PROGRESS IN PHOTOVOLTAICS: RESEARCH AND APPLICATIONS

Prog. Photovolt: Res. Appl. (2016)

Published online in Wiley Online Library (wileyonlinelibrary.com). DOI: 10.1002/pip.2810

RESEARCH ARTICLE

High-efciency Cu2ZnSn(S,Se)4 solar cells fabricated

through a low-cost solution process and a two-step heat
treatment
Shih-Hsiung Wu1,2, Chia-Wen Chang2, Hui-Ju Chen1, Chuan-Feng Shih1*, Yu-Yun Wang2,
Chou-Cheng Li2 and Sheng-Wen Chan2
1
Department of Electrical Engineering, National Cheng Kung University, Tainan, 70101, Taiwan
2
Green Energy and Environment Research Laboratories, Industrial Technology Research Institute, Hsinchu, 31040, Taiwan

ABSTRACT
A method for fabricating high-efciency Cu2ZnSn(S,Se)4 (CZTSSe) solar cells is presented, and it is based on a non-
explosive, low-cost, and simple solution process followed by a two-step heat treatment. 2-Methoxyethanol was used as a
solvent, and Cu, Zn, Sn, chloride salts, and thiourea were used as solutes. A CZTSSe absorber was prepared by sulfurising
and then selenising an as-coated Cu2ZnSnS4 (CZTS) lm. Sulfurisation in a sulfur vapour lled furnace for a long time
(2 h) enhanced the crystallisation of the as-coated CZTS lm and improved the stability of the CZTS precursor, and
selenisation promoted further grain growth to yield a void-free CZTSSe lm. Segregation of Cu and S at the grain bound-
aries, the absence of a ne-grain bottom layer, and the large grain size of the CZTSSe absorber were the main factors that
enhanced the grain-to-grain transport of carriers and consequently the short-circuit current (Jsc) and efciency. The
efciency of the CZTS solar cell was 5.0%, which increased to 10.1% after selenisation. For the 10.1% CZTSSe solar cell,
the external quantum efciency was approximately 80%, the open-circuit voltage was 450 mV, the short-circuit current was
36.5 mA/cm2, and the ll factor was 61.9%. Copyright © 2016 John Wiley & Sons, Ltd.

KEYWORDS
two-step heat treatment; CZTSSe; sulfurisation before selenisation

*Correspondence
Chuan-Feng Shih, Department of Electrical Engineering, National Cheng Kung University, Tainan 70101, Taiwan.
E-mail: cfshih@mail.ncku.edu.tw

Received 25 February 2016; Revised 29 June 2016; Accepted 3 August 2016

1. INTRODUCTION non-vacuum techniques involving nanocrystals [5,10],

Cu2ZnSn(S,Se)4 (CZTSSe) contains economic and earth-
abundant constituents and therefore is an alternative to
commercial CuInxGa(1-x)Se2-based photovoltaic [1]. The
highest efciency that has been achieved by non-vacuum
method for a solar cell is 8.2%, achieved for a Cu2ZnSnSe4
(CZTSe)-based solar cell [2]; for a Cu2ZnSnS4 (CZTS)-
based solar cell, this value is 8% [3]. A champion solar
cell of kesterite CZTSSe containing approximately 90%
Se and 10% S and having an efciency of 12.6% was
proposed by the IBM group [4]. However, this value is
considerably lower than the Shockley–Queisser (S–Q)
limit (32%) [5] and the value for CuInxGa(1-x)Se2
(21.7%) [6].
Various vacuum deposition methods, such as evapora-
tion [7], sputtering [8], and pulsed laser deposition [9], have
been used for fabricating CZTS absorbers. Nevertheless,
electrodeposition [2,3], and solution processes [4,11–15]
have high efciency and are cheaper than vacuum
processes. The maximal efciency of the CZTSe by elec-
trodeposited process is approximately 8.2% [2], and the
maximal efciency of electrodeposited CZTS is nearly
8% [3]. The maximal efciency of 12.6% was obtained
for CZTSSe solar cells fabricated by Todorov et al.
through a hydrazine-based solution approach [4]. How-
ever, hydrazine is highly toxic and explosive. Recently,
dimethyl sulfoxide (DMSO)-based solutions have shown
the potential to be an alternative to hydrazine [11–13,15].
An efciency of 11.2% reported by the Swiss Federal
Laboratories for Materials Testing and Research (EMPA)
for CZTSSe solar cells was prepared by using a
DMSO-based solution [11]. Although the DMSO is safer
than hydrazine, it is still toxic and ammable. In ethylene
glycol monoethylether (EGME)-based solution processes,

Copyright © 2016 John Wiley & Sons, Ltd.

High-efficiency Cu2ZnSn(S,Se)4 solar cells S.-H. Wu et al.

a conversion efciency of 5.1% of CZTS has been the

best result. Furthermore, this value is considerably lower
than those achieved through hydrazine and DMSO
processes [16].
In the CZTSSe absorber, a ne-grain bottom layer is
generally present between the large-grain CZTSSe and
Mo(S,Se)2/Mo substrate. This layer contains numerous
grain boundaries and secondary phases that should be
eliminated for further improving the efciency. EMPA's
work was successful because of the use of three-stage heat
treatment, which increased the grain size of the bottom
layer and eliminated voids during selenisation. However,
the bottom layer was still unavoidable. In particular,
promoting grain growth and controlling the grain
boundary of CZTSSe lms are crucial for efciency im-
provement. Moreover, an increase in the S/Se ratio in-
creases the band bap of CZTSSe, making it a suitable
top cell that can be used to integrate with a low Figure 1. Image of the solution after the completion of the
band-gap chalcopyrite to form a tandem cell. This is an- reaction.
other way to realise practical application of the chalco-
pyrite based solar cells in future. However, the S/Se
ratio is typically smaller than 10% for most high- the sulfurisation before selenisation (SBS) process. After
efciency CZTSSe cells. selenisation, a 50-nm-thick CdS layer, an undoped ZnO
This study demonstrates non-explosive, low-cost, and layer, an Al–ZnO layer, and a Ni–Al electrode were
high-efciency CZTSSe solar cells by using a solution sequentially deposited on the CZTSSe absorber. The fab-
process. 2-Methoxyethanol (EGME), which has no ricated CZTSSe thin lms were characterised by using
explosivity compared with hydrazine, was used as the scanning electron microscopy (JEOL 6500 F at 15 kV),
solvent. We propose that a long-term sulfurisation in the high-resolution transmission electron microscopy (Hitachi
sulfur vapour lled ambient before selenisation of an HF-2000 at 200 kV), X-ray diffraction (XRD, Philips
as-coated CZTS thin lm is the key to obtaining a high- PW3710, Bragg–Brentano type) with Cu Kα radiation
efciency CZTSSe solar cell. A CZTSSe absorber layer (scan rate: 0.04°/s), Raman spectroscopy (Horiba Jobin
with a large grain size was obtained without a ne-grain Yvon T64000 with a 514.5 nm laser source), and energy
bottom layer. Cu and S accumulated at the grain boundary dispersive X-ray spectroscopy (EDS, JEOL JSM-
contributed to grain growth and carrier transport. The con- 6480LV).
version efciency of the CZTSSe solar cell was 10.1%, The cell parameters and 10.1% efciency were certif-
which is a record among solar cells fabricated through icated by the Industrial Technology Research Institute,
EGME solution processes. Taiwan. The device efciency was measured by using
a solar simulator (Wacom WXS-220S-L2), which met
the requirements of IEC60904-3 and JIS-C 88904-
2. EXPERIMENTAL DETAILS 3 AM 1.5G global, and a Keithley 2400 SourceMeter
(certicated by National Institute of Advanced Industrial
A CZTS precursor was synthesised by using an EGME- Science and Technology, No. P14002). A primary
based solution process. First, 1.56 M copper(II) chloride
(CuCl2), 0.95 M zinc(II) chloride (ZnCl2), and 1.00 M
tin(II) chloride (SnCl2) were dissolved in EGME, and
5.52 M thiocarbamide (CH4N2S) was dissolved in another
EGME solution. Subsequently, the two solutions were
mixed and stirred until they completely homogenised
and formed a clear yellow solution, as shown in
Figure 1.
The EGME solution was dropped onto Mo-coated soda
lime glass and spin cast at 5000 rpm. The as-prepared thin
lm was dried at 200 °C. The spin casting/drying cycle was
repeated thrice for forming the precursor, which was sub-
sequently sulfurised at 540 °C in a sulfur atmosphere for
forming a CZTS thin lm. CZTSSe was prepared by
selenising the CZTS thin lm at 520 °C in a selenium Figure 2. Temperature prole of the sulfurisation before
atmosphere. Figure 2 shows the temperature prole of selenisation (SBS) process.

Prog. Photovolt: Res. Appl. (2016) © 2016 John Wiley & Sons, Ltd.
DOI: 10.1002/pip