ARTICLE IN PRESS

Solar Energy Materials & Solar Cells 91 (2007) 1199–1201

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Preparation of Cu2 ZnSnS4 thin films by sulfurizing

sol–gel deposited precursors
Kunihiko Tanaka, Noriko Moritake, Hisao Uchiki
Department of Electrical Engineering, Nagaoka University of Technology, 1603-1 Kamitomioka-machi, Nagaoka, Niigata 940-2188, Japan
Received 18 August 2006; received in revised form 5 December 2006; accepted 2 April 2007
Available online 10 May 2007

Abstract

Cu2 ZnSnS4 (CZTS) thin films were prepared by sulfurizing precursors deposited by the sol–gel method. Copper (II) acetate
monohydrate, zinc (II) acetate dihydrate and tin (II) chloride dihydrate were used as the starting materials of the sol–gel method, and 2-
methoxyethanol and monoethanolamine were used as the solvent and the stabilizer, respectively. The solution was spin coated on soda
lime glass substrates and dried at 300  C. The coated glasses were sulfurized by annealing at 500  C in a hydrogen sulfide-containing
atmosphere. The annealed thin films showed X-ray diffraction peaks attributed to the single phase CZTS. The chemical composition of
the films was almost stoichiometric and the band gap energy was 1:49 eV at room temperature.
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Keywords: Cu2 ZnSnS4 ; Solar cell; Sol–gel method; Precursor sulfurization

1. Introduction
Cu2 ZnSnS4 (CZTS) is one of the most interesting
materials for absorber layer of low-priced thin-film solar
cells because of its suitable optical band-gap of about
1:5 eV and its large absorption coefficient of over 104 cm1 .
The structure of CZTS is analogous to that of the
chalcopyrite type semiconductor of CuInx Ga1x Se2
(CIGS), which is also one of the most interesting materials
for absorber layer of solar cells. The constituent elements
of CZTS are nontoxic and inexpensive because they are
abundant elements in the earth’s crust, although those of
CIGS are toxic (Se) and expensive (In and Ga).
Katagiri et al. have reported the fabrication of CZTS
solar cells with the CZTS absorber layer prepared by
sulfurizing electron-beam-evaporated precursors [1–6]. The
structure of the solar cell was Al/Al:ZnO/CdS/CZTS/Mo-
coated soda lime glass (SLG) and the highest efficiency of
the cell was 5.45%. Seol et al. prepared CZTS thin films by
RF magnetron sputtering [7]. The optical absorption
coefficient of the thin films was about 1:0  104 cm1 in
Corresponding author.
E-mail address: tanaka@vos.nagaokaut.ac.jp (K. Tanaka).
the visible region and the estimated optical band gap
energy was 1:51 eV. Ito and Nakazawa deposited CZTS
thin films by atomic beam sputtering [8]. Friedlmeier et al.
deposited CZTS thin films by thermal evaporation [9].
Tanaka et al. fabricated CZTS thin films by co-evaporation
of elemental sources on quartz glass substrates [10]. While
there have been reports regarding the CZTS preparation as
mentioned above, all of these preparations were done in
vacuum, and therefore the CZTS thin film deposition
processes were quite expensive and complicated.
The sol–gel method is based on hydrolysis and poly-
condensation reactions. Usually, oxyhydrate precursors
can be deposited by the sol–gel method and oxides are
obtained by annealing in air. The method is a very simple
and low-priced process because no vacuum system is
required. However, sulfides cannot be deposited directly by
the sol–gel method. Kavanagh and Cameron reported that
zinc sulfide thin films were produced from films of zinc
oxide obtained by annealing in air oxyhydrate precursors
deposited by the sol–gel method from a solution of metal
alkoxide in ethanol. The zinc oxide films were converted
into zinc sulfide ones by annealing in a hydrogen sulfide-
containing atmosphere [11]. If sulfide films can be obtained
by sulfurizing oxyhydrate precursors directly without the

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doi:10.1016/j.solmat.2007.04.012
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1200 K. Tanaka et al. / Solar Energy Materials & Solar Cells 91 (2007) 1199–1201

oxide conversion process, the sulfide film preparation shown in Fig. 1. A peak marked by a solid square was
process will be very simple. attributed to crystallized SLG by annealing in an N2 þ H2 S
In this report, multicomponent CZTS thin films were (5%) gas atmosphere. The observed XRD pattern showed
prepared by sulfurizing oxyhydrate precursors which were (1 0 1), (1 1 2), (2 0 0), (2 2 0), (3 0 3), (3 1 2) and (3 3 2) peaks
deposited by the sol–gel method. This is revealed to be very of CZTS and the film was oriented to (1 1 2) as same as
simple and inexpensive method for preparing CZTS thin Refs. [5,7,10].
films. Figs. 2 and 3 show the surface and cross-section images
of the CZTS thin film, respectively. A continuous film was
formed from aggregation of granules as shown in Fig. 2,
2. Experiment
although a surface image of the precursor film was very
smooth. The film thickness was 1:2 mm as shown in Fig. 3.
Solutions for CZTS precursors were prepared from
Our film had larger and more densely packed grains than
copper (II) acetate monohydrate, zinc (II) acetate dihy-
the film reported in Ref. [7] and, smaller ones than the films
drate, tin (II) chloride dihydrate, 2-methoxyethanol (2-
reported in Refs. [5,10]. It is well known that the efficiency
metho) and monoethanolamine (MEA). 2-metho and
of polycrystalline solar cells increases with increasing grain
MEA were used as the solvent and the stabilizer,
size in the absorber layer, and therefore, the larger grains
respectively. Copper (II) acetate, zinc (II) acetate and tin
are required for the fabrication of high efficiency solar
(II) chloride of 4:375  102 , 2:1875  102 and
cells. Refs. [7,10] reported that the higher temperature
2:1875  102 mol, respectively, were dissolved in 50 ml of
2-metho, and 5 ml of MEA was added to the solution as the
stabilizer. The solution was stirred at 45  C for 1 h to
dissolve metal compounds completely. A SLG substrate of
26  26 mm2 was treated by ultrasonic cleaning in acetone
and then rinsed with deionized water. The sol solution was
dropped onto the SLG substrate rotating at 4000 rpm for
30 s. After deposition by spin coating, the film was dried in
air at 300  C. The coating and drying processes were
repeated 5 times to obtain thick films. The precursors were
annealed in an N2 þ H2 S (5%) gas atmosphere for 1 h at
500  C. The prepared films were examined with an electron
probe micro analyzer (EPMA, Shimadzu EPMA1600), an
X-ray diffractometer (XRD, Rigaku RAD2), a scanning
electron microscope (SEM, Keyence VE-7800) and an
optical transmittance spectrometer (JASCO V570).

3. Results and discussion

Fig. 2. Surface SEM image of the CZTS thin film.
An annealed film showed an XRD pattern of the single
phase CZTS with no extra phase of oxides or hydroxides as

Fig. 1. XRD pattern of an annealed thin film. Fig. 3. Cross-section SEM image of the CZTS thin film.
 ARTICLE IN PRESS
K. Tanaka et al. / Solar Energy Materials & Solar Cells 91 (2007) 1199–1201
Fig. 4. Absorption coefficient spectrum of the CZTS thin film.
treatment of CZTS films showed increased crystallinity and
grain size. To improve the crystallinity and to grow larger
grains in our films, higher temperature annealing in an
N2 þ H2 S (5%) gas of the precursors is necessary.
The chemical composition of the CZTS thin film
averaged over nine points in a surface area of 5  5 mm2
was almost stoichiometric but slightly S poor,
Cu:Zn:Sn:S ¼ 26:14:13:47. Usually, chemical composition
of sulfides shows deficiency of S. The chemical composi-
tions reported in Refs. [7,10] were Cu:Zn:Sn:S ¼
28:13:12:45 and 25:14:14:48, respectively. Since the solu-
tions contained hydroxide ion, some oxygen would be
contained in the CZTS film. However, quantity of the
oxygen contained in the CZTS thin film could not be
estimated because the EPMA detected the oxygen of the
SLG substrate. There is no report of the effect of the
oxygen in CZTS to the properties of CZTS. To verify the
effect of oxygen to CZTS films, it is necessary to investigate
the CZTS films annealed in air.
Fig. 4 shows an absorption spectrum of the CZTS thin
film where a is the absorption coefficient and hn is the
photon energy. The figure shows a feature of direct gap
semiconductors. The band gap of the film was 1:49 eV and
the absorption coefficient in the visible region was larger
than 104 cm1 , 2:7  104 cm1 at 700 nm ð1:77 eVÞ and
7:4  104 cm1 at 400 nm ð3:1 eVÞ. The band gap energy
reported in Refs. [5,7,8] was 1:4021:45, 1.45 and 1:51 eV,
respectively. The absorption coefficient reported in
1201
Refs. [5,7,8] was 104 2105 cm1 in visible region, over
104 cm1 in visible region and in the order of 104 cm1 at
near the fundamental absorption edge, respectively. These
band gap energies and absorption coefficients are compar-
able with our results.
The feature of the absorption spectrum showed that the
CZTS thin film prepared by sulfurizing the precursor
deposited by the sol–gel method can be applied to the
absorber layer of thin film solar cells.
4. Conclusion
CZTS thin films were prepared by annealing in an N2 þ
H2 S gas atmosphere oxyhydrate precursors deposited by
the sol–gel method. The films showed XRD peaks
attributed to CZTS and had almost stoichiometric
chemical composition and a direct optical gap of 1:49 eV.
Acknowledgement
We would like to thank Professor K. Hamasaki at
Nagaoka University of Technology for letting us use the
SEM.
References
[1] H. Katagiri, N. Sasaguchi, S. Hando, S. Hoshino, J. Ohashi,
T. Yokota, Technical Digest of the International PVSEC-9,
Miyazaki, 1996, p. 745.
[2] H. Katagiri, N. Sasaguchi, S. Hando, S. Hoshino, J. Ohashi,
T. Yokota, Sol. Energy Mater. Sol. Cells 49 (1997) 407.
[3] H. Katagiri, M. Nishimura, T. Onozawa, S. Maruyama, M. Fujita,
T. Sega, T. Watanabe, Proceedings of the Power Conversion
Conference, Nagaoka, 1997, p. 1003.
[4] H. Katagiri, K. Saito, T. Washio, H. Shinohara, T. Kurumadani,
S. Miyajima, Sol. Energy Mater. Sol. Cells 65 (2001) 141.
[5] H. Katagiri, N. Ihigaki, T. Ishida, K. Saito, Jpn. J. Appl. Phys. 40
(2001) 500.
[6] H. Katagiri, Thin Solid Films 480–481 (2005) 426.
[7] J. Seol, S. Lee, J. Lee, H. Nam, K. Kim, Sol. Energy Mater. Sol. Cells
75 (2003) 155.
[8] K. Ito, T. Nakazawa, Jpn. J. Appl. Phys. 27 (1988) 2094.
[9] Th.M. Friedlmeier, N. Wieser, T. Walter, H. Dittrich, H.W. Schock,
Proceedings of the 14th European Conference of Photovoltaic
Science and Engineering and Exhibition, Bedford, 1997, p. 1242.
[10] T. Tanaka, D. Kawasaki, M. Nishio, Q. Guo, Hiroshi Ogawa, Phys.
Stat. Sol. (c) 3 (2006) 2844.
[11] Y. Kavanagh, D.C. Cameron, Thin Solid Films 398–399 (2001) 24.