2Se3 films with a preferred [2 1 1]
orientation showed better electrical transport and lower recombination
loss resulting from lower RS, higher FF, and improved JSC.
Poor collection efficiency may exist near the back-contact region of
Sb2Se3 solar cells, so this issue can be further investigated via tem-
perature-dependent RS measurements (Akari et al., 2018). In particular,
the presence of a blocking contact barrier may limit the majority-carrier
transport at the absorber/back interface region, which can be verified
by measuring RS with decreasing temperature. Furthermore, light-in-
tensity-dependent measurements can be used to understand device
limitations. In particular, dependence of VOC on the incident light in-
tensity and temperature is suitable to distinguish the various re-
combination loss mechanisms, e.g., recombination at the buffer/ab-
sorber interface, in the space-charge region, and in the quasi-neutral
region (Li et al., 2014).
4.7. Device stability
In addition to high efficiency, low cost, and low toxicity, long-term
operation stability is also required to manufacture commercially com-
petitive solar cells and modules. Solar cells are mostly used outdoors, so
operational stability of the devices under damp-heat, light-soaking, and
ultraviolet radiation conditions define the stability criteria. Several
Sb2Se3 studies investigated these issues from this point of view (Koc
et al., 2012; Shongalova et al., 2019; Wen et al., 2018; Wen et al.,
2017). Luo et al. reported the excellent storage stability (100 days) of a
device with a glass/FTO/CdS/Sb2Se3/Au structure. Furthermore, they
241
Solar Energy 201 (2020) 227–246
subjected the unencapsulated device to standard solar irradiation
(AM1.5G) for 15 h, where the device showed only a minor 0.2% ab-
solute decrease in PCE (Luo et al., 2014). Chen et al. also confirmed the
outstanding storage stability (60 days) for a glass/ITO/CdS/Sb2Se3/Au
device structure (Chen et al., 2017b). More interestingly, they observed
the increased PCE (from 6.35% to 6.69%) within 60 days for a glass/
ITO/CdS/Sb2Se3/HTL(PbS)/Au device structure, mainly attributed to
improved VOC via increased carrier density in in PbS layer under am-
bient oxidation.
As shown in Fig. 13, Wang et al. carried out a comparative study on
device stability between CdS/Sb2Se3 and ZnO/Sb2Se3 devices with
randomly oriented ZnO (Wang et al., 2017). Both devices showed no
degradation during the initial ambient storage period of 3 months
without any intentional protection. However, the CdS/Sb2Se3 device
exhibited degradation during the damp-heat and light-soaking tests,
whereas the ZnO/Sb2Se3 device showed good stability. When the 1-nm-
thick Al2O3 layer was sandwiched at the CdS/Sb2Se3 interface, the
stability of the device significantly improved (Fig. 13A,B). Whereas
Zhou et al argued that this degradation is due to the inter-diffusion of
Cd from CdS into absorber layer (Zhou et al., 2017). Furthermore, a
ZnO/Sb2Se3-based device showed very good stability under ultraviolet
aging and thermal cycling tests (Fig. 13C,D). Overall, these results
significantly outperformed many emerging solar cells such as polymer
solar cells (Li et al., 2012), colloidal quantum dot solar cells (Cao et al.,
2016), and hybrid perovskite solar cells (Han et al., 2017; McMeekin
et al., 2016; Saliba et al., 2016), and they almost met the all the re-
quirements set by IEC 61646 “Thin-film terrestrial photovoltaic (PV)
modules – Design qualification and type approval” protocol (Wang
et al., 2017).
5. Summary and future prospects
We reviewed the recent progress in understanding material
A. Mavlonov, et al.
properties and improving device performance of the Sb2Se3-based solar
cells, with special emphases on electrical characteristics of solar cells,
and compared them with fundamental limits based on the S-Q model.
JSC, VOC, and FF values of the current champion Sb2Se3 cell prepared by
a physical method (CSS) with a PCE of 9.2% are found to be equivalent
to 74%, 48%, and 81% of the S-Q limit, respectively. In the case of
Sb2Se3 device fabricated by a chemical method (spin-coating) with PCE
of 3.9%, these ratios are 62%, 40% and 48%, respectively. In these
devices, low JSC values are due to insufficient light absorption and/or
incomplete collection of photo-generated carriers, whereas the low VOC
and FF are due to electrical nonidealities such as interfacial or bulk
recombination or parasitic resistance. Overall, despite the outstanding
device stability and very good current collection (JSC), the present
performance of Sb2Se3 solar cells is mainly limited by VOC deficit.
In the future, the following factors should be considered to further
improve the PCE of Sb2Se3 solar cells:
(1) Enhancement of the photocurrent, i.e., particularly in the short-
wavelength region of the spectrum, by using ZnO, TiO2, or SnO2 to
improve the EQE in the short-wavelength range.
(2) Improvement of the VOC and FF via optimized carrier management.
This is an important but complex task that requires a synchronized
material science and device engineering approach to control and
passivate the recombination mechanisms of charge carriers, to
identify the defects (interface, surface or bulk), and to measure
their formation energies, energy levels, and density. Future in-
vestigations in nanoscale is beneficial to deepen the understanding
of the material properties and improve device efficiency, since
materials with nanoscale structure (nanomaterials or nanosctu-
crures) mostly have unique physical properties.
(3) Systematic investigation of defects, with the goal of passivating the
reported deep defect states. The existence of such defects can be a
reason for low VOC due to the pinning of the Fermi level within the
bandgap. Therefore, a detailed understanding on these defects is
needed to clarify the bottleneck of efficiency enhancement.
(4) Implementation of novel buffer layers, e.g., ZnO, to maintain the
242
Solar Energy 201 (2020) 227–246
Fig. 13. (A) Damp-heat test under 85%
humidity, 85 °C, in the dark and open-
circuited device condition, and (B) light-
soaking test under 76 Ω load, 50 °C in air
and close to maximum output power con-
dition, for indicated device structures. (C)
Ultraviolet aging under 300–450-nm-wa-
velength ultraviolet light for 62 h and (D)
thermal cycling from −40° to 85 °C for 60
cycles in a cryostat for the devices with
randomly oriented ZnO, i.e. r-ZnO/Sb2Se3.
Note that the thickness of the Al2O3 in-
sulating layer is 1 nm, and all tests were
performed in air on unencapsulated de-
vices. Adopted from (Li, K. et al., 2018;
Wang et al., 2017).
stability of the device. Studies showed that the diffusion of Cd from
the CdS buffer layer into the Sb2Se3 absorber layer is the main cause
for poor stability of the device. In addition, preventing the absorber
surface from sputtering damage may further increase the device
performance due to the reduced surface carrier recombination.
(5) Optimization of device fabrication by considering the lattice
matching, as well as electronic band alignment between layers.
Furthermore, optimized device architectures with reduced shunt
passes, e.g., via edges of the device and/or pinholes, are needed to
enhance the charge-carrier transport properties.
(6) Improvement of the absorber/BC interface, aiming to ensure the
ohmic behavior via surpassing the occasionally occurred rollover
effect.
Overall, higher Sb2Se3 PCEs can be achieved by considering the
aforementioned issues related to carrier management. There is room to
overcome the remaining challenges, so it is certain that the efficiency
records will continuously be surpassed in the near future. And ulti-
mately, Sb2Se3-based solar cells will attract the interest of the broader
research community and will gain commercial interest.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgments
This work was supported by the National Natural Science
Foundation of China (NSFC, No. 21850410460). The authors ac-
knowledge the support by NSFC (No. 11774044) and the NSAF Joint
Foundation of China (U1630126), the grant F3-003 of the Basic
Research Foundation of the Uzbekistan Academy of Sciences (TR), the
U.S. Department of Energy (DOE) under Contract No. DEAC36-
08GO28308 with the Alliance for Sustainable Energy, LLC, the manager
A. Mavlonov, et al.
and operator of the National Renewable Energy Laboratory (AZ). The
views expressed in the article do not necessarily represent the views of
the DOE or the U.S. Government.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.solener.2020.03.009.
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