Journal of Physics and Chemistry of Solids 111 (2017) 110–114

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Journal of Physics and Chemistry of Solids

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

Band gap engineering of Cu3FexSn(1-x)S4: A potential absorber material for

solar energy
P. Nazari a, A. Yazdani a, Z. Shadrokh b, B. Abdollahi Nejand b, *, N. Farahani a, R. Seifi a
a
Department of Physics, Tarbiat Modares University, P.O. Box 14115-175, Tehran, Iran
b
Nanomaterial Research Group, Academic Center for Education, Culture, and Research (ACECR) on TMU, Tehran, Iran

A R T I C L E I N F O A B S T R A C T

Keywords: In this work, band gap engineering of quaternary chalcogenides with the general formula of Cu2FexSn(1-x)S4 was
Cu2FeSnS4 conducted by substituting Sn atoms with Fe atoms. The morphology and crystalline structure of the synthesized
Quaternary chalcogenides nanostructured powder were studied by field emission scanning electron microscopy (FESEM) and X-ray
Microstructure
diffraction (XRD), respectively. Optical properties of the nanostructured powder were studied by UV–Vis spec-
Nanocrystalline materials
troscopy. The results indicate that substitution of Sn atoms with Fe atoms could transfer the tetragonal structure of
Band gap engineering
CTS to tetragonal CFTS structure. The 1.54 eV band gap reached in 80 at.% replacement of Sn atoms with Fe
atoms resulting in a tetragonal Cu2FeSnS4 flower-like structure. Moreover, by loading smaller amount of Fe atoms
up to 20 at.%, no Fe atoms incorporation in CTS structure was observed.

1. Introduction
Although the current photovoltaic technologies of Cu(In,Ga)(S,Se)2
(CIGS) and CdTe have already reached commercial production with
sustainable power conversion efficiencies of beyond 21% [1,2], there are
several important environmental constraints on the constituent elements
of these solar cells including the scarcity of Ga, In, and the toxicity of Cd
[1,3]. Besides, using low-cost, earth-abundant, and non-toxic materials in
the fabrication of solar cells has an ever-growing trend in meeting the
market criteria. Accordingly, many chalcogenides compounds such as
Fe3S4 [4], ZnS [5], Cu2SnS3 [6], CZTS [7–10], Cu2ZnSnSe4 [11],
Cu2CoSnS4 [12], and CFTS [13–15] with different photovoltaic proper-
ties have the subject of intense research in the decades. Above all, qua-
ternary chalcogenides compound consisting of Cu, Fe (or Zn), Sn, and S
(or Se) by virtue of eco-rich elements have received extensive attention in
fabrication of potential light absorber with a high absorption coefficient
(104 cm-1) within visible spectrum range, the thought-provoking band
gap of 1.5 eV for CZTS and 1.1 eV for CZTSe, and high stability compared
to the similar absorber categories of organometal halide perovskite
structure [3,16–19]. Aside from bandgap adjustment by substitution of S
with Se, substitution of Zn in the Cu2ZnSnS4(Se4) with Fe atoms has led to
an appropriate band gap engineering potential with optical band gaps of
1.28–1.50 eV for CFTS [20–24] and 1.10–1.25 eV for CFTSe [25], which
makes them opportune compounds for light absorber layer in photovol-
taic applications.
This study represents the band gap engineering of CFTS with different
compositions of Fe to Sn atoms with general Cu2FexSnx-1S4 formula. In
addition to the band gap, the morphology and structure of synthesized
Cu3FexSnx-1S4 are also studied. It was found that an 80 at.% substitution
of Sn with Fe atoms results in a 1.5 eV band gap, which is an appropriate
energy band gap in absorbing the majority of visible light wavelengths in
photovoltaic applications.
2. Experimental section
2.1. Materials
Copper (II) chloride dihydrate (CuCl2⋅2H2O), Iron(II) chloride tetra-
hydrate (FeCl2⋅4H2O), Tin chloride dehydrate (SnCl2⋅2H2O), Thiourea
(TU) (CSN2H4), and ethylene glycol (EG) are all analytical grade and
purchased from Sigma-Aldrich and Merck Company and used as received
without further purification.

* Corresponding author.
E-mail address: B.abdollahi@modares.ac.ir (B. Abdollahi Nejand).

http://dx.doi.org/10.1016/j.jpcs.2017.07.005
Received 28 February 2017; Received in revised form 10 May 2017; Accepted 5 July 2017
Available online 6 July 2017
0022-3697/© 2017 Elsevier Ltd. All rights reserved.
P. Nazari et al.
2.2. Synthesis of CFTS flowerlike structure
In a typical Solvothermal route for the synthesis of Cu2FexSn1-xS4
nanocrystals, 2 mmol Copper(II) chloride dihydrate (CuCl2⋅2H2O), x
mmol Iron(II) chloride tetrahydrate (FeCl2⋅4H2O) (where x ¼ 0, 0.2, 0.4,
0.6, 0.8, and 1), 1-x mmol SnCl2⋅2H2O, 3 mmol Thiourea (TU) (CSN2H4),
and 40 ml ethylene glycol (EG) were mixed and then stirred uniformly
until a milky suspension is achieved. The resulting suspension was
transferred into the Teflon container of a stainless steel autoclave with a
capacity of 50 mL and then moved to an oven (AzarFurnace, Iran) and
kept at 220  C for 24 h. Next, the obtained product was cooled to room
temperature followed by washing it with ethanol and DI water for three
times. Eventually, the sediment was dried in vacuum at 100  C for 12 h.
2.3. Characterization
To study the microstructure and morphology of synthesized powder,
field emission scanning electron microscopy (FE-SEM, S4160 Hitachi
Japan) was used. The phase structures were also investigated by X-ray
diffraction (XRD, Philips Expert- MPD). XRD analysis was performed at a
θ-2θ mode using Cu-Kα with a wavelength of 1.5439 Å radiation. Optical
properties of nanostructured powder were investigated by UV–Vis
spectroscopy using the wavelength range of 190–1000 nm.
3. Results and discussion
To investigate the morphologies of synthesized Cu3FexSnx-1S4 with
different X values of X ¼ 0, 0.2, 0.4, 0.6, 0.8, and 1, the FE-SEM images of
the prepared samples were studied. As demonstrated in Figs. 1a and 2a,
in X ¼ 0 the CTS is grown with spherical morphology with an average
particle size of 2 μm. By incorporation of 20 at.% Fe content, the
Cu3FexSnx-1S4 was grown with flower-like morphology (Figs. 1b and 2b).
Fig. 1. FE-SEM images of synthesized Cu3FexSnx-1S4 with different X values: 0 (a), 0.2(b), 0.4(c), 0.6(d), 0.8(e), and 1(f).
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Journal of Physics and Chemistry of Solids 111 (2017) 110–114
The total flower-like structure was in spherical form, suggesting the
formation of a flower-like structure from a central nucleus. Thus, it can be
stated that at 20 at.% Fe content, the formation of the flower-like
structure of Cu3FexSnx-1S4 initiates from emerged nuclei followed by
growing the petals in radial direction probably because of the ferro-
magnetic behavior of the Fe atoms incorporated in the precursors solu-
tion. As displayed in Fig. 1b, the petals are dense and small with 65 nm
thickness. By further enhancement of the Fe content up to 80 at.%, the
number and thickness of petals along with compactness of the flower-like
structure are decreased while the length of the petals is notably expanded
(Fig. 1c, d, and e).
The average petal thickness of flower-like structures is 65, 46, 33, and
20 nm for X ¼ 0.2, 0.4, 0.6, and 0.8, respectively (Fig. 1b, c, d, e, and
Fig. 2b). Hence, increasing the Fe content establishes radial-oriented
growth of petals, which engenders nanostructured flower-like structure
(Fig. 2b). However, by the complete replacement of Sn atoms with Fe
atoms, the skeleton of the grown CFS structure is also flower-like and
spherical with a considerable increase in the thickness of the petals
(Figs. 1f and 2c). The thickness of the petals in the flower-like CFS is
measured to be around 90 nm (Fig. 1f).
Besides, the growth parameters such as growth temperature, solution
concentration, surfactants, precursors, and engineering the elemental
composition of crystals could cause different crystal structures. Fig. 3
represents the XRD patterns of grown Cu3FexSnx-1S4 structures with
different Fe atoms contents. A pure composition of CTS (X ¼ 0) with no
Fe atoms addition shows a tetragonal Cu3SnS4 structure with the space
group of I-42 m (JCPDS 00-033-0501). Although raising the Fe up to of
20 at.% could not change the structure of tetragonal Cu3SnS4 (Fig. 3),
increasing the Fe atoms to 40, 60, and 80 at.% changes the CTS structure
to tetragonal Cu2FeSnS4. Thus, it is suggested that incorporation of Fe
atoms leads to the formation of the new structure of CFTS, which is well
matched to JCPDS 00-044-1476 with the space group of I-42 m (Fig. 3
P. Nazari et al.
Fig. 2. The schematic of proposed growth of CTS (a), CFTS (b), and CFS (c) nano-
structures at the same growth condition with different X values of X ¼ 0 (a), 0 < X < 1 (b),
and X ¼ 1 (c).
and the inset of Fig. 3). Additionally, the second phase of Cu5FeS4 with
the space group of Fm3m (JCPDS 00-024-0050) in the Fe addition con-
tents of 0.4 and 0.6 is also observed. Overall, the total replacement of Sn
atoms with Fe atoms brings about growing the new structure of ortho-
rhombic Cu5FeS4 (JCPDS 00-042-0586 with the space group of Pbca).
Modification of the elemental composition in the architecture is a
Fig. 3. (a) XRD pattern of Cu3FexSn(1-x)S4 with different Fe atoms loading concentration of X ¼ 0, X ¼ 0.2, X ¼ 0.4, X ¼ 0.6, X ¼ 0.8, and X ¼ 1.
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Journal of Physics and Chemistry of Solids 111 (2017) 110–114
decisive method for band gap engineering of the light absorber material.
As illustrated in Fig. 4, the pure CTS structure with the proposed formula
of Cu3SnS4 (confirmed by XRD results in Fig. 3) shows a 1.18 eV band gap
(Fig. 4a). In the following substitution of 20 at.% of Sn atoms with Fe, the
band gap of the structure is enhanced to 1.26 eV with no structure
transformation (Fig. 4b). Furthermore, increasing the Fe atoms content
up to 40 at.% raises the band gap of the structure to 1.31eV along with
the formation of the new structure of Cu2FeSnS4 (Figs. 3 and 4c).
The further increase in the addition of Fe atoms up to 80 at.% inclines
the band gap of the structure to 1.54 eV with no change in the structure.
The obtained band gap is desirable in absorbing a wide range of sunlight
(Fig. 4d, and e). Finally, the total replacement of Sn atoms with Fe atoms
results in an increase in the band gap to 1.62 eV and transforming the
structure to Cu5FeS4 (Figs. 3 and 4f).
4. Conclusion
In the present work, a compositional replacement of Sn atoms with Fe
atoms was introduced in band gap engineering of the Cu3FexSn(1-x)S4.
The SEM and XRD analyses were used in the study to characterize the
morphology and structural changes, respectively. UV–Vis spectroscopy
was used in measuring the band gap and the band gap shifts in the
different Fe atoms loading concentration. The results demonstrate the
potential band gap changes in different Fe atoms loading concentration.
The 1.54 eV band gap was reached at 80 at.% replacement of Sn atoms
with Fe atoms, resulting in a tetragonal Cu2FeSnS4 flower-like structure.
In the smaller amount of Fe atoms loading up to 20 at.%, no Fe atoms
incorporation in CTS structure was reported.
P. Nazari et al. Journal of Physics and Chemistry of Solids 111 (2017) 110–114

Fig. 4. The hʋ-(αhʋ)2 curve of Cu3FexSn(1-x)S4 with different Fe atoms loading concentration of X ¼ 0, X ¼ 0.2, X ¼ 0.4, X ¼ 0.6, X ¼ 0.8, and X ¼ 1.

Acknowledgments
The authors acknowledge financial support from Tarbiat Modares
University. The authors also acknowledge the Iran Nanotechnology
Initiative Council (INIC) for the partial support of this project.
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