Solar Energy Materials and Solar Cells 189 (2019) 5–10

Contents lists available at ScienceDirect

Solar Energy Materials and Solar Cells

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

Interfacial engineering for high efficiency solution processed Sb2Se3 solar T

cells
Xiaomin Wanga, Rongfeng Tanga, Yiwei Yina, Huanxin Jub, Shi’ang Lia, Changfei Zhua,
⁎
Tao Chena,
a
CAS Key Laboratory of Materials for Energy Conversion, Department of Materials Science and Engineering, University of Science and Technology of China, No. 96 Jinzhai
Road, Hefei, Anhui Province 230026, PR China
b
National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, Anhui 230029, PR China

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

Keywords: As a binary semiconductor, Sb2Se3 possesses appropriate band gap, high absorption coefficient and remarkable
Solar cell air and moisture stability, promising for light absorption material in a practical solar cell. This study demon-
Antimony selenide strates that interfacial enginnering of TiO2/Sb2Se3 by CdS is able to considerably enhance the photovoltaic
Solution process performance in planar heterojunction solar cells. Mechanistic investigations show that the optimized energy
Interfacial enginnering
alignment upon the introduction interfacial layer is responsible for the improved device performance. With this
approach, Sb2Se3 based solar cell delivers a power conversion efficiency of 3.9% with a high current density of
27.2 mA cm−2, which is the highest efficiency in solution processed Sb2Se3 solar cells. This research provides
basic understanding regarding the interfacial engineering of Sb2Se3 solar cell and practical strategy for im-
proving the device efficiency.

1. Introduction thermal decomposition leads to Sb2Se3 sensitizers. In this research, a

To alleviate the reliance on conventional fossil fuels, intensive ef-
forts have been carried out to the development of new generation solar
cells. The major target is to find photovoltaic materials that are cost
effective with high power conversion efficiency (PCE) and long term
stability. To this end, many potential materials have been examined for
device application, such as AgBiS2 [1], Sb2S3 [2–4], Sb2Se3 [5,6], Sb2S3-
XSex [7–9], CuSbS2 [10], and SbSI [11]. As a binary semiconductor,
Sb2Se3 possesses appropriate band gap of 1.1–1.3 eV, with high ab-
sorption coefficient, excellent carrier mobility and remarkable air and
moisture stability [12]. According to Shockley–Queisser limit, PCE of
the device based on Sb2Se3 light absorption material can be boosted to
32% [13]. The investigation on the Sb2Se3 solar cells focused primarily
on the development of various synthetic methods for Sb2Se3 films, for
instance, electrochemical deposition [14], thermal evaporation [5,15]
and solution methods [16–18], aiming at improving the PCE. Notably,
the vacuum deposition method has been demonstrated very successful
for fabrication of planar heterojunction Sb2Se3 solar cells and PCE as
high as 7.6% has been obtained [5,12,19,20]
. In the solution processing, the Seok group fabricated Sb2Se3 sen-
sitized solar cells, where a Sb-Se complex was synthesized [17]. The
PCE of 3.2% was obtained, which is also the state-of-the-art efficiency
in solution processed Sb2Se3 solar cells. The Tang group firstly applied
hydrazine based solution method for the fabrication of Sb2Se3 thin
films, a PCE of 2.26% was achieved in a planar heterojunction solar cell
[16]. In addition, a few attempts have been made for the synthesis of
Sb2Se3 film by thiol-amine complex method [21–23], while these stu-
dies do not report power conversion efficiency (PCE) in complete de-
vice. In this perspective, it is a challenge to fabricate Sb2Se3 absorber
material together with suitable device construction for achieving high
efficiency energy conversion.
Here we employ a chemical method to prepare molecular precursor
solution for the synthesis of Sb2Se3. The dissolution of element anti-
mony and selenium is conducted in a mixture of ethylenediamine (EN)
and ethanethiol (EtSH). Sb2Se3 thin film is then obtained by spin
coating the antimony–selenium (Sb-Se) molecular solution and sub-
sequent thermal annealing. A planar heterojunction solar cell is then
constructed. After the optimization of Sb2Se3 absorber film and em-
bellishment of CdS as interfacial layer between compact TiO2 and
Sb2Se3, we identify that the hole blocking layer CdS is one of the main
factors for enhancement of the device performance.

⁎
Corresponding author.
E-mail addresses: cfzhu@ustc.edu.cn (C. Zhu), tchenmse@ustc.edu.cn (T. Chen).

https://doi.org/10.1016/j.solmat.2018.09.020
Received 24 June 2018; Received in revised form 20 August 2018; Accepted 16 September 2018
0927-0248/ © 2018 Elsevier B.V. All rights reserved.
X. Wang et al.
2. Experimental
2.1. Materials
Antimony (Sb, 99.999%, Sinapharm Chemical Reagent Co., Ltd.),
selenium (Se, ≥ 99.0%, Sinapharm Chemical Reagent Co., Ltd.), an-
hydrous ethylenediamine (En, Analytical Reagent (AR), Sinapharm
Chemical Reagent Co., Ltd.), cadmium nitrate tetrahydrate，(Cd
(NO3)2·4H2O, AR, Sinapharm Chemical Reagent Co., Ltd.) and ammo-
nium hydroxideare (NH3·H2O, 25–28%, Sinapharm Chemical Reagent
Co., Ltd.), 2,2,7,7-tetrakis(N,N-di-p-methoxyphenylamine)-9,9-spirobi-
fluorene (Spiro-OMeTAD, 99.8%, Yingkou Youxuan Trade Co. Ltd.),
titanium (IV) isopropoxide (C12H28O4Ti, 97%, J&K), thiourea (Tu, 98%,
J&K), ethanethiol (EtSH, 98%, J&K), chlorobenzene (C6H5Cl, 99.8%, J&
K), acetonitrile (C2H3N, 99.9%, J&K), lithium bis(tri-
fluoromethylsulfonyl) imide (Li-TFSI, 98%, J&K) and 4-tert-butylpyr-
idine (tBP, 96%, J&K) were all directly used without any further pur-
ification.
2.2. Preparation of precursor solutions
Sb2Se3 precursor solutions was synthesized by referring to the re-
ported method with further modifications [21]. In specific, antimony
and selenium powders with a stoichiometric ratio are dissolved in a
mixed solvent of ethanediamine and ethanethiol with the volume ratio
of 4:1.25. The mixture was then stirred and heated to 90 °C at least
30 min. It turns into a clear dark yellow colored solution after cooling
down.
2.3. Solar cells fabrication
The compact TiO2 layer was deposited on patterned FTO-coated
glass using our reported method [24]. A thin hole blocking layer CdS
thin film was prepared by traditional CBD method at 65 °C for 6 min
[25]. In brief, 10 mL Cd(NO3)2 (15 mM) and 13 mL ammonium hydro-
xide are mixed and stirred for 2 min. Then, 6.4 mL Tu (1.2 M) and
70 mL deionized water are added into above solution in sequence under
stirring.
Sb2Se3 thin film was fabricated by spin-coating Sb2Se3 precursor
solution at a speed of 6000 rpm. The film was immediately pre-heated
on a hot plate in N2-purged glove box at 200 °C for 1 min. Sb2Se3 pre-
cursor film was then annealed at a preheated hotplate 400 °C for 2 min
in glove box. Afterwards, the Spiro-OMeTAD solution prepared by
dissolving 36.6 mg Spiro-OMeTAD powder, 14.5 μL tBP and 9.5 μL Li-
TFSI solution (520 mg mL−1 in acetonitrile) in 1 mL chlorobenzene was
spread out on Sb2Se3 thin film and spin-coated at a speed of 3000 rpm
for 30 s. Then, the Spiro-OMeTAD layer was baked at 100 °C for 10 min.
Finally, the Au counter electrode was deposited by a thermal eva-
porator under a pressure of 5.0 × 10−4 Pa. The active area of the
Fig. 1. (a) Thermogravimetric analysis of solidified Sb-Se precursor solution (inset showing Sb-Se solution) (b) X-ray diffraction patterns of the Sb2Se3 precursor thin
films annealing at different temperatures from 300 °C to 500 °C in N2 filled glove box.
6
Solar Energy Materials and Solar Cells 189 (2019) 5–10
device was defined as 0.12 cm2.
2.4. Characterization and measurements
Thermogravimetric analysis (TGA) was used to study the weight loss
of Sb2Se3 by a TGA Q5000 instrument under nitrogen atmosphere at a
heating rate of 10 °C/min with temperature increasing from 25 °C to
800 °C. The crystallinity of samples were investigated by X-ray dif-
fraction (XRD) using a Bruker Advance D8 diffractometer equipped
with graphite-monochromatized Cu K (radiation (λ = 1.5406 Â). The
surface and cross-section morphologies of the Sb2Se3 thin films were
characterized by Field emission SEM (FE-SEM siron 200). UV–vis
spectroscopy was characterized by UV–vis–NIR 3600 spectrometer. UPS
(Synchrotron radiation photoemission spectroscopy, He I excitation,
30 eV, referenced to the Femi edge of argon etched gold) was im-
plemented to detect the Femi level and valence band of Sb2Se3 film. The
valance band (VB) spectra were measured with photon energy of 30 eV.
A sample bias of − 5 V was applied to observe the secondary electron
cutoff (SEC). The work function (ϕ) can be determined by the difference
between the photon energy and the binding energy of the secondary
cutoff edge. Capacitance–voltage (C-V) measurements were conducted
by electrochemical workstation (Zahner Mess Systeme PP211) with a
frequency of 10 kHz at room temperature in darkness and the AC am-
plitude was 5 mV. DC bias voltage was changed from −0.5 to 1.0 V.
Electrochemical impedance spectroscopy (EIS) was performed using the
same electrochemical workstation at a bias potential of − 0.3 V in
darkness with the frequency ranging from 1 Hz to 4 MHz. Finally,
current–voltage measurements of Sb2Se3 solar cell were performed in a
Newport Sol3A Class AAA Solar Simulator (450 W, Oriel, model 9119).
Test was under an AM1.5 illumination to produce a 100 mW cm−2 solar
irradiation at room temperature. The external quantum efficiency
(EQE, Model SPIEQ. 200) was measured using a single source illumi-
nation system (halogen lamp) combined with a monochromator.
3. Results and discussion
In the preparation of molecular precursor solution, the volume ratio
of EN and EtSH is set to 4:1.25. To seek optimal Sb/Se ratio for device
fabrication based on absorption layer of Sb2Se3, Sb/Se ratios of 1:1.25,
1:1.5, and 1:1.75 in the precursor solution are investigated. It turns out
that elemental antimony cannot be completely dissolved when Sb/Se
ratio is lower than 1:1.5. On the other hand, when Sb/Se ratios exceeds
1:1.5, Sb2Se3 thin films show poor surface morphology and in turn
leading to poor surface coverage and a relative low efficiency (Fig. S1,
Fig. S5a). Therefore, we conduct the film fabrication using precursor
solution with Sb/Se ratio of 1:1.5. In this case, Sb and Se powders are
quickly dissolved in the mixed solvent and form optically transparent
solution (Fig. 1a, inset), which is stable for months. For film deposition,
the solution is spin-coated onto the TiO2 compact layer coated FTO
X. Wang et al.
surface.
In order to find suitable thermal decomposition condition for Sb2Se3
film fabrication, we conducted thermogravimetric analysis (TGA) of the
precursor solution. Before measurement, the precursor solution was
dried at 100 °C for ~12 h. The Sb–Se solution shows first significant
weight loss at around 200 °C (Fig. 1a), solvent evaporation is expected
in this step. In order to dissociate the solvent, preannealing temperature
for the Sb2Se3 film synthesis is thus determined to be 200 °C. For device
fabrication, crystallinity of the absorber films should be enhanced; thus
the sample films are further annealed at high temperatures in N2 filled
glove box. At 300 °C, the diffraction at 15.0°, 16.9°, 23.9°, 28.2°, and
34.1° are assigned as the (020), (120), (130), (211), (240) crystal planes
(JCPDS No.15-0861) of orthorhombic stibnite Sb2Se3. Further in-
creasing the annealing temperature leads to improved crystallinity
(Fig. 1b).
Complete solar cell device is fabricated using TiO2 and (2,2,7,7-
tetrakis(N,N-di-p-methoxyphenylamine)-9,9-spirobifluorene) (Spiro-
OMeTAD) as electron and hole transporting materials (HTM), respec-
tively. A typical cross sectional image of the device is shown in
(Fig. 2a). The thicknesses for TiO2 compact layer, Sb2Se3 and Spiro-
OMeTAD are about 52 nm, 140 nm and 65 nm, respectively. Current
density-voltage (J-V) curves are obtained under one Sun illumination
(AM 1.5G). Our optimization on the annealing temperature dependent
device performance shows that annealing of Sb2Se3 film at 400 °C is
suitable for generation of high PCE (Table S1). The J-V curve is shown
in Fig. 2b. The control device (in absence of CdS interlayer) shows
open-circuit voltage (VOC) of 275.1 mV, short-circuit current density
(JSC) of 19.7 mA cm−2 and a fill factor (FF) of 37%, with a final PCE of
2.0%.
To improve device performance, CdS as an interlayer is fabricated
onto TiO2 surface by chemical bath deposition (CBD). This treatment is
also under the consideration that CdS possesses suitable band position
and has higher carrier mobility compared with TiO2 [26]. In addition,
ultra-thin CdS adhering to the surface of TiO2 can avoid the direct
contact between TiO2 and Sb2Se3 so that the negative effect of oxygen
vacancy in TiO2 is able to be suppressed [27]. In order to maintain high
transparency for light utility, a very thin layer of CdS is fabricated by
controlling the chemical bath deposition time for only 4–6 min
7
Solar Energy Materials and Solar Cells 189 (2019) 5–10
Fig. 2. (a) Cross sectional SEM image of the
device composed of FTO/TiO2/Sb2Se3/Spiro-
OMeTAD/Au. (b) Current density–voltage
curves of the devices without CdS (black line)
and with CdS (red line). (c) Surface SEM image
of the Sb2Se3 film deposited on TiO2/CdS. (d)
Elements mapping of CdS as interlayer onto
TiO2. (For interpretation of the references to
color in this figure legend, the reader is re-
ferred to the web version of this article.).
(experimental details are provided in Supporting information). Since
CdS film is very thin, XRD characterization does not show diffraction of
CdS (Fig. S2). Instead, elemental mapping indicates that CdS evenly
distribute on the surface of TiO2 compact layer (Fig. 2d, Fig. S3). The
following device fabrication is the same as above using TiO2 as sole hole
block layer. Sb2Se3 film displays flat surface morphology. With CdS as
an interfacial layer, the device generates VOC, JSC and FF of 324.8 mV,
23.9 mA cm−2 and 41.7%, corresponding to a PCE of 3.2% (Fig. 2b). All
of the device parameters are considerably enhanced when compared
with the device without CdS interlayer (Table 1).
In order to illustrate the energy alignment with this device config-
uration, we measured the energy levels of as-synthesized Sb2Se3 film by
ultraviolet photoelectron spectroscopy (UPS, synchrotron radiation
photoemission spectroscopy). The value of secondary electron cutoff
(SEC) of Sb2Se3 is measured to be 25.7 eV (Fig. 3a) and the work
function (ψ) was calculated using the relation of ψ = photon energy
(hν) - secondary electron cutoff (SEC). Thus, ψ is calculated to be
4.30 eV [28]. From the valance band (VB) spectrum, we obtain the
absolute value of Sb2Se3 by comparing the differences between VB and
Fermi surface position, it is estimated as 0.63 eV (Fig. 3b). By analysing
the work function and band gap (1.23 eV, Fig. S4a), the VB and con-
duction band (CB) of Sb2Se3 are −4.93 eV and −3.70 eV, respectively.
The CB and VB of TiO2 are −4.10 eV and −7.40 eV [29,30], and those
of CdS are −3.90 eV and −6.20 eV [31]. A schematic diagram of the
relative energy levels of TiO2, CdS and the Sb2Se3 is depicted in Fig. 3c.
In this case, the CB maximum of CdS is in intermediate position of
Table 1
Photovoltaic performance VOC, JSC, FF, and PCE of the Sb2Se3 based devices
without (W/O) and with CdS interlayer measured under 1 Sun illumination
(AM 1.5).
Device VOC (mV) JSC (mA/cm2) FF (%) PCE (%)
W/O CdS 275.1 19.7 37.7 2.0
With CdS 324.8 23.9 41.7 3.2
340.0 27.2 41.9 3.9a
a
Photovoltaic parameters of the best device with CdS as interlayer.
X. Wang et al.
Sb2Se3 and TiO2. Therefore, CdS serving as a buffer layer is able to
relieve the rapid drop of conduction band maximum between Sb2Se3
and TiO2 and leads to improvement in VOC. Similar phenomenon is
observed in conventional CdS/CdTe solar cells, the big gap of conduct
band position between CdS and CdTe leads to the reduction of VOC.
Besides, we also carry out capacitance–voltage (C–V) measurement to
analyse the built-in field in our solar cells. According to the Mott–-
Schottky equation [6,15,32], the relationship of capacitance (C), bias
voltage (V), and built-in voltage (Vbi) is demonstrated in C-V curves
(Fig. 3d). The intercept of the fitted line with horizontal axis represents
the Vbi. From the plot, a higher Vbi (0.365 V) of the device with CdS
interlayer can be observed, which is consistent with the J-V char-
acteristic where the device with CdS possess higher VOC.
Electrochemical impedance spectrum (EIS) under dark is measured
to further investigate the interface charge transfer process. A rational
assumption is that the addition layer of CdS may lead to the reduction
of the contact resistance and carrier recombination. We employ the
Fig. 4. (a) Nyquist plots for the Sb2Se3 solar cell devices without CdS and (b) with CdS interlayer (inset equivalent circuit employed to fit the Nyquist plots),
experimental data are shown as dotted circles and the fitted results are shown as solid lines.
8
Solar Energy Materials and Solar Cells 189 (2019) 5–10
Fig. 3. (a) Secondary electron cutoff and (b)
valance band collected from ultraviolet pho-
toelectron spectroscopy of Sb2Se3 films. (c) A
schematic diagram of the relative energy levels
of TiO2, CdS and the Sb2Se3. (d) Mott–Schottky
capacitance curves for Sb2Se3 solar cell devices
without CdS (black), with CdS (red) interlayer
and linear fitting (green). (For interpretation of
the references to color in this figure legend, the
reader is referred to the web version of this
article.).
same equivalent circuit as that of planar heterojunction Sb2S3 solar cells
(inset in Fig. 4a) [24]. According to EIS analysis and the fitted para-
meters (Table S2), the device without CdS layer shows lower re-
combination resistance R2 (31.6 Ω cm2) and higher contact resistance
R3 (8.5 Ω cm2). However, the EIS analysis of device with CdS shows
only one semicircle, it is well fitted by using a shunt circuit compared
with the device without CdS interlayer (Fig. 4b). This observation in-
dicates that CdS effectively improved the interfacial charge transfer in
TiO2/CdS/Sb2Se3, leading to only one interfacial resistance (R2) was
detected. In other words, the device with double blocking layers shows
higher recombination resistance and infinitesimally contact resistance,
which impedes the recombination of electrons and holes. Besides, dark
J-V characteristic of device with CdS interfacial engineering shows
lower leakage current (Fig. S4b), the reduced recombination contribute
to the improved JSC and FF.
To further optimize the performance of Sb2Se3 solar cells, we at-
tempt to utilize poly(3-hexylthiophene) (P3HT) as HTM, which
X. Wang et al.
demonstrated excellent device performance in Sb2S3 solar cells when
compared with Spiro-OMeTAD [33,34]. In this study, it is found that
the VOC can be improved 20 mV with P3HT as HTM, while the en-
hancement is annihilated by the reduction in JSC and FF (Figs. S5b).
Finally, solar cells with maximum efficiency is obtained by using a Sb/
Se ratio equaling to 1:1.5 in precursor solution with Spiro-OMeTAD as
HTM. The maximum efficiency obtained in our study is 3.9% (Fig. 5a),
exhibiting JSC of 27.2 mA cm−2, VOC of 340.0 mV, and FF of 41.9%. The
external quantum efficiency (EQE) spectrum (Fig. 5b) shows a very
broad absorption region extended to about 1050 nm, which is con-
sistent with the absorption edge as shown in Figs. S6. The JSC value
(27.0 mA cm−2) integrated from the EQE spectrum is very close to that
obtained from the J–V measurement of Fig. 5a (27.2 mA cm−2), in-
dicating the reliability of the device characterization. This JSC is also
comparable to the vacuum deposited state-of-the-art Sb2Se3 solar cell,
which are 27.7–29.9 mA cm−2 [12,20].
Finally, stability of the device is investigated. As shown in Fig. 5c,
the device performance exhibit no degradation after 8 months of am-
bient storage (30–50% humidity without encapsulation). In this test,
PCE of the device shows a slight increase to 4.1% (Fig. S7) in the initial
days, the modification of interface contact is believed to improve per-
formance during aging. To accelerate the device degradation, the de-
vice is stored in 95% relative humidity for 500 h. It turns out that only
8% PCE degradation is observed. In this case, the VOC and JSC of the
device shows good damp stability (Fig. 5d), and the performance de-
gradation is primarily resulted from the FF. Since the organic HTM was
applied in the device, the degradation would be attributed mainly to
the Spiro-OMeTAD. The incorporation of lithium salt additive in Spiro-
OMeTAD is one of the critical reasons for the degradation which has
been intensively discussed in pervoskite solar cells [35]. The main
reason is that lithium salt is in form of lithia after the oxidation of Spiro-
OMeTAD and showed strong deliquescent behavior, which have ag-
gravated cell performance degradation. It is rational that the device
would maintain excellent stability once stable inorganic HTM is applied
[12,19].
9
Solar Energy Materials and Solar Cells 189 (2019) 5–10
Fig. 5. (a) Current density–voltage
(J–V) curves of the champion device
with CdS interlayer. (b) External
quantum efficiency and corresponding
integrated JSC of the champion device
with CdS interlayer. (c) The efficiency
evolution of a device without sealing in
30–50% relative humidity for 240 days
and then 95% relative humidity for
500 h. (d) VOC and JSC evolutions of
Sb2Se3 solar cell stored in air with re-
lative humidity of 95% without en-
capsulation.
4. Conclusions
In summary, this research manifests that CdS is able to serve as an
interlayer between TiO2 and Sb2Se3 to optimize the band alignment.
Electrochemical characterization shows that the incorporation of CdS
significantly increases charge transport across the interface and sup-
presses the charge recombination. As a result, the power conversion
efficiency is enhanced from 2.0% to 3.9%. Remarkably, the obtained
JSC of 27.2 mA cm−2 is comparable to the value of the high efficiency
devices prepared by thermal evaporation process. Our research estab-
lished an efficient strategy to use double buffer layer to increase the
power conversion efficiency of solution processed Sb2Se3 solar cell.
Acknowledgements
This work was supported by the Fundamental Research Funds for
the Central Universities under No. WK2060140023, WK2060140022,
CX3430000001, WK2060140024, the Major/Innovative Program of
Development Foundation of Hefei Center for Physical Science and
Technology (2016FXZY003), National Natural Science Foundation of
China (21503203) and the Recruitment Program of Global Experts.
Notes
The authors declare no competing interests.
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.solmat.2018.09.020.
References
[1] M. Bernechea, N.C. Miller, G. Xercavins, D. So, A. Stavrinadis, G. Konstantatos,
Solution-processed solar cells based on environmentally friendly AgBiS2 nano-
crystals, Nat. Photon. 10 (2016) 521–525.
X. Wang et al.
[2] Y.C. Choi, D.U. Lee, J.H. Noh, E.K. Kim, S.I. Seok, Highly improved Sb2S3 sensi-
tized-inorganic-organic heterojunction solar cells and quantification of traps by
deep-level transient spectroscopy, Adv. Funct. Mater. 24 (2014) 3587–3592.
[3] Y.C. Choi, S.I. Seok, Efficient Sb2S3-sensitized solar cells via single-step deposition
of Sb2S3 using S/Sb-ratio-controlled SbCl3-thiourea complex solution, Adv. Funct.
Mater. 25 (2015) 2892–2898.
[4] H. Lei, G. Yang, Y. Guo, L. Xiong, P. Qin, X. Dai, X. Zheng, W. Ke, H. Tao, Z. Chen,
B. Li, G. Fang, Efficient planar Sb2S3 solar cells using a low-temperature solution-
processed tin oxide electron conductor, Phys. Chem. Chem. Phys. 18 (2016)
16436–16443.
[5] Y. Zhou, L. Wang, S. Chen, S. Qin, X. Liu, J. Chen, D.-J. Xue, M. Luo, Y. Cao,
Y. Cheng, E.H. Sargent, J. Tang, Thin-film Sb2Se3 photovoltaics with oriented one-
dimensional ribbons and benign grain boundaries, Nat. Photonics 9 (2015)
409–415.
[6] Z. Li, H. Zhu, Y. Guo, X. Niu, X. Chen, C. Zhang, W. Zhang, X. Liang, D. Zhou,
J. Chen, Y. Mai, Efficiency enhancement of Sb2Se3 thin-film solar cells by the co-
evaporation of Se and Sb2Se3, Appl. Phys. Express 9 (2016) 052302.
[7] Y. Zhang, J. Li, G. Jiang, W. Liu, S. Yang, C. Zhu, T. Chen, Selenium‐graded
Sb2(S1−xSex)3 for planar heterojunction solar cell delivering a certified power
conversion efficiency of 5.71%, Sol. RRL 1 (2017) 1700017.
[8] O.A. Jaramillo-Quintero, M.E. Rincón, G. Vásquez-García, P.K. Nair, Influence of
the electron buffer layer on the photovoltaic performance of planar Sb2(SxSe1-x)3
solar cells, Prog. Photovolt. Res. Appl. (2018) 1–9.
[9] Y.C. Choi, Y.H. Lee, S.H. Im, J.H. Noh, T.N. Mandal, W.S. Yang, S.I. Seok, Efficient
inorganic-organic heterojunction solar cells employing Sb2(Sx/Se1-x)3graded-com-
position sensitizers, Adv. Energy Mater. 4 (2014) 1301680.
[10] Y.C. Choi, E.J. Yeom, T.K. Ahn, S.I. Seok, CuSbS2 -sensitized inorganic-organic
heterojunction solar cells fabricated using a metal-thiourea complex solution,
Angew. Chem. Int. Ed. 54 (2015) 4005–4009.
[11] R. Nie, H.-s. Yun, M.-J. Paik, A. Mehta, B.-w. Park, Y.C. Choi, S.I. Seok, Efficient
solar cells based on light-harvesting antimony sulfoiodide, Adv. Energy Mater.
(2017) 1701901.
[12] L. Wang, D.-B. Li, K. Li, C. Chen, H.-X. Deng, L. Gao, Y. Zhao, F. Jiang, L. Li,
F. Huang, Y. He, H. Song, G. Niu, J. Tang, Stable 6%-efficient Sb2Se3 solar cells
with a ZnO buffer layer, Nat. Energy 2 (2017) 17046.
[13] W. Shockley, H.J. Queisser, Detailed balance limit of efficiency of p‐n junction solar
cells, J. Appl. Phys. 32 (1961) 510–519.
[14] T.T. Ngo, S. Chavhan, I. Kosta, O. Miguel, H.J. Grande, R. Tena-Zaera,
Electrodeposition of antimony selenide thin films and application in semiconductor
sensitized solar cells, ACS Appl. Mater. Interfaces 6 (2014) 2836–2841.
[15] Z. Li, X. Chen, H. Zhu, J. Chen, Y. Guo, C. Zhang, W. Zhang, X. Niu, Y. Mai, Sb2Se3
thin film solar cells in substrate configuration and the back contact selenization,
Sol. Energy Mater. Sol. Cells 161 (2017) 190–196.
[16] Y. Zhou, M. Leng, Z. Xia, J. Zhong, H. Song, X. Liu, B. Yang, J. Zhang, J. Chen,
K. Zhou, J. Han, Y. Cheng, J. Tang, Solution-processed antimony selenide hetero-
junction solar cells, Adv. Energy Mater. 4 (2014) 1301846.
[17] Y.C. Choi, T.N. Mandal, W.S. Yang, Y.H. Lee, S.H. Im, J.H. Noh, S.I. Seok, Sb(2)Se
(3) -sensitized inorganic-organic heterojunction solar cells fabricated using a single-
source precursor, Angew. Chem. Int. Ed. 53 (2014) 1329–1333.
[18] X. Wang, R. Tang, C. Wu, C. Zhu, T. Chen, Development of antimony sulfide–se-
lenide Sb 2 (S, Se) 3 -based solar cells, J. Energy Chem. 27 (2018) 713–721.
10
Solar Energy Materials and Solar Cells 189 (2019) 5–10
[19] C. Chen, L. Wang, L. Gao, D. Nam, D. Li, K. Li, Y. Zhao, C. Ge, H. Cheong, H. Liu,
H. Song, J. Tang, 6.5% certified efficiency Sb2Se3 Solar cells using PbS colloidal
quantum dot film as hole-transporting layer, ACS Energy Lett. 2 (2017) 2125–2132.
[20] X. Wen, C. Chen, S. Lu, K. Li, R. Kondrotas, Y. Zhao, W. Chen, L. Gao, C. Wang,
J. Zhang, Vapor transport deposition of antimony selenide thin film solar cells with
7.6% efficiency, Nat. Commun. 9 (2018) 2179.
[21] D.H. Webber, J.J. Buckley, P.D. Antunez, R.L. Brutchey, Facile dissolution of sele-
nium and tellurium in a thiol–amine solvent mixture under ambient conditions,
Chem. Sci. 5 (2014) 2498.
[22] C.L. McCarthy, D.H. Webber, E.C. Schueller, R.L. Brutchey, Solution-phase con-
version of bulk metal oxides to metal chalcogenides using a simple thiol-amine
solvent mixture, Angew. Chem. Int. Ed. 54 (2015) 8378–8381.
[23] D.H. Webber, R.L. Brutchey, Alkahest for V2VI3 chalcogenides: dissolution of nine
bulk semiconductors in a diamine-dithiol solvent mixture, J. Am. Chem. Soc. 135
(2013) 15722–15725.
[24] X. Wang, J. Li, W. Liu, S. Yang, C. Zhu, T. Chen, A fast chemical approach towards
Sb2S3 film with a large grain size for high-performance planar heterojunction solar
cells, Nanoscale 9 (2017) 3386–3390.
[25] J. Li, G. Chen, C. Xue, X. Jin, W. Liu, C. Zhu, Cu2ZnSnS4−xSex solar cells fabricated
with precursor stacked layer ZnS/Cu/SnS by a CBD method, Sol. Energy Mater. Sol.
Cells 137 (2015) 131–137.
[26] I. Hwang, K. Yong, Novel CdS hole-blocking layer for photostable perovskite solar
cells, ACS Appl. Mater. Interfaces 8 (2016) 4226–4232.
[27] I. Hwang, M. Baek, K. Yong, Core/shell structured TiO2/CdS electrode to enhance
the light stability of perovskite solar cells, ACS Appl. Mater. Interfaces 7 (2015)
27863–27870.
[28] M. Kamruzzaman, L. Chaoping, F. Yishu, A.K.M. Farid Ul Islam, J.A. Zapien,
Atmospheric annealing effect on TiO2/Sb2S3/P3HT heterojunction hybrid solar
cell performance, RSC Adv. 6 (2016) 99282–99290.
[29] B. Wang, X. Xiao, T. Chen, Perovskite photovoltaics: a high-efficiency newcomer to
the solar cell family, Nanoscale 6 (2014) 12287–12297.
[30] J. Peng, T. Duong, X. Zhou, H. Shen, Y. Wu, H.K. Mulmudi, Y. Wan, D. Zhong, J. Li,
T. Tsuzuki, K.J. Weber, K.R. Catchpole, T.P. White, Efficient indium-doped TiOx
electron transport layers for high-performance perovskite solar cells and perovskite-
silicon tandems, Adv. Energy Mater. 7 (2017) 1601768.
[31] K. Du, G. Liu, X. Chen, K. Wang, PbS quantum dots sensitized TiO2 nanotubes for
photocurrent enhancement, J. Electrochem. Soc. 162 (2015) E251–E257.
[32] X. Du, Z. Chen, F. Liu, Q. Zeng, G. Jin, F. Li, D. Yao, B. Yang, Improvement in open-
circuit voltage of thin film solar cells from aqueous nanocrystals by interface en-
gineering, ACS Appl. Mater. Interfaces 8 (2016) 900–907.
[33] S.H. Im, C.S. Lim, J.A. Chang, Y.H. Lee, N. Maiti, H.J. Kim, M.K. Nazeeruddin,
M. Gratzel, S.I. Seok, Toward interaction of sensitizer and functional moieties in
hole-transporting materials for efficient semiconductor-sensitized solar cells, Nano
Lett. 11 (2011) 4789–4793.
[34] J.A. Chang, S.H. Im, Y.H. Lee, H.J. Kim, C.S. Lim, J.H. Heo, S.I. Seok, Panchromatic
photon-harvesting by hole-conducting materials in inorganic-organic heterojunc-
tion sensitized-solar cell through the formation of nanostructured electron channels,
Nano Lett. 12 (2012) 1863–1867.
[35] J. Liu, Y. Wu, C. Qin, X. Yang, T. Yasuda, A. Islam, K. Zhang, W. Peng, W. Chen,
L. Han, A dopant-free hole-transporting material for efficient and stable perovskite
solar cells, Energy Environ. Sci. 7 (2014) 2963–2967.