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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


Cu2SnS3 (Baranowski et al., 2015; Chantana et al., 2017d; Hossain
Photovoltaic (PV) technologies offer a clean, sustainable solution to et al., 2018), CuSbS2 (Dittrich et al., 2007; Xue et al., 2015), FeS2 (Luo
meet the increasing global energy demand via direct conversion of solar et al., 2015), Cu2ZnSnSe4 (Hartnauer et al., 2016), CuSbSe2 (Xue et al.,
radiation (or other sources of radiation) into electricity (Green, 2019; 2015), Sb2(S,Se)3 (Wang, W. et al., 2018), Sb2Se3 (Wen et al., 2017) and
Ramanujam et al., 2016). According to the Shockley-Queisser (S-Q) SnSe (Razykov et al., 2018a)—have been investigated as alternatives
detailed-balance model, a single-junction solar cell with an optimum for the highly efficient, environmentally friendly, stable, and cost-ef-
bandgap of Eg ≈ 1.14 eV of the absorber layer can yield a maximum fective thin-film solar cells.
power-conversion efficiency (PCE) of 33.3% (Alharbi and Kais, 2015). Antimony selenide (Sb2Se3) belongs to a family of inorganic binary
In reality, Cu(In,Ga)Se2- and CdTe-based PV technologies, which are V2-VI3 compounds (e.g., Bi2S3, Bi2Se3, Bi2Te3, Sb2S3, Sb2Se3, Sb2Te3)
the most common thin-film solar cells, have PCEs of 22.6% and 22.1% (Zeng et al., 2016). The Sb2Se3 material and related compounds exist
at the laboratory scale and 19.2% and 18.6% at module level, respec- naturally in the form of the mineral stibnite and have orthorhombic
tively (Green et al., 2018; Jackson et al., 2016). However, the high price structure, which is formed by (Sb4Se6)n ribbons stacked in parallel in
of In and Ga as well as the toxicity of Cd may limit their very large-scale the [0 0 1] direction (Kondrotas et al., 2018; Zhou et al., 2015). Despite
(multi-terawatt) use (Zakutayev, 2017). Hence, many Earth-abundant 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. Solar Energy 201 (2020) 227–246

Bi2S3, and Sb2Se3—have been reported for PV applications (Kondrotas 2. History of Sb2Se3 research
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- In 1950, Dögnes synthesized Sb2Se3 and showed that it was iso-
theless, it can be a suitable candidate for multijunction tandem solar structural with Sb2S3. Because Sb2S3 had a longer research history, this
cells. As for Bi2S3, its lowest unoccupied molecular orbital (LUMO or finding was beneficial to understand the physical properties of the
conduction band) has been found to be lower in energy compared to material via comparative studies (Dönges, 1950; Hofmann, 1933). In
those in Sb2S3 and Sb2Se3, which is unfavorable for electron injection 1957, Tideswell et al. confirmed that these two compounds had similar
from the absorber into the buffer layer (Patrick and Giustino, 2011). features (Tideswell et al., 1957). Furthermore, they precisely calculated
Overall, atomistic calculations have shown that Sb2Se3-based solar cells the Sb2Se3 lattice parameters (a = 11.62 ± 0.01 Å,
hold higher potential among V2-VI3 compounds (Patrick and Giustino, b = 3.962 ± 0.007 Å, c = 11.77 ± 0.01 Å), which are almost iden-
2011). Although this work focuses on Sb2Se3-based thin-film solar cells, tical with recent data (Chandrasekharan and Kunjomana, 2009; Voutsas
we note that they share many similarities with those based on other V2- et al., 1985). In the 1960s, several Sb2Se3 physical properties were in-
VI3 compounds, e.g. Sb2S3 and Sb2(S,Se)3, hence the readers are re- vestigated. Uphoff et al. studied the thermoelectric properties of
ferred to recent comparative study by Lei et al. on these materials for amorphous and crystalline Sb2Se3 films (Uphoff and Healy, 1963) and
more details (Lei et al., 2019). found that the material parameters depended on structure. Between the
Among these V2-VI3 materials, Sb2Se3 has recently attracted tre- 1970s and 1990s, the number of reports on physical properties of
mendous interest for use as a PV light absorber as well as battery (Ou Sb2Se3 thin films gradually increased. As a result, knowledge expanded
et al., 2017; Tian et al., 2019) and photochemical applications (Liang significantly on the optical, electrical, structural, electronic, and mag-
et al., 2017; Wu et al., 2019), because of its promising optoelectronic netic properties of the material. In the 1990s and 2000s, Sb2Se3 was
properties and favorable environmental characteristics. Sb2Se3 is not on used as a supporting material (or passive element) in solar cells.
the lists of highly toxic materials by American, European Union, or Although synthesis and characterization of Sb2Se3 thin films had
Chinese regulation authorities, nor in the lethal dose LD50 or lethal been carried our since 1950s, early studies on Sb2Se3-based solar cells
concentration LCt50 data. The abundance of Sb and Se elements in the reported the PCE below 1% in 1982 (Bhattacharya and Pramanik,
Earth’s crust is 0.2 and 0.05 ppm, respectively (Zeng et al., 2016; Zhou 1982), 2002 (Rajpure and Bhosale, 2002), and 2009 (Messina et al.,
et al., 2014), and Sb2Se3 has good physiochemical stability (Koc et al., 2009). However, active research on Sb2Se3 solar cells began in 2014,
2012). Fig. 1 highlights the recent research advances as well as future probably after reports on TiO2-sensitized inorganic–organic solar cells
research areas of Sb2Se3-based thin-film solar cells. As shown in Fig. 1, (PCE of 3.2%), TiO2/Sb2Se3 and CdS/Sb2Se3 thin film solar cells (PCE of
thin films with preferential (221) crystal orientation and low defect 2.26% and 1.9%) by Seok et al. (Choi et al., 2014c) and Tang et al. (Luo
density are desired to increase the PCE. Furthermore, proper band et al., 2014; Zhou et al., 2014), respectively. Hence, the role of this
alignment between constituent layers and the thin-film absorber mor- material changed from being a passive component to being the active
phology must be considered. Another important research direction is component in PV. Afterwards, Tang and co-workers put significant ef-
the defect physics of Sb2Se3, including the effects of Se vacancies (VSe) fort into developing the Sb2Se3 thin-film PV architecture, reaching PCEs
on PV performance. It is clearly shown from current density–voltage (J- of 3.7% at the end of 2014 (Leng et al., 2014), 5.6% in 2015 (Zhou
V) curves that future research challenges are related primarily to re- et al., 2015), 6.5% in 2017 (Chen et al., 2017b), and 7.6% in 2018 (Wen
ducing open-circuit voltage (VOC) deficit via carrier management. et al., 2018). Most of these champion cells were prepared by using rapid
Overall, Sb2Se3 is receiving growing research interest within the PV thermal evaporation (RTE), except the one with 7.6%, which was pre-
community because of its favorable material properties and rapidly pared by vapor transport deposition (VTD) (Wen et al., 2018). They
improving PCE. Although more than 100 papers have been published have claimed that one-dimensional Sb2Se3 ribbons are beneficially
on Sb2Se3-based thin-film solar cells in the last decade, no recent aligned vertically to maintain high carrier transport throughout the
comprehensive review exists on this PV technology. We note that re- Sb2Se3 layer. Very recently, Li et al. reported on Sb2Se3 solar cells
cently, Wang et al. and Lei et al. discussed, in part, the development of fabricated by closed-space sublimation with a PCE of 9.2%, i.e., the
Sb2Se3 thin-film solar cells in their 2018 and 2019 studies dedicated to highest efficiency to date (Li et al., 2019). Fig. 2A depicts the PCE of
Sb2(S,Se)3-based thin-film solar cells (Lei et al., 2019; Wang, X. et al., Sb2Se3 and other Sb-containing thin-film solar cells. As shown,
2018). In 2016, Tang et al. briefly reviewed the material and optoe- Sb2(S,Se)3 and Sb2S3 have reached the PCE of 6.6% and 7.5%, respec-
lectronic properties and device performance of Sb2Se3 (Zeng et al., tively. In contrast, CuSbS2 and CuSbSe2 have only yielded PCE of 3.2%
2016), but many works have been reported on Sb2Se3 material and and 5%, respectively. Overall, these achievements have proven the fact
device performance since that time and therefore, an up-to-date review that Sb-containing thin-film absorbers are suitable for PV application,
is necessary. whereas the current highest efficiency has placed the Sb2Se3 solar cell
Here, we review recent research advances and remaining challenges in a visible position (cf. Fig. 2B).
of Sb2Se3 thin-film absorber materials and PV solar cells on the path Recently, Sb2Se3 has received growing research interest as observed
toward high efficiency. Following this introduction (Section 1), we based on several literature reports (Fig. 2C). In the literature, Sb2Se3
briefly summarize the history of research on Sb2Se3–based thin-film has been successfully prepared by chemical growth methods, such as
solar cells (Section 2) so as to put the recent advances in perspective. spin coating (Choi et al., 2014c; Wang et al., 2019; Zhou et al., 2014)
Next, we introduce the Sb2Se3 properties (Section 3)—including crystal and electrodeposition (ED) (Ngo et al., 2014), atomic layer deposition
structure, electronic structure, electrical properties, point defects, de- (Mahuli et al., 2019), as well as physical growth methods, such as VTD
fect chemistry and optical properties—for both crystalline and amor- (Hu, X. et al., 2018a; Hu, X. et al., 2018b; Wen et al., 2018), RTE (Chen,
phous Sb2Se3 materials. Then, we discuss the fabrication and perfor- C. et al., 2018; Chen et al., 2017b; Wang et al., 2017), magnetron
mance of Sb2Se3 devices (Section 4), including absorber deposition sputtering (MS) (Liang et al., 2018; Tang et al., 2019a; Yuan et al.,
methods, buffer layer, hole-transport layer and back contacts, and 2016a; Yuan et al., 2016b), and close-spaced sublimation (CSS) (Li, D.-
transparent electrode layers. We also discuss the effect of shunt re- B. et al., 2018; Li et al., 2019; Shen et al., 2018). To date, the physical
sistance (RSh) and series resistance (RS) on device performance and deposition methods have yielded higher device performance than the
summarize the resulting device stability. Finally, we highlight current chemical deposition methods. It has been demonstrated that Sb2Se3
status, challenges as well as future research directions in Sb2Se3 solar cells can be prepared using both substrate and superstrate con-
(Section 5). 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;

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

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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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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 a high-temperature CdCl2 or Cd-free halogen treatment in CdTe solar
main reason for anisotropic carrier transport. Due to the 1D structure, cells (Bosio et al., 2016). In comparison, such passivation may not be
the grain boundaries (GBs) that form parallel to the ribbons would be required in Sb2Se3, yet controlling the film orientation is one of the key
inherently benign to charge-carrier recombination. This is particularly factors to achieve high efficiency solar cell due to the anisotropic
beneficial to reduce a major source of losses at GBs, which may exist in physical properties (Zhou et al., 2015).
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 3.3. Electronic structure
character (Caracas and Gonze, 2005). Within the [Sb4Se6]n ribbons, the
atoms are covalently bonded, whereas there are weak van der Waals The electronic structure of Sb2Se3 has been investigated in detail by
interactions between ribbons. Investigations by local density approx- several research groups (Caracas and Gonze, 2005; Deringer et al.,
imation (LDA) from density functional theory (DFT) revealed that the 2015; Hurych et al., 1974; Koc et al., 2012; Sajid-ur-Rehman et al.,
electron density is concentrated within the ribbons (Tan et al., 2017) 2018). Research studies using LDA and generalized gradient approx-
and that grain boundaries in Sb2Se3 are electrically benign (Zhou et al., imation (GGA) within DFT framework showed that Sb2Se3 is an in-
2015). It was calculated that surfaces orthogonal to the (0 0 1) pla- direct-bandgap semiconductor (Koc et al., 2012; Vadapoo et al., 2011).
ne—e.g., (0 1 0), (1 1 0), and (1 2 0) surfaces—are the most prevalent Fig. 3A illustrates the partial and total DOS of Sb2Se3. As shown, the
due to the lowest surface energies as well as absence of covalent bond lowest VB appears between −14 and −12 eV, which is generated by
breakage and no dangling bonds. In addition, the average surface po- Se-4s states. The VB located between −10 and −7 eV is mainly
tential of Sb2Se3 films has been found to be 9.1 mV, which is drastically dominated by Sb-5s states. The highest-occupied VB between about
lower than that in CIGS or CZTS (> 100 mV) (Zhou et al., 2015). Thus, −5.5 eV and 0 eV is dominated by Se-4p states and Sb-5p states; yet,
it can be hypothesized that in Sb2Se3, recombination loss by defects can values of Sb-5p density are lower compared to that of Se-4p. However,
be minimized if the surfaces are terminated by the suitably orientated Sb-5p states have a larger contribution to the CB compared to the Se-4p
[Sb4Se6]n ribbons—namely, (1 0 0), (0 1 0), (1 1 0), and (1 2 0) planes. states. Overall, for the formation of a Sb2Se3 band structure, the 5s and
This is different from the best-known PV light absorbers with 3D 5p orbitals of Sb atoms are more dominant compared to 4s and 4p
structures, where the breakage of covalent bonds introduces defect orbitals of Se atoms.
states at the GBs (Schmidt et al., 2008; Yin et al., 2014). In 3D poly- Fig. 3B shows that the valence band maximum (VBM) of Sb2Se3 is
crystalline thin-film solar cells, carrier recombination at the GBs can be located between the Γ and S points in the first Brillouin zone (BZ),
suppressed by passivation—e.g., via carefully engineering the Cu-defi- whereas the conduction band minimum (CBM) is located between the Γ
cient GBs in CIGS thin-film solar cells (Ramanujam and Singh, 2017) or 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

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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). 3.4. Electrical properties
Note that these optical bandgap values are underestimated compared to
experimental data. This is mainly caused by the exchange correlation As discussed earlier, 1D ribbon-like morphology of Sb2Se3 results in
approximation used for the DFT calculation. anisotropic charge-transport properties. In general, the Sb2Se3 films are
In addition to electronic band structure, another important material p-type (Lai et al., 2012a; Lai et al., 2012b). However, some Sb2Se3
property is vibrational response, which can be evaluated using Raman samples show n-type conductivity when the extrinsic dopants of Te (Wu
spectroscopy. Fig. 3D depicts the Raman spectra of Sb2Se3 thin films et al., 2015), Bi (Li et al., 2011; Sankapal et al., 2001), or intrinsically
grown at 25 °C and 290 °C, respectively (Liu, X. et al., 2014). At both higher Sb content (> 60%) (Mustafa et al., 2011) are introduced.
temperatures, two Raman peaks were observed at 190 and 253 cm−1, Moreover, selenium vacancy (VSe) can be also an n-type defect or a
corresponding to the heteropolar Sb-Se and nonpolar Sb-Sb vibrations donor. Because the p-type conductivity of the Sb2Se3 absorber has been
that are characteristics of Sb2Se3 (Liu, Y.-Q. et al., 2014,). However, two used for solar cells, discussions presented in this work focus on p-type
more Raman bands were depicted at 373 and 451 cm−1, which are Sb2Se3 unless otherwise mentioned.
characteristics of Sb2O3 and indicate the presence of Sb2O3 in Sb2Se3 In the past, Rodriguez-Lazcano et al. studied the photosensitivity of
(Cebriano et al., 2012). Thus, in addition to Sb2Se3 phases, experi- Sb2Se3 thin films, where the dark and illuminated conductivity values
mental works showed the presence of secondary phases such as Sb2O3 were found to be 2 × 10−8 and 1 × 10−6 (Ω cm)−1, respectively
in the measured samples. (Rodriguez-Lazcano et al., 2005). Yuan et al. reported the high hole
The chemical states of Sb2Se3 thin films are typically studied by X- mobility of 22 cm2V−1s−1 in Sb2Se3 films (Yuan et al., 2016b), which is
ray photoelectron spectroscopy (XPS) measurements. Fig. 4 shows the even higher than in CZTS (10 cm2V−1s−1) (Huang et al., 2014) or PbSe
magnified XPS spectra for as-deposited (A, C, D) and plasma-etched (B) (< 1 cm2V−1s−1) (Liu et al., 2010). Yet, orientating the crystal grains
Sb2Se3 films (Liu, X. et al., 2014). As shown, along with the binding important to increase the solar cell efficiency by maintain the maximal
energies of Sb-4d, Sb-3d, and Se-3d, the binding energy of O-1s peak mobility and minimal recombination (Phillips et al., 2017). However,
was also observed in as-deposited films (Fig. 4A), which is consistent reported free charge-carrier density (∼1013 cm−3) is much lower than
with the existence of Sb2O3 observed in Raman studies and other re- the optimal value of 1016 cm−3 for solar cells (Chen et al., 2017a), and
ports (Honma et al., 2000). In comparison, the O-1s peak of Sb2O3 was it may be difficult to measure accurately. Hence, several works have
not observed in the plasma-treated sample (surface etching down to been dedicated to increase the free charge-carrier density in Sb2Se3,
∼10 nm by Ar+ source (Fig. 4B), indicating that Sb2O3 is only pre- which will be discussed in the next section.
sented on the surface of the Sb2Se3 thin film. Shongalova et al. showed In early work on Sb2Se3, large 0.2–1.0 eV variation of activation
that oxidation can also be possible reason for Sb2O3 formation energy (Ea) of crystalline Sb2Se3 was found. This variation was attrib-
(Shongalova et al., 2018b). Recent studies also confirmed that the uted to the difference in the Fermi level that is pinned at a different
Sb2O3 can be removed by chemical treatments, e.g., using (NH4)2S position in the energy gap in the range of 0.54–0.66 eV (Gilbert et al.,
aqueous solution, which can dissolve Sb2O3, Se, and Sb2Se3 (Chen et al., 1974), or to the thickness dependence of Ea in Sb2Se3 films (El-Salam
2017c; Xia et al., 2015). 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

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with x from 0.0 to 0.9 (Zayed et al., 1995). The reported high activation have formation energy below 1.5 eV, which are expected to be present
energies strongly suggest the presence of deep traps (Iovu et al., 2007). in the film in reasonable concentrations (Fig. 5B). However, under Se-
Wen et al. also found that the bulk defect density in VTD-grown Sb2Se3 rich condition, the formation energies of several problematic defects are
films is about 1014 cm−3 (interface defect density 2.8 × 1010 cm−3) moved to higher energy positions (See Fig. 5C). Overall, studies have
(Wen et al., 2018), which is higher than that in CdTe-based solar cells shown that intrinsic defects have lower concentration under Se-rich
(1011 to 1013 cm−3) (Versluys et al., 2004). Hence, the density of these condition compared to Sb-rich condition, which can clarify to some
deep traps should be reduced to enhance the VOC and solar cell per- extent why higher device performances have depicted for the samples
formance. 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
3.5. Defects 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-
Defects have a crucial influence on device performance by causing imating a maximum achievable VOC to be around 0.47 V. However,
degradation of optical and electrical properties (Möller, 1991), so sev- recent experimental studies have shown that solar cells with VOC of
eral researchers have investigated intrinsic defects in Sb2Se3 using ad- 0.57 V (Zhao et al., 2018b) or even 0.64 V (Zhao et al., 2018a) can be
mittance spectroscopy measurements (Hu, X. et al., 2018b), First- fabricated.
principles Calculations (Huang et al., 2019), and hybrid Density Func- In addition to intrinsic defects, several effects are also expected from
tional Theory (Savory and Scanlon, 2019). Hu et al. found three elec- extrinsic doping, including bandgap modulation (Asaduzzaman et al.,
trically active defects located at 0.3–0.4 eV, 0.2–0.6 eV, and 0.5–0.6 eV 2016; Mohamed and Rohani, 2011), grain-size enhancement (Yang
above the VBM, which were denoted D1, D2, and D3, respectively. The et al., 2012), defect passivation (Altamura et al., 2016; Liu et al., 2015),
D1 and D2 defects were found to be bulk defects, and their activation conductivity increase (Grundmann, 2015; Hu, L. et al., 2018; Li et al.,
energy increased with increasing cell efficiency. The D3 defect was 2013), and photoactivity improvement (Altamura et al., 2016; Liu
found to be an interface or near-interface defect and had no obvious et al., 2015). Li et al. (Li, Y. et al., 2016b) reported that Mg was found to
relationship with efficiency of the solar cells. However, the nature of be inert to the electric properties of Sb2Se3, whereas Fe introduced n-
these defects, e.g., electron or hole traps, was not stated. Wen et al. type doping. However, free charge-carrier concentration remained low
reported that Sb2Se3 solar cells have one electron-trap (E1) and two (about 1013 cm−3), i.e., similar to those of the undoped Sb2Se3, perhaps
hole-trap states (H1 and H2). The E1 was argued to be associated with due to problems with incorporating dopant into the Sb2Se3 crystal. In
the formation of antimony antisite (SbSe) defects, whereas H1 and H2 contrast, Costa et al. (Costa et al., 2018) reported that Fe-doped Sb2Se3
defects were attributed to antimony vacancy (VSb) and selenium antisite films grown by co-electrodeposition are p-type with high carrier density
(SeSb) defects, respectively (Wen et al., 2018). Interestingly, E1 and H2 ranging from 3.7 × 1016 cm−3 (undoped) to 1.0 × 1019 cm−3. The
defects have similar densities; hence, authors correlated this with the highest free charge-carrier density was reported for a 5% concentration
formation of defect pairs, presumably a [SbSe + SeSb] complex. of Fe ions relative to Sb content in the solvent. The free charge-carrier
Note that VSb and SeSb are found theoretically to be the dominant density was found to decrease with further increase in the Fe con-
acceptor defects in Sb2Se3 films (Liu et al., 2017). On the other hand, centrations up to 20% and 50%, arguably due to donor defects that
VSe was reported to act not only as an n-type donor that competes with partially compensate acceptor defects and/or due to formation of Sb2O3
the p-type conductivity, but also, it reduces the solar cell performance secondary phases.
by acting as a recombination center for the photo-generated charge Furthermore, Alemi and coworkers reported on Sb2Se3 films doped
carriers (Zeng et al., 2016). In other words, the formation of VSe should with several transition metals and lanthanides, namely, Lu3+, Ho3+,
be avoided. To reduce the VSe-related recombination loss. Leng et al. Nd3+, Sm3+, and Gd3+, and co-doped with Lu3+/Yb3+ and Lu3+/Er3+
performed post-selenization treatment (Leng et al., 2014). Li et al. (Li, (Alemi et al., 2011a, b; Alemi et al., 2012; Hanifehpour et al., 2013).
Z. et al., 2016) also showed that the carrier concentration of the Sb2Se3 The electrical conductivity of the doped Sb2Se3 films was slightly im-
absorber layer can be increased as a result of the additional evaporation proved compared to that of undoped films, which further increased
of Se, which is probably due to the passivation the hole trap centers with increasing temperature. Chen et al. reported on Sn-doped Sb2Se3
caused by VSe. In addition to increased free charge-carrier density, they films (Chen, S. et al., 2018). They found that Sn-doping also enhanced
observed lower recombination loss, which was attributed to improved the electrical conductivity of the films, which yielded free charge-car-
heterojunction quality. This could also be due to prolonged Se eva- rier density of about 2 × 1016 cm−3. In addition to aforementioned
poration suppressed the formation of a Sb2O3 layer on the surface of the dopants, alkaline doping (Na) has also been investigated on RTE-grown
as-deposited Sb2Se3 thin films. Sb2Se3 films, inspired by its success in Cu2SnS3 (Chantana et al.,
In previous studies, the properties of intrinsic defects in binary 2017c), Cu2ZnSnSe4 (López-Marino et al., 2016) and CIGS (Pianezzi
Sb2Se3 were expected to be simple (Liu et al., 2017). However, very et al., 2014) solar cells. However, Na doping was found to degrade the
recently, Huang et al. (Huang et al., 2019) and Savory et al. (Savory and performance of the Sb2Se3-based solar cells, and it showed negligible
Scanlon, 2019) have reported that the defect chemistry of quasi-one- influence on the conductivity of the film (Li, Y. et al., 2016a). The
dimensional (Q1D) Sb2Se3 is rather complicated compared to conven- authors argued that Na diffuses in the film and remains inert between
tional semiconductors, e.g. CdTe. With other words, it has been argued (Sb4Se6)n ribbons.
that the identical defects located on non-equivalent atomic sites might Overall, more systematic and quantitative investigations on doped
have different properties, e.g. formation energy, because of the low Sb2Se3 films are needed to clarify the doping effects toward efficient
symmetry of the Q1D structure (Fig. 5A). Although these two studies electrical properties in the Sb2Se3 films. In addition, a comparative
have general similarity on expectations and results, we note various study on various growth methods could probably be beneficial to se-
results. For instance, Huang et al. reported that VSe1, VSe2, VSe3, SbSe1, parate the effective influence of the dopants from side effects, e.g., poor
SbSe2 and SbSe3 are donor defects, whereas VSb1, VSb2, SeSb1, and SeSb2 crystal quality or formation of unintentional defects during the de-
are acceptor defects. Furthermore, it has been predicted that 2SeSb1, position process.
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 3.6. Optical properties
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 The optical properties of Sb-Se compounds strongly depend on both
electrons and holes. They showed that under Sb-rich conditions, several crystal structure and chemical composition. Polycrystalline Sb2Se3 films
defects, e.g. VSe (all sites), SbSe (all sites) and the Sb interstitial (Sbi), with stoichiometric composition exhibit Eg within the range of

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

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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).

Eg, the absorber layer should have a high absorption coefficient Mustafa et al. investigated the temperature- and composition-de-
(α > 104 cm−1) to effectively generate the electron-hole pairs. Flat pendent optical parameters of a-Sb2Se3 grown by thermal evaporation.
electronic bands of Sb2Se3 are suggested to yield enhanced light ab- The bandgap of a-Sb2Se3 decreases with increasing Sb content and with
sorption due to the high DOS present in the valence and conduction increasing temperature. For different composition ratios, Eg values were
band extremes (Yu et al., 2013). This is also reflected by experimental obtained using linear, nonlinear, Varshni, and Bose-Einstein equations.
data, where Sb2Se3 films have a high absorption coefficient in the range Among them, the Varshni equation yielded the best fitting with Eg and
of 105 cm−1 for hν > Eg (Lai et al., 2012a; Lai et al., 2012b; Li, D.-B. the rate of Eg change values of 1.43 eV and 9.30 × 10−4 eV/K, re-
et al., 2018; Liang et al., 2017; Liu et al., 2015; Steinmann et al., 2015). spectively. Furthermore, they found that optical absorption of a-Sb2Se3
This value is very beneficial for PV applications and much higher than obeys the indirect-transition process. The composition-dependent var-
that of other novel PV absorber layers (Fernandes et al., 2010; iation of the Eg was also observed in other publications, which mono-
Kazmerski et al., 1983; Lakhdar et al., 2014; Sun et al., 2011). Thick- tonically decreases with increasing Sb/Se ratio (Fouad et al., 1997;
ness-dependent studies showed that photons with wavelengths Mueller and Wood, 1972; Rajpure et al., 1997; Torane et al., 1999;
λ > 800 nm are completely absorbed within 400-nm-thick Sb2Se3 film Wood et al., 1973). This composition-dependent Eg was explained by
(cf. Fig. 6A) (Chen et al., 2015), which is lower than the thickness of the chemical-bond approach (Shaaban et al., 2007): (a) atoms of dif-
conventional thin-film solar cell absorbers. Moreover, high dielectric ferent kinds (Sb-Se) combine more favorably than with the same kind
constant (εr) values are favorable for the absorber layer because they (Sb-Sb). Consequently, bonds between atoms of the same kind will only
lead to better screening of the photo-generated charge carriers from occur if there is an excess of a certain type of atom. (b) The sequence of
electrically charged defects. Investigations show that Sb2Se3 has higher bond formation depends on decreasing bond energy and goes until all
εr values (> 18 ε0) compared to those of CdTe (10.0 ε0) and CuInSe2 the available valences of the atoms are saturated. And (c) each atom is
(14.3 ε0) (Chen et al., 2017a; Madelung, 2012). This higher εr leads to coordinated by 8-N atoms, where N is the number of outer shell elec-
lower exciton binding energy (Eexc), which is required for effective trons. Based on this theory, increasing the antinomy content leads to a
dissociation of excitons into free electrons and holes upon light illu- decrease of low-probability Se-Se bonds. Thus, by adding Sb to SbxSe1-x,
mination (Lawal et al., 2018). the average bond energy of the compound decreases, and the bandgap
Reflection loss is one of the limitations in PV technology which can decreases.
be minimized by antireflective coating (Yao and He, 2014). As shown in On the other hand, Shimakawa showed that the optical bandgap of
Fig. 6B, the Sb2Se3 reflection loss of direct illumination was found to be the a-Sb2Se3 films can be explained using the following equation
40%, which further dropped to 10% for a CdS/Sb2Se3 heterojunction (Shimakawa, 1981):
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 Eg (Sb, Se) (Y ) = YEg (Sb) + (1 − Y ) Eg (Se), (1)
photocurrent in the Sb2Se3 solar cells. Compared to the crystalline
Sb2Se3 (c-Sb2Se3), amorphous Sb2Se3 (a-Sb2Se3) showed suppression of where Y, Eg(Sb), and Eg(Se) are the volume fraction of Sb element,
reflectivity (Fig. 6B) in the visible and near-ultraviolet. This suppression bandgap of Sb (0.15 eV), and bandgap of Se (1.95 eV), respectively
was argued to be due to the sensitivity of the resonant p-bonds transi- (Shimakawa, 1981). As shown in Fig. 7A, this calculation is in good
tions to the absence of long-range order and/or due to influence of the agreement with experimental data. Also, El-Sayad et al. (El-Sayad et al.,
disorder on the CB DOS resulting from reduced Sb-5d band-overlap 2009) reported on structural and optical properties of nearly stoichio-
contributions (Shaffer et al., 1972). This CB DOS argument was sup- metric a-Sb2Se3 thin films grown by thermal evaporation, as a function
ported by XPS data, showing that c-Sb2Se3 and a-Sb2Se3 showed similar of heat-treatment temperature, where annealing was performed in a
magnitude of the VB DOS (Wood et al., 1972). 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
3.7. Amorphous Sb2Se3 transition from amorphous to crystalline at higher temperatures (Costa
et al., 2017; Kamruzzaman et al., 2017). In contrast to polycrystalline
A literature survey shows that the room-temperature and/or low- Sb2Se3 films, which exhibit both indirect- and direct-bandgap optical
temperature (< 150 °C) grown Sb2Se3 thin films are amorphous, in- transitions, a-Sb2Se3 films show only indirect bandgap with a relatively
dependent of the deposition process. The optical bandgap of a-Sb2Se3 high 0.49-eV Urbach’s tail, compared to 0.32 eV for polycrystalline
was found to be 1.39 ± 0.02 eV using ellipsometry measurement films annealed at 473 K.
(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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4. Solar cell fabrication 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
4.1. Summary of solar cell fabrication 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
Unlike silicon-based solar cells, thin-film solar cells have two typical with a thickness of only about 1–4 µm (Bosio et al., 2018). CdTe has a
configurations: substrate and superstrate configurations (cf. Fig. S1). In cubic zincblende crystal structure with a high melting point of 1,092 °C
a substrate configuration, the layers are deposited with a bottom-up (Belas et al., 2003). Unlike ternary and quaternary compounds, the
approach, i.e., deposition starts with the back contact and ends with the physical and chemical properties of the CdTe films—e.g., stoichiometry,
top transparent electrode (TE) layer, which is on the light-exposed side. morphology, phase, and defect density—can be controlled more di-
Hence, this configuration allows the use of opaque substrates such as rectly (Steinmann et al., 2015). Despite its high melting point, recent
commercially available rigid and/or flexible thin metallic foils, cera- advances of deposition techniques allowed deposition of CdTe at rela-
mics, and polymers. In a superstrate configuration, the layers are de- tively low temperature (< 450 °C) (Romeo et al., 2018) using various
posited with a top-down approach, where the deposition starts with the growth methods (Ojo and Dharmadasa, 2016; Paudel et al., 2014;
top TE layer, i.e., the light-exposed side, and the process ends with the Rimmaudo et al., 2017). However, CdTe thin-film solar cells deposited
deposition of metallic back-contact. Consequently, only highly trans- at low temperatures have showed relatively low PCE (16%) compared
parent substrates are required for this configuration because light has to to those deposited at high temperature (22.1%) (Green et al., 2018;
pass through the substrate and reach the absorber layer. In the case of Romeo et al., 2018). Over some 40 years, CdTe research achievements
the superstrate configuration, which is more common for Sb2Se3, the have yielded a PCE of 22.1% at lab scale and 18.6% at the module level,
solar cells work as follows: the n-type TE and CdS layers transmit the which are commercially available from the U.S. PV supplier, First Solar
photons to the Sb2Se3 layer, which can contribute for electron-hole pair (Bosio et al., 2018; Green et al., 2018). The champion CdTe thin-film
generation. The photons with higher energy (> 2.4 eV) do not con- solar cells with the VOC of 887.2 mV, JSC of 31.69 mA/cm2, and fill
tribute for this process due to their absorption in the TE (Eg > 3 eV) factor (FF) of 78.5% have yielded the record cell efficiency of 22.1%
and/or CdS (Eg = 2.4 eV) layers (Hamri et al., 2019). Photo-generated (Green et al., 2018). If these parameters are compared with the values
minority-charge carriers (electrons) move from p-type Sb2Se3 to n-type from the S-Q limit, JSC/JS-Q ≈ 0.96, which is an indication of good
CdS due to the creation of a built-in electric field at the p-n hetero- carrier collection resulting from high absorption coefficient. However, a
junction between the Sb2Se3/CdS interface, then these electrons move voltage deficit of VOC/VS-Q ≈ 0.75 is suggested to be due to the re-
into the TE layer. On the other hand, holes are attracted by the p-type combination losses at the interface and/or crystal grains of the poly-
hole-transport layer and collected by the back contact. In the conven- crystalline CdTe (Polman et al., 2016). However, concerns regarding
tional high-efficiency solar cells, each component layer of the solar cell toxicity of Cd and scarcity of Te necessitate the development of alter-
contributes in its own way to enhance the PCE of the device. Fig. 8 native solar cell materials to further increase the production capacity
shows the common Sb2Se3–based thin-film solar cell with substrate and reduce the cost—e.g., via omitting the additional recycling systems
configuration, which consists of glass/BC/HTL/Absorber/CdS/ that are required for commercial CdTe modules.
window/TE/Anti-reflective coating/Grid layers. As shown, the thin- In contrast to CdTe, Sb2Se3 is a low-toxicity, cost-effective com-
film device structure is made of several layers and interfaces. As a re- pound that also has excellent optoelectric properties such as an optimal
sult, not only the quality of the absorber layer, but also properties of bandgap of 1.1 eV and high absorption coefficient of 105 cm−1.
other layers and interfaces, e.g. absorber/BC, buffer/absorber, and TE/ Interestingly, Sb2Se3 has also been investigated for more than 40 years,
buffer, affect the PV performance (Minemoto et al., 2001b; Minemoto but its use as a solar cell absorber has only been seen recently. Sb2Se3
and Murata, 2015). Fig. 8 depicts the technical issues that have an ef- possesses a smaller bandgap than CdTe, so a theoretical JSC of 44.23
fect on the device performance. In particular, the influence of the mAcm−2 is expected, which is higher compared to 32.88 mAcm−2 for
crystal orientation (in Sb2Se3 bulk), sputtering damage and the rollover CdTe due to extended photon absorption in the infrared (IR) spectral
effects (at the interface and surface of Sb2Se3) needs further detailed region (Rühle, 2016). Due to its simple binary structure and lower
investigations in nanoscale, since materials with nanoscale structure melting point of 611 °C compared to CdTe (1092 °C), it has been pos-
(nanomaterials or nanosctucrures) mostly have unique physical prop- sible to deposit Sb2Se3 in the form of high-quality microcrystals at re-
erties (Hübler and Osuagwu, 2010). latively low temperatures (300–400 °C) without the complexity of
To understand the status of the Sb2Se3 solar cells, it is instructive to phase and composition control. Such low temperatures allow the use of
compare them with CdTe solar cells. CdTe is one of the most successful flexible polymer substrates as well as more cost-effective TEs, e.g., Al-

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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doped ZnO (AZO), with wider bandgap and better optoelectric prop- efficiency of 9.2% with JSC = 32.58 mAcm−2, VOC = 400 mV, and
erties. Furthermore, unlike the 3D cubic crystal structure of CdTe, FF = 70.3% was obtained from a ZnO:Al/ZnO/CdS/TiO2/Sb2Se3/
Sb2Se3 consists of pseudo-1D ribbons that make this material scientifi- MoSe2/Mo substrate configuration (Li et al., 2019).
cally interesting. Such low-dimensional features can be beneficial to Rapid Thermal Evaporation. The deposition principle of RTE is very
obtain electronically passive GBs due to fewer dangling bonds, com- similar to the CSS method. Hence, the source-to-substrate distance is
pared to 3D bonded absorber materials that have strong (covalent) about < 10 mm. Unlike CSS, RTE uses a very short growth time of a
bonds in all dimensions (Steinmann et al., 2015; Zakutayev, 2017). To few tens of seconds that may further lower the processing costs.
date, a Sb2Se3 record efficiency of 9.2% has been obtained with JSC of Although deposition time is short, RTE has been found to be sufficient
32.58 mAcm−2, VOC of 0.4 V, and FF of 70.3% (Li et al., 2019). Recent for nucleation of crystals and morphology control (Zhou et al., 2015).
advances in the PCE of Sb2Se3-based solar cells are summarized in Table Most RTE-deposited Sb2Se3 films have not required additional heat
S1. In the following section, we introduce the growth methods used for treatment, so this method has been very productive for preparing sev-
solar cell fabrication, then analyze the limitations of device perfor- eral champion solar cells over the past 4–5 years with PCEs in the range
mance. 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,
4.2. Absorber deposition methods 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
Preparation of high-quality materials with good surface morphology need for further improvement of crystalline quality by reducing the
as well as low defect and pinhole density is required to reduce the re- defect density, which is mainly caused by the small distance between
combination losses and device shunting to obtain high-performance source and the substrate, as well as very short deposition time, which
solar cells. However, high-quality absorber growth is a very complex makes it difficult to mix the vapors of elements. 2) Because RTE is a
task that involves optimizing deposition conditions and heat-treatment vacuum-based method, deposition cost can be higher compared to non-
procedures as well as selecting partner compounds with suitable lattice vacuum chemical growth methods. Despite the existence of these pro-
parameters and electronic properties. Moreover, apart from conven- blems, RTE has been one of the best methods to fabricate Sb2Se3 solar
tional inorganic solar cells with cubic crystal structure, the pseudo-1D cells in laboratory scale.
structure of Sb2Se3 offers unique opportunities for efficient charge Vapor Transport Deposition. In the VTD method, the most important
transport and low recombination behavior, but also adds new chal- deposition parameters that can influence the growth kinetics and ma-
lenges for material preparation. Controlled nucleation is required terial quality are source-to-substrate distance, source and substrate
during the growth of anisotropic materials because the transport temperatures, and partial pressure of ambient gases. VTD-grown sam-
properties of the device depend on anisotropic physical properties. ples have shown higher crystalline quality and lower defect density
Thus, optimization of growth parameters to prepare the film without compared to RTE-grown samples. Hence, VTD-deposited Sb2Se3 thin-
(or with fewer) pinholes, desired surface roughness, and with alignment film solar cells yielded the highest efficiency of 7.6% with JSC = 29.9
of grains with proper direction is required to maintain good transport mAcm−2, VOC = 420 mV, and FF = 60.4% for a simple ITO/CdS/
properties. Sb2Se3/Au solar cell structure (Wen et al., 2018).
So far, the deposition of Sb2Se3 thin films has been explored by Spin Coating. Spin coating is a non-vacuum chemical deposition
several growth methods. Physical deposition methods for preparing method. Several parameters such as solution pH, ion concentrations,
Sb2Se3 include physical vapor deposition (Bibin and Kunjomana, 2019), complexing agents, temperature, rotation speed, and number of coating
thermal evaporation (Butt et al., 2018), vacuum evaporation (Mustafa layers can be adjusted to control kinetics and thermodynamics of the
et al., 2009), rapid thermal evaporation (Wang et al., 2017), vapor spin-coating growth process. This method is not only simple and cost
transport deposition (Liu et al., 2017), magnetron sputtering (Liang effective, but also has several advantages such as easy dopability. For
et al., 2017; Liang et al., 2018; Shongalova et al., 2018a; Tang et al., example, introducing the extrinsic dopants into the films can easily be
2019b), close-spaced sublimation (Hutter et al., 2018b; Li, D.-B. et al., achieved by adding respective solute of dopants in the precursor solu-
2018; Li, G. et al., 2018) chemical molecular beam deposition (CMBD) tion, which is important for optimizing the physical properties of the
(Razykov et al., 2018b), and pulsed laser deposition (PLD) (Yu et al., solar cells. Using this method (Choi et al., 2014c), Sb2Se3-sensitized
2010). Chemical methods for Sb2Se3 growth include electrodeposition inorganic–organic heterojunction solar cells with single-source Sb2Se3
(Kwon et al., 2017), chemical-bath deposition (Rodriguez-Lazcano precursor (Se-SPP) achieved the PCE of 3.9% with JSC = 27.2 mA/cm2,
et al., 2005), successive ionic-layer adsorption and reaction (SILAR) VOC = 340 mV, and FF = 41.9% for a FTO/TiO2/CdS/Sb2Se3/HTL/Au
(Pathan and Lokhande, 2004), solvothermal synthesis (Ma et al., 2011), device structure (Wang et al., 2019).
spin coating (Kim et al., 2017; Wang et al., 2019), and vapor–liquid- To summarize these different methods, Fig. 9 shows the J-V curve
solid (VLS) growth (Yang et al., 2009). Among them, physical deposi- and external quantum efficiency (EQE) spectra of Sb2Se3 devices fab-
tion methods—namely RTE, CSS, and VTD—have yielded higher PCE ricated by the aforementioned growth techniques. In general, the de-
compared to chemical methods, whereas spin coating has been pro- vice parameters, e.g. PCE, JSC and FF, exhibit a strong correlation with
mising among the chemical methods. Hence, we briefly introduce these series resistance of the solar cell which is discussed in details in Section
four growth methods for Sb2Se3 preparation in the following section. In 4.6. As expected, the CSS-grown champion cell has the highest FF,
addition to growth methods, several post-treatment processes—namely, whereas the cell prepared by spin coating had the lowest FF. Because
heat treatment (Wen et al., 2017), chemical treatment (Chen et al., VTD and RTE devices were prepared by the same research group using
2017c; Leng et al., 2014; Li, Z. et al., 2016), and doping (Chen, S. et al., an identical device structure of ITO/CdS/Sb2Se3/Au, the devices have a
2018; Li, Y. et al., 2016a)—have been applied to enhance the material similar J-V curve; however, the former cell has a slightly higher current
properties and device performance, as is also discussed below. density compared to the latter. This difference is mainly due to the
Close-Spaced Sublimation. Relatively low cost and high growth rate improved crystalline quality of the VTD Sb2Se3 film. On the other hand,
are the main advantages of CSS. This method has been widely used to the CSS cell has a higher EQE in the long-wavelength spectral region
deposit semiconductor compounds such as CdTe (Alamri, 2003) for PV compared to other counterparts. Since the EQE of the solar cell at the
applications. Recently, this method was also used to fabricate Sb2Se3 infrared spectral range is strongly related to rear surface recombination,
solar cells (Hutter et al., 2018a; Li, D.-B. et al., 2018). Sb2Se3 source the diffusion lengths as well as the absorption of the photons, the higher
(powder) and substrate are placed in the bottom and top of the graphite red response of the CSS cell might be due to improved device structure.
box, respectively. Most CSS-deposited Sb2Se3 solar cells have been However, this champion device showed a low EQE in the low-wave-
fabricated with a superstrate configuration. However, the highest length region. This is probably correlated with the reduced

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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- other hand, novel buffer layers, i.e., SnO2, TiO2, and ZnO, have similar
ture. Interestingly, similar double buffer layers of CdS/TiO2 were used lattice parameters with Sb2Se3 film.
in VTD and spin-coated devices, but the latter cell showed a higher EQE In Sb2Se3 solar cells, the importance of minimizing lattice mismatch
in the short-wavelength region compared to the former cell. The reason was realized as early as 1982 (Bhattacharya and Pramanik, 1982); yet,
for this performance difference is still unclear. most studies on this issue have been qualitative. Phillips et al. observed
Post-deposition annealing is an efficient approach to passivate that Sb2Se3 thin films grown on TiO2 exhibited voids, which were at-
electrically active defects. As discussed, the oxidation of the Sb2Se3 tributed to contamination of the surface and/or strain relief due to
surface with a 1.15-nm-thick oxide was observed in some studies where lattice mismatch (Phillips et al., 2017). Similarities between SnO2
Sb2Se3 was annealed in air. To avoid forming this oxide layer during the buffer layer and commonly used TEs of ITO (In2O3:Sn) and FTO
heat treatment, post-annealing under an air-free environment (e.g., (SnO2:F) are expected to produce less lattice mismatch. Lu et al. re-
under N2 or Se(vapor)/N2 flow) has been suggested (Costa et al., 2017; ported that for SnO2/Sb2Se3 solar cells, the lowest interfacial defects
Kamruzzaman et al., 2017). These studies found that as-grown Sb2Se3 density was for SnO2 film annealed at 480 °C (Lu et al., 2018). Liu et al.
films were amorphous and that after thermal treatment, all films reported that the lattice mismatch and dangling bonds at the CdS/
showed a pure orthorhombic Sb2Se3 phase. It was also found that Sb2Se3 interface were the main causes for increased defect states (Liu
300 °C is optimal for PV application, whereas at higher annealing et al., 2015). When they deposited the Sb2Se3 under an oxygen en-
temperatures (400 and 500 °C), heat treatment caused the crystal- vironment, the device performance was significantly enhanced com-
lographic texturing of films in the (1 2 0) direction, which is detrimental pared to that of the reference device; the improvement was correlated
for PV performance. In addition to these studies, Chen et al. demon- with reduced lattice mismatch or passivated dangling bonds at the CdS/
strated that recombination losses at GBs can be reduced by introducing Sb2Se3 interface. Wang et al. showed that the ZnO/Sb2Se3 interface had
n-type Cu interstitial doping at GBs using low-temperature CuCl2 heat lower defects density when randomly oriented ZnO was used, compared
treatment (Chen, C. et al., 2018). to [0 0 1]-oriented ZnO (Wang et al., 2017). First-principles calculations
of nitrogen-doped Sb2Se3 also showed that lattice parameters of the
4.3. Buffer layer host material can be altered by doping due to the large difference in
electronic polarizability between the cations and dopants, and an
The buffer layer is usually an n-type material that is used to form a elasto-optic effect triggered by the lattice expansion or contraction
p-n heterojunction with a p-type absorber layer. The bandgap of the (Sajid-ur-Rehman et al., 2018). Overall, both experimental and theo-
buffer layer should be wide enough to transmit light into the absorber retical works have shown that the lattice matching at the buffer/Sb2Se3
layer. From an electrical perspective, photo-generated electrons in the interface can be further improved by using novel buffer layers (Fig. 7B)
absorber layer move toward the TE layer through the buffer layer. To and/or by controlling the lattice parameters of Sb2Se3.
avoid energy losses in these regions, lattice matching and proper band In addition to lattice matching, electronic band alignment at the
alignment (in energy) must be considered. Fig. 7B shows the lattice interface should be optimized to avoid unintentional energy losses at
constant versus bandgap of buffer (red color) and absorber (blue color) the interfaces. As shown in Fig. S2, if the CBM of the buffer layer is
used in thin-film solar cells. Lattice mismatch at the interface may lead higher than that of the absorber layer, the interface is defined as a
to interfacial defects, Fermi-level pinning, and band alignment issues “spike,” where a barrier is formed against photo-generated electrons
that can limit device performance. leading to a decrease in JSC and FF. In contrast, when the CBM of the
One of the most commonly used buffer layers in thin-film solar cells buffer layer is lower than that of the absorber, this interface is defined
is CdS (Al-Douri et al., 2014; Al-Douri et al., 2013; Ibraheam et al., as a “cliff,” which leads to an increase of JSC; yet, VOC decreases due to
2016), even though it has different lattice matching with different ab- the increased carrier recombination rate. Hence, proper band alignment
sorber layers. For example, the interface of the CdS/Cu(In,Ga)Se2 het- with a minimization of CB mismatch is required in solar cells. In the
erojunction has a very small lattice mismatch of < 1% (Furlong et al., case of CIGS-based solar cells, excellent device performance was sug-
1998; Lindahl et al., 2013). However, the lattice mismatch was found to gested when CB position of the buffer layer higher by 0–0.4 eV com-
be 10% for the CdS/CdTe interface (Terheggen et al., 2004), where pared to that of the absorber layer (Minemoto et al., 2001b). It has been
nanocrystalline CdS grains were suggested to reduce the strain (Burst observed that when buffer layers with tunable bandgap were used in
et al., 2016). For CdS/Cu2ZnSnS4, a lattice mismatch of 7% is reported, thin-film solar cell structures— e.g., in Cu(In,Ga)Se2 (Minemoto et al.,
whereas the substitution of a CdS buffer layer with ZnS yielded a 2011), Cu(In,Ga)(Se,S)2 (Chantana et al., 2017b), Cu2ZnSn(S,Se)4
smaller value of 1% (Kaur et al., 2017). As shown in Fig. 7B, a large (Hironiwa et al., 2015) and CH3NH3Pb3-xClx perovskite heterojunctions
lattice mismatch (> 10%) is expected between CdS and Sb2Se3; how- (Minemoto and Murata, 2015)—the PCE of these thin-film solar cells
ever, it has been widely used in the Sb2Se3 solar cell structure. On the was enhanced.

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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).

Engineering of the buffer/absorber interface in solar cells has been and increase the VOC and RSh (Chantana et al., 2018a; Li et al., 2015).
demonstrated to improve device performance due to improved carrier- Overall, optimization of buffer layer properties may lead to further
transport properties and reduced recombination losses. In particular, improvement of device performance.
recombination losses through trap states might be minimized by
avoiding the misalignment between the CBM of the buffer and absorber 4.4. Hole-transport layer and back contact
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 Collection efficiency of photo-generated carriers can be improved
effective collection of photo-generated carriers (i.e., electrons in the by using a hole-transport layer (HTL) between the absorber/back-con-
case of Sb2Se3). To date, CdS is the most commonly used buffer layer in tact by reducing the resistance of the back contact (Choi et al., 2014a).
Sb2Se3 solar cells mainly because of its easy preparation via well-es- Li and co-authors reported that the HTL of 4,4′,4″,4″′-(9-octylcarbazole-
tablished chemical-bath deposition and acceptable CB alignment 1,3,6,8-tetrayl)tetrakis(N,N-bis(4-methox-yphenyl) aniline) (CZ-TA)
(Fig. 10). However, CdS has some drawbacks, namely: 1) unintentional reduced the back-contact resistance in Sb2Se3 solar cells and led to
absorption of photons in the CdS layer at higher photon energies due to increased photo-generated carrier collection (Fig. 11A), whereas the
its low bandgap of 2.4 eV (Matsuo et al., 2015), 2) detrimental effects PCE of the device significantly improved (6.84%) (Li, D.-B. et al., 2018).
on the device performance via diffusion of Cd into Sb2Se3 (Zhou et al., As shown in Fig. 11B, the EQE(-1 V)/EQE(0 V) ratio deviated from unity
2017), 3) high lattice mismatch (cf. Fig. 7B), and 4) toxicity (Zhou for the Sb2Se3 solar cells without a HTL at long wavelengths > 600 nm,
et al., 2014). Hence, several alternative buffer layers have been in- which indicates a poor carrier-collection efficiency near the back con-
vestigated for Sb2Se3 solar cells. tact that has been improved for devices with a HTL. Chen et al. (Chen
Recently, Sb2Se3/buffer heterojunctions have been prepared using et al., 2017b) showed that when a PbS quantum dot film was used as a
various buffer layers such as ZnO, TiO2, SnO2, and CdSe. Wen et al. HTL, it minimized carrier recombination loss at the back contact, but
investigated ZnO/Sb2Se3 solar cells and found that not only crystalline also contributed to photocurrent by its own near-infrared absorption. In
orientation of the absorber layer but also the defects in ZnO are im- addition to HTL strategy to achieve ohmic behavior at absorber/BC
portant for improving device performance (Wen et al., 2017). Tang and interface, Zhang et al. (Zhang et al., 2019) showed that expensive Au
co-workers (Li, K. et al., 2018) showed that PCE of Sb2Se3-based thin- contacts can be substituted with cost-effective materials such as NiOx
film solar cells can be improved by using tunable-bandgap Zn1-xMgxO HTL and Ni back contact, whereas optimal thickness of NiOx layer is
as a buffer layer, which was initially used in CIGS-based solar cells in found to be 7 nm. Furthermore, the Mo back-contact selenization in
order to decrease the majority carrier recombination via the buffer/ substrate device configuration led to enhanced (2 2 1)-orientation of the
CIGS interface defects (Minemoto et al., 2001a; Minemoto et al., 2003). Sb2Se3 absorber layer and improved quality of the heterojunction, re-
In addition to aforementioned single buffer-layer structures, double sulting to an increase in the VOC and FF (Li et al., 2017). However, the
buffer-layer strategies have also been considered in order to reduce the rollover effect was observed in CIGS-based solar cells due to the for-
shunting path between absorber and TE layers by utilizing a highly mation of MoSe2 layer between the absorber/BC interface (Kato et al.,
resistive second buffer layer, e.g. i-ZnO (Ishizuka et al., 2005) or 2016). In other words, this effect can be explained by the presence of a
Zn1-xMgxO (Chantana et al., 2017b). In Sb2(S,Se)3 solar cells, a TiO2/ barrier, i.e. likely at the BC interface, which prevents the carrier
CdS double buffer layer has been used to achieve a high VOC of 792 mV transport in the cell by acting as Schottky diode. In Sb2Se3-based solar
by increasing the RSh (Wang, W. et al., 2018), where TiO2 has been used cells, this effect has also been observed occasionally from temperature
as a window layer. For ZnO/Zn1-xMgxO/Sb2Se3 devices with a double dependent J-V curve at low temperatures (Chen et al., 2017b; Kumar
buffer, improved device performance (4.45%) has been reported com- et al., 2019; Li, D.-B. et al., 2018), yet detailed investigation is needed
pared to the control device with single ZnO buffer layer (Li, K. et al., for clarification.
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
4.5. Transparent electrode layer
further improve this device structure. Furthermore, a highly resistive
buffer layer was also found to be beneficial to reduce the recombination
The TE has a direct influence on device performance. In general, TE

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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. cells with a window layer (ZnO (Yuan et al., 2016a; Yuan et al., 2016b))
First, the conduction band offset between TE/buffer interface is needed are rare. On the other hand, most of the window and TE layers have
to be optimized, where TE layers with tunable bandgap, e.g. Al-doped been prepared by sputtering method due to its several advantages, e.g.
Zn1-xMgxO, are preferred (Chantana et al., 2017a; Murata et al., 2015; scalability to large areas, reproducibility and low-cost (Ellmer, 2000).
Nishimura et al., 2019). Second, TE layer should have both high optical In literature, low-surface carrier recombination at the CIGS/buffer in-
transparency and high electrical transport properties. Increasing the terface was achieved by preventing the absorber surface from sput-
free charge carrier density in TE layer may reduce the electrical re- tering damage during the subsequent layer growth (Chantana et al.,
sistivity, yet optical transparency suffers from increased free carrier 2018b). However, to the best of our knowledge the influence of sput-
absorption. This existing trade-off between the optoelectric parameters tering damage has not been addressed for Sb2Se3-based thin-film solar
can only be optimized via maintaining the high mobility of free charge cells.
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 4.6. Effect of shunt and series resistances on device performance
Sb2Se3 tend to change above this temperature range (cf. Section 3.7).
To date, the most commonly used TEs are wide-bandgap (> 3 eV) Both shunt and series resistances also influence the device perfor-
In2O3:Sn (ITO), ZnO:Al (AZO), and SnO2:F (FTO). ITO is widely used as mance. Overall, high shunt resistance (RSh) is beneficial to maintain
a TE in many optoelectronic applications, e.g., flat-panel display, light- high VOC, whereas low series resistance (RS) is beneficial to increase the
emitting diodes, and solar cells. Hence, ITO-coated substrates are JSC values. Also, high FF can be maintained if RSh values are increased
commercially available or can easily be prepared using well-established and RS values are decreased. Low RSh affects the performance of the
techniques. However, scarcity and high price of In is the main issue for solar cell by reducing the FF and VOC (Hutter et al., 2018b). Usually,
finding an alternative for ITO electrodes (Mallick and Basak, 2018). On high RSh enables device reproducibility via high VOC and good junction
the other hand, FTO has better thermal stability (> 500 °C) than ITO, quality (Zhou et al., 2015). In contrast, low RSh may result from existing
which has been the reason for its wide use in high-temperature-pro- pinholes in the absorber and/or a current pathway through the device
cessed CdTe-based solar cells. However, the high processing tempera- edges (Bosio et al., 2018).
ture of FTO makes it more challenging to obtain in-house compared to As shown in Fig. 12A, Sb2Se3-based solar cells showed an increased
ITO. PCE at higher RSh values, which was more obvious for CdS than for
Recent studies showed that Earth-abundant, non-toxic, and low-cost other single buffer layers. Solar cells with double buffer layers (e.g.,
AZO films can be fabricated with comparable physical properties. From SnO2/CdS and CdS/ZnO and TiO2/CdS) have higher RSh, but there was
the stability perspective, AZO films have good thermal stability up to no obvious correlation between RSh and PCE. One can see from Table S1
400–450 °C, which makes it possible to deposit high-quality Sb2Se3 that the devices with double buffers layers have higher VOC but lower
films (at < 450 °C) on AZO-coated substrates by considering the JSC compared to the ones with a single buffer layer. Thus, it seems that
proper band alignment. However, in the literature, FTO (Kulkarni et al., the double buffer layers limit the current flow through the device.
2015; Leng et al., 2014; Li, K. et al., 2018; Li, Z. et al., 2016; Liu, X. However, we note that in recent works, e.g., Wang et al. (Wang et al.,
et al., 2014; Lu et al., 2018; Ngo et al., 2014; Wang et al., 2017; Wang 2019), Shen et al. (Shen et al., 2018), and Liang et al. (Liang et al.,
et al., 2015; Wen et al., 2017; Zhou et al., 2014; Zhou et al., 2015) and 2018), the authors successfully used respective TiO2/CdS, SnO2/CdS
ITO (Liu et al., 2015; Wen et al., 2018; Zhou et al., 2017) have been and ZnO/CdS double buffer layers to maintain not only high RSh and
widely used, whereas reports on AZO (Li et al., 2019; Yuan et al., VOC, but also, high JSC. Unlike RSh—and independent of growth
2016a; Yuan et al., 2016b) are rare. Hence, detailed investigations on methods and materials used—RS has a direct influence on PCE. As
TEs can be a new opportunity for further improving the device per- shown in Fig. 12B, the PCE systematically increases with decreasing RS.
formance and ensuring low-cost manufacturing. Fig. 12C shows the influence of RS and RSh in the J-V curve of the solar
In thin-film solar cells, the window layer is often used next to the TE cell. According to the equivalent circle, RS is inversly proportional to
layer and has an essential role to minimize recombination losses and JSC. In other words, high RS acts as a blocking layer in the solar cell;
enhance the PCE. In particular, the window layer minimizes uninten- hence, it limits the current flow (Fig. 12D).
tional shunt-current carrier recombination via pinholes of the buffer In solar cells, crystalline quality and optoelectrical properties of the
and/or absorber layer (Akari et al., 2018; Kamaruddin et al., 2017). In absorber layer and proper band alignment between layers are important
conventional thin-film solar cells, ZnO has been widely used as a to reduce the RS. As discussed above, Zhou et al. found that there is a
window layer between the TE and buffer layers to enhance the shunt correlation between the device performance and orientation of Sb2Se3
resistance (RSh) of the device, whereas reports on Sb2Se3-based solar 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

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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 subjected the unencapsulated device to standard solar irradiation
∼1,600 Ω, i.e., confirming a similar junction quality, whereas RS in- (AM1.5G) for 15 h, where the device showed only a minor 0.2% ab-
creased with increasing value of the (1 2 0) peak. The authors suggested solute decrease in PCE (Luo et al., 2014). Chen et al. also confirmed the
that the [1 2 0]-oriented grain consists of (Sb4Se6)n ribbons aligned outstanding storage stability (60 days) for a glass/ITO/CdS/Sb2Se3/Au
horizontally, i.e., in parallel with the substrate; hence, grains with this device structure (Chen et al., 2017b). More interestingly, they observed
orientation limit the transport properties due to the anisotropic nature the increased PCE (from 6.35% to 6.69%) within 60 days for a glass/
of the film. On the other hand, Sb2Se3 films with a preferred [2 1 1] ITO/CdS/Sb2Se3/HTL(PbS)/Au device structure, mainly attributed to
orientation showed better electrical transport and lower recombination improved VOC via increased carrier density in in PbS layer under am-
loss resulting from lower RS, higher FF, and improved JSC. bient oxidation.
Poor collection efficiency may exist near the back-contact region of As shown in Fig. 13, Wang et al. carried out a comparative study on
Sb2Se3 solar cells, so this issue can be further investigated via tem- device stability between CdS/Sb2Se3 and ZnO/Sb2Se3 devices with
perature-dependent RS measurements (Akari et al., 2018). In particular, randomly oriented ZnO (Wang et al., 2017). Both devices showed no
the presence of a blocking contact barrier may limit the majority-carrier degradation during the initial ambient storage period of 3 months
transport at the absorber/back interface region, which can be verified without any intentional protection. However, the CdS/Sb2Se3 device
by measuring RS with decreasing temperature. Furthermore, light-in- exhibited degradation during the damp-heat and light-soaking tests,
tensity-dependent measurements can be used to understand device whereas the ZnO/Sb2Se3 device showed good stability. When the 1-nm-
limitations. In particular, dependence of VOC on the incident light in- thick Al2O3 layer was sandwiched at the CdS/Sb2Se3 interface, the
tensity and temperature is suitable to distinguish the various re- stability of the device significantly improved (Fig. 13A,B). Whereas
combination loss mechanisms, e.g., recombination at the buffer/ab- Zhou et al argued that this degradation is due to the inter-diffusion of
sorber interface, in the space-charge region, and in the quasi-neutral Cd from CdS into absorber layer (Zhou et al., 2017). Furthermore, a
region (Li et al., 2014). ZnO/Sb2Se3-based device showed very good stability under ultraviolet
aging and thermal cycling tests (Fig. 13C,D). Overall, these results
4.7. Device stability significantly outperformed many emerging solar cells such as polymer
solar cells (Li et al., 2012), colloidal quantum dot solar cells (Cao et al.,
In addition to high efficiency, low cost, and low toxicity, long-term 2016), and hybrid perovskite solar cells (Han et al., 2017; McMeekin
operation stability is also required to manufacture commercially com- et al., 2016; Saliba et al., 2016), and they almost met the all the re-
petitive solar cells and modules. Solar cells are mostly used outdoors, so quirements set by IEC 61646 “Thin-film terrestrial photovoltaic (PV)
operational stability of the devices under damp-heat, light-soaking, and modules – Design qualification and type approval” protocol (Wang
ultraviolet radiation conditions define the stability criteria. Several et al., 2017).
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., 5. Summary and future prospects
2017). Luo et al. reported the excellent storage stability (100 days) of a
device with a glass/FTO/CdS/Sb2Se3/Au structure. Furthermore, they We reviewed the recent progress in understanding material

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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).

properties and improving device performance of the Sb2Se3-based solar stability of the device. Studies showed that the diffusion of Cd from
cells, with special emphases on electrical characteristics of solar cells, the CdS buffer layer into the Sb2Se3 absorber layer is the main cause
and compared them with fundamental limits based on the S-Q model. for poor stability of the device. In addition, preventing the absorber
JSC, VOC, and FF values of the current champion Sb2Se3 cell prepared by surface from sputtering damage may further increase the device
a physical method (CSS) with a PCE of 9.2% are found to be equivalent performance due to the reduced surface carrier recombination.
to 74%, 48%, and 81% of the S-Q limit, respectively. In the case of (5) Optimization of device fabrication by considering the lattice
Sb2Se3 device fabricated by a chemical method (spin-coating) with PCE matching, as well as electronic band alignment between layers.
of 3.9%, these ratios are 62%, 40% and 48%, respectively. In these Furthermore, optimized device architectures with reduced shunt
devices, low JSC values are due to insufficient light absorption and/or passes, e.g., via edges of the device and/or pinholes, are needed to
incomplete collection of photo-generated carriers, whereas the low VOC enhance the charge-carrier transport properties.
and FF are due to electrical nonidealities such as interfacial or bulk (6) Improvement of the absorber/BC interface, aiming to ensure the
recombination or parasitic resistance. Overall, despite the outstanding ohmic behavior via surpassing the occasionally occurred rollover
device stability and very good current collection (JSC), the present effect.
performance of Sb2Se3 solar cells is mainly limited by VOC deficit.
In the future, the following factors should be considered to further Overall, higher Sb2Se3 PCEs can be achieved by considering the
improve the PCE of Sb2Se3 solar cells: aforementioned issues related to carrier management. There is room to
overcome the remaining challenges, so it is certain that the efficiency
(1) Enhancement of the photocurrent, i.e., particularly in the short- records will continuously be surpassed in the near future. And ulti-
wavelength region of the spectrum, by using ZnO, TiO2, or SnO2 to mately, Sb2Se3-based solar cells will attract the interest of the broader
improve the EQE in the short-wavelength range. research community and will gain commercial interest.
(2) Improvement of the VOC and FF via optimized carrier management.
This is an important but complex task that requires a synchronized Declaration of Competing Interest
material science and device engineering approach to control and
passivate the recombination mechanisms of charge carriers, to The authors declare that they have no known competing financial
identify the defects (interface, surface or bulk), and to measure interests or personal relationships that could have appeared to influ-
their formation energies, energy levels, and density. Future in- ence the work reported in this paper.
vestigations in nanoscale is beneficial to deepen the understanding
of the material properties and improve device efficiency, since Acknowledgments
materials with nanoscale structure (nanomaterials or nanosctu-
crures) mostly have unique physical properties. This work was supported by the National Natural Science
(3) Systematic investigation of defects, with the goal of passivating the Foundation of China (NSFC, No. 21850410460). The authors ac-
reported deep defect states. The existence of such defects can be a knowledge the support by NSFC (No. 11774044) and the NSAF Joint
reason for low VOC due to the pinning of the Fermi level within the Foundation of China (U1630126), the grant F3-003 of the Basic
bandgap. Therefore, a detailed understanding on these defects is Research Foundation of the Uzbekistan Academy of Sciences (TR), the
needed to clarify the bottleneck of efficiency enhancement. U.S. Department of Energy (DOE) under Contract No. DEAC36-
(4) Implementation of novel buffer layers, e.g., ZnO, to maintain the 08GO28308 with the Alliance for Sustainable Energy, LLC, the manager

242
A. Mavlonov, et al. Solar Energy 201 (2020) 227–246

and operator of the National Renewable Energy Laboratory (AZ). The minerals, with A= Bi, Sb and B= S, Se. Phys. Chem. Minerals 32 (4), 295–300.
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