Materials Letters 256 (2019) 126636

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Materials Letters
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The non-aqueous chemical bath deposition of Sb2S3 thin films using

SbCl3-thioacetamide complex solution in DMF and the photovoltaic
performance of the corresponding solar cells
Kai Lv, Chengwu Shi ⇑, Yang Yang, Haoyu Fu, Fuling Guo, Qi Wang
School of Chemistry and Chemical Engineering, Anhui Province Key Laboratory of Advanced Catalytic Materials and Reaction Engineering, Hefei University of Technology,
Hefei 230009, PR China

a r t i c l e i n f o a b s t r a c t

Article history: The Sb2S3 seed layer was deposited on the TiO2 compact layer by repeated step-by-step spin-coating
Received 10 August 2019 6.67 mM SbCl3 solution in methanol and 10 mM Na2S solution in methanol/water (v/v, 95/5) to induce
Received in revised form 27 August 2019 the non-aqueous chemical bath deposition of the Sb2S3 thin film. The precursor solution of 40 mM
Accepted 5 September 2019
SbCl3 and 80 mM thioacetamide in DMF was pretreated at 100 °C for 120 min to prevent the dissolution
Available online 6 September 2019
of the Sb2S3 seed layer. The Sb2S3 thin film with the thickness of 80 nm was successfully grown on the
Sb2S3 seed layer at 120 °C for 80 min using the pretreated precursor solution of SbCl3-thioacetamide com-
Keywords:
plex in DMF. The corresponding solar cells with the architecture of FTO/TiO2 compact layer/Sb2S3 thin
Non-aqueous chemical bath deposition
SbCl3-thioacetamide complex solution in
film/spiro-OMeTAD/Au achieved an open-circuit voltage of 0.60 V, a short-circuit photocurrent density
DMF of 11.15 mA
cm 2, a fill factor of 0.40 and a photoelectric conversion efficiency of 2.70%. The non-
Sb2S3 aqueous chemical bath deposition using SbCl3-thioacetamide complex solution in DMF can provide a
Solar energy materials new approach for the preparation of the Sb2S3 thin film.
Thin films Ó 2019 Elsevier B.V. All rights reserved.

1. Introduction CdS layer and the corresponding CdS/Sb2S3 heterojunction solar

Sb2S3 was an efficient absorber material for solar cells because
of its high absorption coefficient (a > 104 cm 1 in visible range),
suitable bandgap of 1.7–1.8 eV, excellent stability and
environmental-friendly characteristics [1–3]. Various Sb2S3 depo-
sition technologies have been developed including chemical bath
deposition (CBD) [3–6], pyrolysis [7–10], successive ionic layer
absorption and reaction (SILAR) [11], thermal evaporation [12]
and atomic layer deposition (ALD) [13]. Seok et al. applied CBD
and pyrolysis to prepare Sb2S3 sensitized mesoporous TiO2 thin
films. The corresponding solar cells achieved the photoelectric con-
version efficiency (PCE) of 5.5% for CBD using SbCl3-Na2S2O3 com-
plex aqueous solution and 6.4% for pyrolysis using SbCl3-thiourea
complex solution in DMF. By the thioacetamide treatment, the
PCE can increase from 5.5% to 7.5% [3,8]. We prepared Sb2S3 sensi-
tized TiO2 nanorod arrays by repeated step-by-step spin-coating
6.67 mM SbCl3 solution in methanol and 10 mM Na2S solution in
methanol/water (v/v, 95/5) via SILAR, and the corresponding solar
cells exhibited the PCE of 3.76% [11]. Jiang Tang et al. applied rapid
thermal evaporation to deposit 700 nm thick Sb2S3 thin film on the
⇑ Corresponding author.
E-mail address: shicw506@hfut.edu.cn (C. Shi).
cells without using the hole transport materials obtained the PCE
of 3.5% [12]. Tao Chen et al. employed the pyrolysis of the
antimony-butyldithiocarbamic acid complex solution in ethanol
to prepare 137 nm thick Sb2S3 thin film and the corresponding
solar cells with the architecture of FTO/TiO2 compact layer/Sb2S3
thin film/spiro-OMeTAD/Au displayed the PCE of 4.3% [8]. By Cs-
doping of the Sb2S3 thin film, the PCE can improve to 6.56% [9].
Kim et al. used ALD to prepare the 100 nm thick Sb2S3 thin film
on the TiO2 compact layer and the corresponding solar cells with
the architecture of FTO/TiO2 compact layer/Sb2S3 thin film/P3HT/
Au showed the PCE of 5.77% [13]. To the best of our knowledge,
the non-aqueous CBD of Sb2S3 thin films using SbCl3-
thioacetamide complex solution in DMF has not been reported.
2. Experimental
The non-aqueous chemical bath deposition of Sb2S3 thin films
using SbCl3-thioacetamide complex solution in DMF was carried
out by three steps: preparation of the Sb2S3 seed layer, preparation
and pretreatment of the precursor solution, and deposition of the
Sb2S3 thin films. The detailed process parameters were shown in
Fig. 1. The architecture of the assembled solar cells was FTO/TiO2
compact layer/Sb2S3 thin film/spiro-OMeTAD/Au. The preparation

https://doi.org/10.1016/j.matlet.2019.126636
0167-577X/Ó 2019 Elsevier B.V. All rights reserved.
2 K. Lv et al. / Materials Letters 256 (2019) 126636

Fig. 1. The schematic diagram of non-aqueous chemical bath deposition of the Sb2S3 thin film.

of the spiro-OMeTAD layer was same as the literature [9]. And the
preparation of the TiO2 compact layer, gold electrode, the charac-
terizations of XRD, UV–Vis, SEM and photovoltaic performance
measurement were similar to our previous reports [14,15]. The
active area of solar cells was 0.12 cm2, defined by the black and
opaque film with the square aperture (3 mm  4 mm) adhered
on FTO.
3. Results and discussion
The non-aqueous chemical bath deposition of Sb2S3 thin films
using SbCl3-thioacetamide complex solution in DMF was com-
posed of three steps: the preparation of the Sb2S3 seed layer, the
preparation and pretreatment of the precursor solution, and the
deposition of the Sb2S3 thin films. If the Sb2S3 seed layer was not
predeposited on the TiO2 compact layer, the Sb2S3 thin films can-
not be obtained by the non-aqueous chemical bath deposition. If
the precursor solution of SbCl3 and thioacetamide in DMF was
not pretreated, the Sb2S3 seed layer would be dissolved in precur-
sor solution of the non-aqueous chemical bath deposition. Because
the deposition temperature was 120 °C and lowered the boiling
point of DMF (152.8 °C), this preparation of Sb2S3 thin films using
SbCl3-thioacetamide complex solution in DMF should be called
the non-aqueous chemical bath deposition method. Fig. 2 showed
XRD patterns, UV–Vis absorption spectra and SEM images of the
Sb2S3 thin films with the non-aqueous chemical bath deposition

Fig. 2. XRD patterns, UV–Vis absorption spectra and SEM images of the Sb2S3 thin films The non-aqueous chemical bath deposition time: (a, b, c, d) 80 min, (e, f) 120 min.
 K. Lv et al. / Materials Letters 256 (2019) 126636
Table 1
Photovoltaic performance parameters of the Sb2S3 thin film solar cells with different non-aqueous chemical bath deposition time.
Time (min) Voc (V)
70 0.61
80 0.60
100 0.55
120 0.49
Fig. 3. SEM images of the Sb2S3 thin film on the TiO2 nanorod array and the photocurrent-photovoltage characteristic of the corresponding solar cell.
time of 80 min and 120 min. From Fig. 2(a), the Sb2S3 thin film with
annealing at 300 °C for 3 min showed the diffraction peaks at
2h = 15.7, 17.5°, 22.3°, 24.9°, 28.5°, 29.3°, 35.5° and 47.3°, corre-
sponding to the spacing of (2 0 0), (1 2 0), (2 2 0), (1 3 0), (2 3 0),
(2 1 1), (2 4 0) and (1 5 1) planes of the stibnite phase (PDF#42-
1393) and a preferred orientation along (1 2 0) plane was observed.
To the Sb2S3 thin film without annealing, the Sb2S3 diffraction
peaks not appeared except for that of FTO. The result demonstrated
that the Sb2S3 thin film using the non-aqueous chemical bath
deposition was amorphous forms and can be converted to crystal
forms after annealing. From Fig. 2(b), the absorption onset of the
Sb2S3 thin films red-shifted from 550 nm without annealing to
750 nm with annealing and the optical band gap of the crystal
Sb2S3 thin film was 1.65 eV, which was in accordance with the pre-
vious reports [4,11]. When the non-aqueous chemical bath deposi-
tion time extended from 80 min to 120 min, the surface
morphology of Sb2S3 thin films changed from uneven to flat and
the pinholes in Sb2S3 thin films increased. The average thickness
of Sb2S3 thin films was 80 nm for 80 min and 200 nm for
120 min. Therefore, the thickness of the Sb2S3 thin films can be
easily adjusted by changing the non-aqueous chemical bath depo-
sition time.
Table 1 listed the photovoltaic performance parameters of the
Sb2S3 thin film solar cells with different non-aqueous chemical
bath deposition time. When the deposition time increased from
80 min to 100 min and 120 min, the open-circuit voltage (Voc),
short-circuit photocurrent density (Jsc), fill factor (FF) and PCE
decreased. The result may be related to the increase of the Sb2S3
thin film thickness, which did not guarantee carrier transporting
because of the insufficient carrier diffusion length for the thicker
Sb2S3 thin films. And the result was consistent with the literature
[13]. When the deposition time decreased from 80 min to
70 min, the Voc and FF increased, and the Jsc decreased. This result
should be due to the decrease of the Sb2S3 thin film thickness.
Therefore, the 80 nm thick Sb2S3 thin film solar cells achieved Voc
of 0.60 V, Jsc of 11.15 mA
cm 2, FF of 0.40 and PCE of 2.70%.
The Sb2S3 thin films can be also prepared on the substrate of
TiO2 nanorod arrays using the non-aqueous chemical bath deposi-
tion. The length, diameter and areal density of the TiO2 nanorod
array were 200 nm, 20 nm and 720 lm 2 [15]. Fig. 3 displayed
3
2
Jsc (mA
cm ) FF PCE (%)
6.31 0.57 2.20
11.15 0.41 2.70
4.98 0.39 1.05
4.39 0.35 0.76
SEM images of the Sb2S3 thin film on the TiO2 nanorod array with
the deposition time of 120 min and the photocurrent-photovoltage
characteristic of the corresponding solar cell. From Fig. 3(a, b), it
was found that some pinholes were distributed on the surface of
the Sb2S3 thin film and the total film thickness was 400 nm. From
Fig. 3(c), the corresponding solar cells exhibited Voc of 0.45 V, Jsc of
1.73 mA
cm 2, FF of 0.34 and PCE of 0.26%. The PCE of Sb2S3 thin
film solar cells based on the TiO2 compact layer and TiO2 nanorod
array was lower than that in previous literature [9,12,13]. This
result may be related to the stoichiometric ratio of the resulting
Sb2S3 thin film using the non-aqueous chemical bath deposition.
EDS analysis showed that the atom ratio of Sb and S in the
80 nm thick Sb2S3 thin film was 1:1.04, which was much lower
than the theoretical stoichiometric ratio of Sb2S3. Further research
is ongoing for the relationship of the Sb/S ratio in the precursor
solutions and the resulting thin films and the influence of the Sb/
S stoichiometric ratio on the carrier diffusion length in the result-
ing thin films.
4. Conclusions
The Sb2S3 thin films were firstly deposited on the TiO2 compact
layer and TiO2 nanorod array by the non-aqueous chemical bath
deposition using the SbCl3-thioacetamide complex solution in
DMF. The non-aqueous chemical bath deposition was successfully
developed and can provide a new approach for the preparation of
the Sb2S3 thin film.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
This work was financially supported by the National Natural
Science Foundation of China (51272061, 51472071) and Talent
Project of Hefei University of Technology (75010-037004, 75010-
037003).
4 K. Lv et al. / Materials Letters 256 (2019) 126636

References [8] X. Wang, J. Li, W. Liu, S. Yang, C. Zhu, T. Chen, Nanoscale 9 (2017) 3386–3390.
[9] C. Jiang, R. Tang, X. Wang, H. Ju, G. Chen, T. Chen, Sol. RRL 3 (2019) 1800272.
[10] Q. Zheng, C. Wang, G. Ma, M. Jin, S. Cheng, Y. Lai, J. Yu, Mater. Lett. 243 (2019)
[1] R. Kondrotas, C. Chen, J. Tang, Joule 2 (2018) 857–878.
104–107.
[2] X. Wang, R. Tang, C. Wu, C. Zhu, T. Chen, J. Energy Chem. 27 (2018) 713–721.
[11] C. Ying, C. Shi, K. Lv, C. Ma, F. Guo, H. Fu, Mater. Today Commun. 19 (2019)
[3] Y.C. Choi, D.U. Lee, J.H. Noh, E.K. Kim, S.I. Seok, Adv. Funct. Mater. 24 (2014)
393–395.
3587–3592.
[12] S. Yuan, H. Deng, D. Dong, X. Yang, K. Qiao, C. Hu, H. Song, H. Song, Z. He, J.
[4] Y. Itzhaik, O. Niitsoo, M. Page, G. Hodes, J. Phys. Chem. C 113 (2009) 4254–
Tang, Sol. Energy Mater Sol. Cells 157 (2016) 887–893.
4256.
[13] D.-H. Kim, S.-J. Lee, M.S. Park, J.-K. Kang, J.H. Heo, S.H. Im, S.-J. Sung, Nanoscale
[5] P.P. Boix, Y.H. Lee, F. Fabregat-Santiago, S.H. Im, I. Mora-Sero, J. Bisquert, S.I.
6 (2014) 14549–14554.
Seok, ACS Nano 6 (2012) 873–880.
[14] C. Ma, C. Shi, K. Lv, C. Ying, S. Fan, Y. Yang, Nanoscale 11 (2019) 8402–8407.
[6] E. Zimmermann, T. Pfadler, J. Kalb, J.A. Dorman, D. Sommer, G. Hahn, J.
[15] Z. Zhang, C. Shi, K. Lv, C. Ma, G. Xiao, L. Ni, J. Energy Chem. 27 (2018) 1214–
Weickert, L. Schmidt-Mende, Adv. Sci. 2 (2015) 1500059.
1218.
[7] Y.C. Choi, S.I. Seok, Adv. Funct. Mater. 25 (2015) 2892–2898.