Materials Science in Semiconductor Processing 25 (2014) 159–162

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Materials Science in Semiconductor Processing

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

Structural and optical properties of Cu2FeSnS4 thin film

synthesized via a simple chemical method
Hao Guan a,b,n, Honglie Shen b, Baoxiang Jiao a, Xu Wang a
a
School of Materials Engineering, Yancheng Institute of Technology, 9 Yinbing Street, Yancheng 224051, PR China
b
College of Materials Science and Technology, Nanjing University of Aeronautics and Astronautics, 29 Yudao Street, Nanjing 210016,
PR China

a r t i c l e i n f o abstract

Available online 2 December 2013 Cu2FeSnS4 thin film, with potential as an effective photovoltaic absorber, was prepared
Keywords: by sulfurizing a (Cu,Sn)S/FeS-structured precursor prepared via successive ionic layer
Cu2FeSnS4 absorption and reaction combined with chemical bath deposition. X-Ray diffraction,
Thin film scanning electron microscopy, X-ray photoelectron spectroscopy, and UV-vis-NIR absor-
Chemical method bance measurements showed that the Cu2FeSnS4 thin film exhibits large agglomeration of
Sulfurization rod-shaped grains, a bandgap of Eg ¼ 1.22 eV, and a high optical absorption coefficient
( 4104 cm  1).
& 2013 Elsevier Ltd. All rights reserved.

1. Introduction Zhang et al. synthesized CFTS nanocrystals with a bandgap

Chalcopyrite semiconductors such as Cu2ZnSnS4 and
Cu2ZnSnSe4 are of great interest owing to their direct
bandgap of  1.5 eV and high optical absorption coefficient,
which make them suitable for potential applications in thin-
film solar cells [1–4]. Power conversion efficiencies of solar
cells based on Cu2ZnSnS4 and Cu2ZnSn(S, Se)4 as high as 8.4%
and 11.1% have been reported [5,6]. Related to Cu2ZnSnS4,
Cu2FeSnS4 (CFTS) is also considered a possible photovoltaic
material because it has a suitable bandgap (1.2–1.5 eV) [7]
and its constituents are abundantly available.
Several methods including vacuum and non-vacuum
methods have been developed for preparation of CFTS
compounds [8–10]. Compared to vacuum methods, non-
vacuum methods are promising because they are simple and
inexpensive and do not need sophisticated instrumentation.
Thus, non-vacuum methods can reduce the fabrication costs
for CFTS. Yan et al. used a simple hot-injection method to
synthesize quaternary tetragonal CFTS nanocrystals [11].
n
Corresponding author at: School of Materials Engineering, Yancheng
Institute of Technology, 9 Yinbing Street, Yancheng 224051, PR China.
E-mail address: guanhao@ycit.cn (H. Guan).
of  1.5 eV that attracted interest as a low-cost substitute for
thin-film solar cells [7]. Jiang et al. used a solvothermal
process to synthesize CFTS nanoparticles [12]. However,
CFTS nanoparticles must be synthesized as nanocrystal ink
to form CFTS thin films before application in solar cells. To
the best of our knowledge, solution-based chemical synth-
esis of CFTS thin films has rarely been reported. Here we
report on a simple chemical method for preparing CFTS thin
films on glass substrates. The structure, morphology,
valence, and optical properties of the films were also
investigated.
2. Experimental
SnCl2  2H2O, CuCl2  2H2O, and Na2S were obtained as
analytical-grade reagents from Nanshi Reagents and were
used without further purification. Before deposition of the
precursor film, the glass substrate was ultrasonically
cleaned with acetone and then deionized water. A mixed
solution of SnCl2 (0.03 M) and CuCl2 (0.06 M) in deionized
water was used as the cationic precursor, and Na2S
(0.12 M) in deionized water as the anionic precursor. For
the deposition process, glass was immersed in the cationic

1369-8001/$ - see front matter & 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.mssp.2013.10.021
160 H. Guan et al. / Materials Science in Semiconductor Processing 25 (2014) 159–162
precursor solution and Sn2 þ and Cu2 þ ions adsorbed on
the substrate. The glass was rinsed with deionized water
to remove unabsorbed Sn2 þ and Cu2 þ ions. Then the
substrate was immersed in the anionic precursor solution
and S2– ions reacted with Sn2 þ and Cu2 þ ions. The
substrate was again rinsed with deionized water to
remove unabsorbed material. After 60 cycles of successive
ionic layer adsorption and reaction (SILAR), a composite
layer of (Cu,Sn)S was obtained.
Then aqueous FeSO4  7H2O (1 M), Na2S2O3  5H2O (1 M)
and C10H14N2O8Na2  2H2O (Na2-EDTA) (0.1 M) were added.
A clear solution formed after stirring at room temperature
for 10 min. Sulfuric acid was added to adjust the pH to 2
and the solution was kept at 80 1C. A glass substrate with a
layer of (Cu,Sn)S was inserted into the solution and left for
a deposition time of approximately 90 min. The thickness
of the deposited film was  2 μm.
After deposition, the films were rinsed with deionized
water and annealed in a furnace at 500 1C for 20 min in
N2 þH2S (5%; flow rate 1 L/min) at atmospheric pressure
for conversion to CFTS. The heating rate was approxi-
mately 5 1C/min to allow full ionic diffusion. The system
was then allowed to cool down naturally.
Structural studies were carried out using a PANalytical
X’Pert PRO diffractometer with Cu Kα radiation at a wave-
length of 0.15406 nm. The microstructure was recorded
using an LEO-1530VP scanning electron microscope. X-Ray
photoelectron spectra were measured using a Thermo
Scientific Escalab 250 instrument and calibrated using an
XPS handbook. Transmittance and reflectance spectra were
recorded in the wavelength range 300–2000 nm using a
Varian Cary 5000 spectrophotometer.
3. Results and discussion
A typical X0ray diffraction (XRD) pattern for an
annealed film is shown in Fig. 1. The XRD pattern matches
well with the stannite structure of Cu2FeSnS4 (JCPDS No.
44-1476) in the tetragonal space group I-42m. No other
characteristic peaks for other crystalline forms are
observed. Lattice parameters for the CFTS film calculated
from the XRD pattern are a¼5.43 Å, b¼5.43 Å, and
c ¼10.79 Å, which match well with standard data for bulk
CFTS powder, indicating a stoichiometric CFTS composi-
tion. The main (1 1 2) plane shows a high peak intensity
and narrow full-width at half-maximum (FWHM). This
indicates that the annealed film has good crystallinity. The
average grain size calculated from the FWHM value for
the (1 1 2) plane according to the Scherrer equation is
 16.6 nm. To obtain high solar cell efficiency, nanocrystals
in the film must form larger crystal grains [13,14]. The
possible CFTS formation mechanism can be explained as
follows. First, Cu þ and Sn4 þ ions are obtained by the SILAR
method. Then Cu2S reacts with SnS2 to form Cu2SnS3.
Finally, Cu2SnS3 reacts with FeS, obtained via chemical
bath deposition, to form Cu2FeSnS4.
Although the phase can be identified by XRD, it cannot
be distinguished clearly owing to the similarity of the
crystal structure of CFTS and Cu2SnS3. The inset in Fig. 1
shows the Raman spectrum of the annealed film. A strong
peak at 319 cm–1 and a shoulder peak at 278 cm–1 are
Fig. 1. XRD pattern for the CFTS film. Inset: Raman spectrum for the
CFTS film.
evident, in accordance with results reported in the litera-
ture for tetragonal CFTS [15,16]. In addition, two shoulder
peaks at approximately 352 and 239 cm–1 correspond to a
Cu2SnS3 phase, which cannot be confirmed by XRD
because of the low content. The intensity of the peak
located at 319 cm–1 is high, indicating the annealed film
has good crystallinity, confirming the XRD result.
SEM images of the precursor (Cu,Sn)S/FeS film are
shown in Fig. 2a,b and images of the CFTS films in
Fig. 2c,d. It is evident that the surface of the precursor is
covered with large numbers of microaggregates that have
a diameter of 1 μm and are closely attached to each
other, in accordance with a hydroxide cluster mechanism.
By contrast, although the surface morphology of the
annealed CFTS film is still coarse, large rod-shaped grains
of 200–300 nm in width and a few voids are observed,
which are beneficial for photovoltaic applications. The
images also show that the CFTS nanoparticles grew along
a preferential orientation during annealing. In addition,
some small crystalline grains are evident, which we
attribute to non-optimized annealing. In future work we
will focus on optimizing the annealing conditions.
Fig. 3 shows XPS spectra of the four constituent
elements of the CFTS thin film. The Cu 2p peaks located
at 933.4 and 953.3 eV indicative of Cu(I) with a peak
separation of 19.9 eV is in agreement with the standard
separation of 19.8 eV [17]. The Fe 2p peaks located at 711.6
and 725.3 eV show peak splitting of 13.7 eV, which does
not overlap the Sn 2p3/2 peak located at 716.7 eV, indicat-
ing Fe(II) [18]. The Sn 3d peaks located at 486.8 and
495.2 eV confirm Sn(IV), with peak separation of 8.4 eV
[19]; the peak located at 496.7 eV, as observed by Mali
et al. [20], may be a shake-up peak and requires further
analysis. The S 2p peaks located at 161.6 and 162.6 eV fall
in the range 160–164 eV for S in sulfides [21]. The results
indicate that the main chemical states of the four elements
are Cu þ , Fe2 þ , Sn4 þ , and S2–, corresponding to the states
in the nominal CFTS chemical formula. Moreover, the
stoichiometric Cu/Fe/Sn/S ratio is approximately 2.03:1.12:
0.97:4.15, which is close to the nominal 2:1:1:4 ratio for
CFTS, in agreement with the XRD analysis.
 H. Guan et al. / Materials Science in Semiconductor Processing 25 (2014) 159–162 161

Fig. 2. Low- and high-magnification SEM images of (a,b) a (Cu,Sn)S/FeS film and (c,d) a CFTS film.

Fig. 3. XPS spectra for the CFTS film: (a) Cu 2p; (b) Fe 2p; (c) Sn 3d; and (d) S 2p.
162 H. Guan et al. / Materials Science in Semiconductor Processing 25 (2014) 159–162
Fig. 4. Optical absorption coefficient curve for the CFTS film. Inset:
Optical bandgap estimation for the CFTS film.
The optical absorption spectrum of the CFTS film is
shown in Fig. 4. The film has a large optical absorption
coefficient (4104 cm  1) in the visible region, indicating it
is suitable for thin-film solar cell applications. Saturation
of the optical absorption coefficient is also evident at a
photon energy close to 2.3 eV. As shown in the inset, the
optical bandgap energy of the film can be estimated by
extrapolating the linear part of a (αhν)2 versus hν plot. The
optical bandgap of the CFTS film is  1.22 eV (evaluation
error 70.02 eV). This is lower than literature values, which
we attribute to the presence of Cu2SnS3 phase in the
annealed film.
4. Conclusion
A simple chemical method was developed for fabrica-
tion of CFTS thin films. A (Cu,Sn)S/FeS precursor was
prepared via a combination of SILAR and chemical deposi-
tion. After annealing, the CFTS film was relatively compact
with large rod-shaped grains. The optical bandgap of the
CFTS film is 1.22 eV, indicating it has suitable optical
properties for solar cell applications.
Acknowledgments
This research was financially supported by the National
Natural Science Foundation of China (Grant No. 51202211),
the Jiangsu Innovation Program for Graduate Education
(CXLX12_0146), and the Research Fund of the Key Labora-
tory for Advanced Technology in Environmental Protection
of Jiangsu Province (AE201364).
References
[1] J.Y. Chane-Ching, A. Gillorin, O. Zaberca, A. Balocchi, X. Marie, Chem.
Commun. 47 (2011) 5229.
[2] O. Volobujeva, J. Raudoja, E. Mellikov, M. Grossberg, S. Bereznev,
R. Traksmaa, J. Phys. Chem. Solids 70 (2009) 567.
[3] R.A. Wibowo, E.S. Lee, B. Munir, K.H. Kim, Phys. Status Solidi a 204
(2007) 3373.
[4] F. Liu, Y. Li, K. Zhang, B. Wang, C. Yan, Y. Lai, Z. Zhang, J. Li, Y. Liu., Sol.
Energy Mater. Sol. Cells 94 (2010) 2431.
[5] B. Shin, O. Gunawan, Y. Zhu, N.A. Bojarczuk, S.J. Chey, S. Guha, Prog.
Photovolt. Res. Appl. 21 (2013) 72.
[6] T.K. Todorov, J. Tang, S. Bag, O. Gunawan, T. Gokmen, Y. Zhu,
D.B. Mitzi, Adv. Energy Mater 3 (2013) 34.
[7] X. Zhang, N. Bao, K. Ramasamy, Y.H.A. Wang, Y. Wang, B. Lin,
A. Gupta, Chem. Commun. 48 (2012) 4956.
[8] T.L. Evstigneeva, Y.K. Kabalov, Crystallogr. Rep. 46 (2001) 368.
[9] Z. Gui, R. Fan, X. Chen, Y. Hu, Z. Wang, Mater. Res. Bull. 39 (2004) 237.
[10] L.H. Ai, J. Jiang, J. Mater. Chem. 22 (2012) 20586.
[11] C. Yan, C. Huang, J. Yang, F. Liu, J. Liu, Y. Lai, J. Li, Y. Liu, Chem.
Commun. 48 (2012) 2603.
[12] X. Jiang, W. Xu, R. Tan, W. Song, J. Chen, Mater. Lett. 102-103 (2013)
39.
[13] T. Tanaka, D. Kawasaki, M. Nishio, Q. Guo, H. Ogawa, Phys. Status
Solidi c 3 (2006) 2844.
[14] Q.J. Guo, S.J. Kim, M. Kar, W.N. Shafarman, R.W. Birkmire, E.A. Stach,
R. Agrawal, H.W. Hillhouse, Nano Lett. 9 (2008) 2982.
[15] C. Huang, Y. Chan, F.Y. Liu, D. Tang, J. Yang, Y.Q. Lai, J. Li, Y.X. Liu,
J. Mater, Chem. A 1 (2013) 5402.
[16] C. Rincon, M. Quintero, E. Moreno, C. Power, E. Quintero, J.A. Henao,
M.A. Macias, G.E. Delgado, R. Tovar, M. Morocoima, Solid State
Commun. 151 (2011) 947.
[17] Y.F. Liu, M.Y. Ge, Y. Yue, Y. Sun, Y.Z. Wu, X. Chen, N. Dai, Phys. Status
Solidi RRL 5 (2011) 113.
[18] L. Li, X. Liu, J. Huang, M. Cao, S. Chen, Y. Shen, L. Wang, Mater. Chem.
Phys. 133 (2012) 688.
[19] R.S.C. Smart, W.M. Skinner, A.R. Gerson, Surf. Interface Anal. 28
(1999) 101.
[20] S.S. Mali, B.M. Patil, C.A. Betty, P.N. Bhosale, Y.W. Oh, S.R. Jadkar,
R.S. Devan, Y.R. Ma, P.S. Patil, Electrochim. Acta 66 (2012) 216.
[21] X. Mo, C.Y. Wanga, L.Y. Haoa, M. You, Y.R. Zhu, Z.Y. Chen, Y. Hu, Mater.
Res. Bull. 36 (2001) 1925.