Materials Letters 151 (2015) 61–63

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Synthesis, structure, optics and electrical properties of Cu2FeSnS4

thin film by sputtering metallic precursor combined with rapid
thermal annealing sulfurization process
Xiankuan Meng a, Hongmei Deng b, Jun He a, Lin Sun a, Pingxiong Yang a,n, Junhao Chu a
a
Key Laboratory of Polar Materials and Devices, Ministry of Education, Department of Electronic Engineering, East China Normal University,
Shanghai 200241, China
b
Laboratory for Microstructures, Shanghai University, 99 Shangda Rd, Shanghai 200444, China

art ic l e i nf o a b s t r a c t

Article history: Cu2FeSnS4 (CFTS) thin film has been synthesized by rapid thermal annealing sulfurization of radio-
Received 20 January 2015 frequency magnetron sputtered precursor. X-ray diffraction pattern indicates that all phases belong to
Accepted 11 March 2015 CFTS with tetragonal structure. The strain which exists in the film is calculated to be 8.29
10  3 using
Available online 20 March 2015
the Williamson–Hall method. Raman spectrum and infrared reflectivity present two A1, two B and three
Keywords: E optical vibration modes. The band gap of CFTS is evaluated to be 1.42 eV by the transmission spectrum.
Cu2FeSnS4 The electrical properties of CFTS with the structure of glass/Mo/CFTS/CdS/i-ZnO/AZO have also been
Sputtering discussed. The open circuit voltage (Voc) is 110 mV, short circuit density (Jsc) is 2.5 mA cm  2 and fill
Solar cell factor (FF) is 26.3%. These results are helpful to the preparation and further study of CFTS thin films for
Sulfurization
the solar cell application.
& 2015 Elsevier B.V. All rights reserved.

1. Introduction per second and well-defined hold temperatures. These advantages

Various types of semiconductors such as CdTe, Cu(In, Ga)Se2
(CIGS) and TiO2, etc., have been extensively studied for thin film
solar cells. Nevertheless, due to the toxicity of Cd and the limited
availability of In and Ga, naturally abundant and non-toxic photo-
voltaic materials are of considerable interest [1–4]. Quaternary
semiconductor Cu2FeSnS4 (CFTS) is one of promising photovoltaic
materials as an alternative absorber layer for the development of
low-cost and environment-friendly thin film solar cells due to its
analogous crystal structures to CIGS, suitable band gap and high
absorption coefficient [4]. Recently, techniques such as the
ultrasound-assisted microwave irradiation [2], hot injection [3]
and solution-based [4] have been applied to prepare the CFTS thin
films. However, the above methods for synthesizing CFTS are
usually complex and time-consuming. Radio-frequency (RF) mag-
netron sputtering is considered to be an alternative technique to
obtain metallic precursor because of its obvious advantages in
achieving stable and uniform deposition for large-scale production
[5]. The following sulfurization of metallic precursor is performed
by using rapid thermal processing (RTP) which has an automation-
control system to provide typically up to few hundred degrees
n
Corresponding author. Tel.: þ 86 21 54345157; fax: þ86 21 54345119.
E-mail address: pxyang@ee.ecnu.edu.cn (P. Yang).
will help reduce processing time and simplify fabrication proce-
dure [5].
In this letter, the compositional, structural, optical and elec-
trical properties of CFTS have been investigated. Moreover, the
band gap based on the band structure and the orbital hybridiza-
tion theory has also been discussed. This study may offer mean-
ingful insight into the promising Cu–Fe–Sn–S system photovoltaic
materials for low-cost power generation.
2. Experimental
Two-step method (RF magnetron sputtering and post-
annealing process) was used to synthesize the CFTS thin film on
glass substrate (25 mm
25 mm). The metallic precursor was
deposited sequentially from Sn, Fe and Cu targets, respectively,
under a high-purity Ar gas atmosphere (20 sccm). The sputtering
pressures were 1.2, 1.6 and 1.6 Pa for Sn, Fe and Cu layers,
respectively, and the precursor was placed in a graphite box with
sulfur powder (0.5 g) to synthesize CFTS thin film using RTP
tubular furnace. The reaction temperature of sulfurization was
set to 550 1C, and then the sample cooled to room temperature
naturally in the tubular furnace. The atomic ratio of CFTS was
estimated to be Cu:Fe:Sn:S¼25.21:13.17:13.37:48.25, which close
to the stoichiometry ratio of 2:1:1:4. To investigate the electrical

http://dx.doi.org/10.1016/j.matlet.2015.03.046
0167-577X/& 2015 Elsevier B.V. All rights reserved.
62 X. Meng et al. / Materials Letters 151 (2015) 61–63
properties of CFTS, thin film was synthesized on Mo-coated glass
(25 mm
25 mm) using the above-mentioned experimental para-
meters. CdS thin film as buffer layer was deposited by chemical
bath deposition (CBD) under an atmospheric pressure using
CdSO4, ammonia and (NH2)2SC mixed aqueous solution (PH:
12.27) at 75 1C for 10 min. Intrinsic ZnO (i-ZnO) and aluminum-
doped ZnO (AZO, 2% Al2O3) thin films were deposited by RF
sputtering process at room temperature. No metal grid was
deposited on the thin film solar cell.
The structure of the CFTS was analyzed by X-ray diffraction
(XRD; Bruker D8 Advance), Raman scattering (Jobin Yvon Lab RAM
HR 800UV Micro PL, 488 nm lasers) and infrared reflection (IR)
measurement (Bruker Vertex 80 V). Scanning electronic micro-
scopy (SEM, FEI, S-4700) with an energy dispersive X-ray spectro-
scopy (EDX) compositional analyzer was used to analyze the cross-
sectional micrograph and the composition of the CFTS thin film.
Optical and electrical properties of CFTS were measured by
UV–vis-NIR spectroscopy (Hitachi U-3900) and AM1.5 global
spectrum (ABET technologies, Sun2000), respectively. All mea-
surements were performed at room temperature.
3. Results and discussion
Fig. 1(a) shows XRD pattern of CFTS thin film. The peaks can be
attributed to (0 0 2), (1 1 0), (1 1 2), (1 0 3), (202/211), (220/204),
(312/116/215) and (332/305) of CFTS (ICDD-PDF# 44–1476),
respectively, corresponding to a tetragonal structure and space
group of 142m. No impurity phases in CFTS are observed as shown
in Fig. 1(a). The tetragonal distortion (c/2a) is an important
parameter in compounds [6], which calculated to be 0.97 (i.e.,
a ¼5.539 and c ¼10.75 Å derived from the XRD data), namely the
strain exists during the CFTS grain growth. The strain (ε) can be
given by the Williamson–Hall equation [7],
Kλ
βhkl cos θhkl ¼ þ 4ε sin θhkl
D
where K is the shape factor (K ¼0.89); λ is the wave length of the
X-rays (λ ¼0.154056 nm); θhkl is Bragg diffraction angle and βhkl is
the full width at half maximum of hkl diffraction peak; D is the
crystallite size. As shown in Fig. 1(b), a plot is drawn by taking
4 sin θhkl along X-axis and βhkl cos θhkl along Y-axis and the strain
present in the material is extracted from the slope of the linear fit
made to the plot. The value of the strain is estimated to be
8.29
10  3, which may affect the quality of CFTS thin film.
Fig. 2(a) shows the Raman scattering result for the top surface
of the CFTS thin film. The penetration depth of this measurement,
considering the excitation wavelength used, 488 nm, is expected
to be close to 150 nm [8]. Peaks located at 318 and 286 cm  1 are
identified with the A1 modes and weaker peaks of 72, 141, 252, 301
Fig. 1. (a) The XRD pattern of CFTS. (b) Williamson–Hall method plots, and ε represents the strain.
and 340 cm  1 are assigned to the B/E modes of CFTS, which
obtained by fitting of spectrum with Lorentzian curves as shown in
Fig. 2(a) [9]. All these peaks are in line with the result reported by
Himmrich et al. [9], meaning the as-synthesized CFTS is pure
phase. Considering the penetration depth of the Raman, IR whose
spectrum passed through the CFTS thin film and reflection from
the Mo substrate has been adopted. Fig. 2(b) shows the IR pattern,
infrared-active B/E modes of CFTS are located at 76, 97, 121, 141,
252, 304, and 340 cm  1. A weaker peak of MoS2 phase can be
observed [Fig. 2(b)] nearly at 378 cm  1 [10], which may weaken
the open circuit voltage (Voc) of thin film solar cells [11]. No
impurity phases (e.g., CuxS and FeS) in the CFTS thin film are
observed which further confirmed the results of XRD and Raman
as shown in Figs. 1(a) and 2(a), respectively.
Fig. 3 shows the band gap (Eg) of CFTS, and the value is determined
to be 1.42 eV as shown in the partial enlarged view of Fig. 3 which is
consists with the ideal Eg (1.4 eV) according to the Shockley–Queisser
limit [12]. The value of Eg is different with the previous reports of 1.28,
1.35 and 1.5 eV [2–4], which attributes to the different element
composition. As shown in the inset of Fig. 3, the band gap is
determined by the band-to-band electron transition from valence
band (VB) to conduction band (CB) directly. As reported, the conduc-
tion band minimum state is mainly on a Sn and S hybrid orbital, and
the valence band maximum state arises mostly from Cu–S coupling
[13]. The various components will affect the hybridization degree of
Cu–S and Sn–S, then drive the redistribution of electrons in CB and VB,
and finally tune the band structure [14], corresponding to the change
in Eg, which explains why the reported CFTS have different Eg.
Fig. 4 shows the J–V characteristic of CFTS. The electrical
properties parameters Voc, short circuit density (Jsc) and fill factor
(FF) of CFTS are 110 mV, 2.5 mA cm  2 and 26.3%, respectively, as
shown in Fig. 4. From the inset of Fig. 4, a structure of glass/Mo/
CFTS/CdS/i-ZnO/AZO can be observed, and the thickness of CFTS is
about 600 nm with the grain throughout the whole absorbing
layer. Solar cell with the above-mentioned structure has a low
ð1Þ efficiency of 0.07% due to the 600 nm absorbed layer is too thin to
absorb a significant portion of the incident light, which will lead to
decrease in Jsc and Voc [15]. Furthermore, no metallic grid electrode
was prepared on the top of CFTS solar cell can also reduce the Jsc
and Voc.
4. Conclusions
In summary, a CFTS thin film has been formed by two-step
process. XRD, Raman and IR spectroscopy showed that the as-obt-
ained CFTS was of tetragonal structure. Thin film had a closely packed
cross-sectional surface, and the band gap of CFTS was about 1.42 eV.
The electrical properties of CFTS showed that the Voc was 110 mV, Jsc
was 2.5 mA cm  2, and FF was 26.3%. These results might lay
 X. Meng et al. / Materials Letters 151 (2015) 61–63 63

Fig. 2. (a) Raman result of CFTS (black line) and Lorentzian profile fitting (red line). A separate contribution to each peak in the fitting is shown by blue lines. (b) IR
reflectance spectrum of CFTS. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

Acknowledgements

This work was supported by the National Natural Science

Foundation of China (61474045), the State Key Basic Research
Program of China (2013CB922300).

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Fig. 4. J–V characteristics and the cross-sectional SEM image (inset) of CFTS thin
film solar cell.

foundation for solar cell application of Cu–Fe–Sn–S system thin films.

In order to improve the conversion efficiency, the chemical composi-
tion of absorber layer and annealing parameters should be optimized
and the physical properties of other layers will be researched, too.