Colloidal Synthesis of Wurtzite Cu2FeSnS4 Nanocrystals
Xiaoyan Zhang1,2, Ningzhong Bao3, Karthik Ramasamy1, Baoping Lin*2, and Arunava Gupta*1
1
MINT Center, Department of Chemistry, The University of Abalama, Tuscaloosa, AL, 35401, U.S.A.
2
School of Chemistry and Chemical Engineering, Southeast University, Nanjing, 211189, P. R. China
3
State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing University of Technology,
Nanjing, P. R. China
Abstract — Quaternary Cu2FeSnS4 (CFTS) nanocrystals
exhibiting a new wurtzite phase have been synthesized using a
solution-based method. The optimum temperature to obtain
phase-pure wurtzite CFTS is ~210 °C. As the reaction
temperature is increased from 210 °C to 310 °C, a mixture of
wurtzite and zinc blende CFTS is obtained. The morphology of
the as-synthesized wurtzite CFTS is oblate spheroids with an
average size of 20nm. The corresponding band gaps of CFTS
nanocrystals synthesized at different temperatures varies between
1.54 eV-1.49 eV. Based on the results, CFTS with optimal band
gap, low-toxicity composition and earth-abundant elements
appears attractive as a low-cost substitute for use in thin film
solar cells.
Index Terms — Nanocrystals, wurtzite structure, Cu2FeSnS4,
optical property.
I. INTRODUCTION
Thin film solar cells based on semiconductor nanocrystals,
known as the third generation solar cells, are promising for
lowering the fabrication cost of solar cells. Different types of
semiconducting materials, including CdTe/CdSe, Cu(InxGa1-
x)Se2(CIGS), dye-sensitized TiO2, and organic materials, etc.,
have been extensively studied. However, there is considerable
interest in inexpensive, non-toxic, earth-abundant photovoltaic
materials in order to deal with the limited supply of indium
and gallium and the toxicity of cadmium. In recent years,
semiconducting Cu2ZnSnS4 (CZTS) has been extensively
studied as an alternative material with direct band gap (~1.5
eV), high absorption coefficient (~104 cm-1) and earth-
abundant elements.1 Photovoltaic devices fabricated using
CZTS nanocrystals have shown efficiencies as high as 7.2 %.2
Related to CZTS (kesterite), the naturally occurring mineral
stannite3, Cu2FeSnS4 (CFTS) can be a viable alternative
provided it exhibits the requisite optical and transport
characteristics.
Recent advances in nanocrystal synthesis have led to the
development of inexpensive non-vacuum methods, such as
spin-coating, doctor-blading, spray-printing, and drop-casting
for the fabrication of solar cells. The composition, crystal
structure and morphology of nanocrystals influence the
performance of the fabricated solar devices. Recently, a new
hexagonal wurtzite structure has been reported for CuInS2,
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CuInxGa1-xS26, and Cu2ZnSnS47 nanocrystals, in which the
cations are randomly distributed. They offer flexibility for
stoichiometry and consequently the ability to tune the Fermi
energy over a wider range. A hydrothermal method has
previously been utilized to synthesize CFTS with the stannite
structure,4 which results in the formation of large crystallites.
Recently, tetragonal CFTS nanocrytals have been synthesized
using a hot-injection method by Yan et al.5 Herein, we report
on the synthesis of CFTS nanocrystals with cation-disordered
wurtzite structure, along with their optical properties.
II. SYNTHESIS OF CFTS NANOCRYSTALS
All reactions were carried out in a fume hood under inert
conditions. In a typical synthesis of CFTS nanocrystals with
the wurtzite structure, 1 mmol Cu(acac)2, 0.5 mmol Fe(acac)3
and 0.5 mmol SnCl4.5H2O were mixed with 10 mL oleylamine
(OLA) in a four neck flask and stirred under nitrogen for 30
min at room temperature. The solution was subsequently
heated up to 150 °C and a mixture of 0.25 ml 1-dodecanethiol
(1-DDT) and 1.75 ml tert-dodecanethiol (t-DDT) were quickly
injected into the solution and subsequently heated up to 210
°C and maintained at this temperature for 30 min. The mixture
was subsequently cooled down to room temperature, and a
mixture of hexane and ethanol was used to precipitate the
product and collect it via centrifugation.
The morphology and size distribution of the nanocrystals
were determined using transmission electron microscopy
(TEM, FEI Tecnai F-20). For this purpose, the nanocrystals
were dispersed in hexane and spray-dried on a TEM copper
grid. X-ray powder diffraction (XRD, Bruker D8) was used to
study the structure of the nanocrystals, and the optical
absorption characteristics was measured using UV-Vis diffuse
reflectance spectra (UV-Vis, Varian Cary 50). The samples for
UV-Vis measurements were dispersed in hexane with ~0.02%
OLA as surfactant. The composition of the nanocrystals was
determined using Energy-dispersive X-ray spectroscopy
(EDX).
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 III. RESULTS AND DISCUSSION
The morphology of the CFTS nanocrystals has been
investigated using transmission electron microscopy (TEM).
Figure 1 (a) (b) show the TEM images of CFTS nanocrystals
Fig. 1 (a) (b) TEM images of wurtzite CFTS nanocrystals
synthesized at 210 oC at different magnifications; (c) HRTEM image
of an individual nanocrystal; (d) simulated crystal structure for
wurtzite CFTS.
with average size of approximately 20nm in the form of oblate
spheroids. High resolution TEM (HRTEM) image of a typical
nanocrystal (Fig. 1c) exhibits clear lattice fringes with
measured d spacing of 0.317 ± 0.006 nm, corresponding to
the (002) lattice planes of the wurtzite structure. Preferential
growth along the [001] direction has previously been noted for
the growth of wurtzite CIGS6 and CZTS7 nanocrystals. Figure
1(d) shows the simulated crystal structure for wurtzite CFTS.
Wurtzite-phase CFTS can be obtained from wurtzite ZnS by
substitution of Zn(II) with Cu(I), Fe(II) and Sn(IV). The sulfur
ion remains the same, coordinating with Cu(I), Fe(II) and
Sn(IV) equally. In the crystal structure, Cu, Fe and Sn atoms
are not ordered and statistically occupy the same position, with
the occupation for each atom being 50%, 25% and 25%.
The structure of the CFTS nanocrystals has been further
examined using X-ray diffraction (XRD). Bulk CFTS
crystallizes in the stannite structure, and three different crystal
structures – cubic ( P 4 3m ; a = 5.42 Å)8, and tetragonal
−
−
(stannite I 4− 2m , a =5.45 Å, c =10.76 Å and P 4 ,a = 5.43 Å,
c = 5.41 Å)3,4 have been reported for CFTS. However, the
experimental data for CFTS nanocrystals synthesized in OLA
at 210 oC do not match with the reported XRD patterns.
Instead, the pattern can be indexed to a new wurtzite phase.
Since the standard XRD pattern for wurtzite CFTS is not
available in the database, we have simulated the diffraction
pattern for wurtzite CFTS based on the structure (Figure 1d).
As shown in Figure 2, the experimental data (Figure 2a)
matches well with the simulated pattern (simulated wurtzite),
confirming that the CFTS nanocrystals synthesized at 210 °C
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has the wurtzite structure (P63mc, a = b=3.846 Å, c=6.344 Å).
With increasing the reaction temperature, the intensity of
(002)/(111) peak for wurtzite/zinc blende structure increases,
as shown in Figure 2b-d. Meanwhile, the diffraction peak
Fig. 2 XRD patterns of the Cu2FeSnS4 nanocrystals synthesized at (a)
210, (b) 240, (c) 280, and (d) 310 oC; bottom plots show simulated
XRD patterns for wurtzite and zinc blende Cu2FeSnS4 nanocrystals,
respectively.
around 32.8o, which corresponding to the (200) planes for zinc
blende structure, appears at 310 oC (Figure 2d). However, the
crystal structure of CFTS synthesized at 310 oC is a mixture of
wurtzite and zinc blende structure. Phase-pure zinc blende
CFTS has been synthesized using OA and ODE as solvent,
which has been discussed elsewhere9.
The average elemental composition of the synthesized
CFTS nanocrystals was determined by Energy-Dispersive X-
ray Spectroscopy (EDX). As shown in Table 1, the ratio of Cu,
Fe, Sn and S at different temperatures are close to the desired
2:1:1:4 ratio. Note that for the CFTS nanocrystals synthesized
at 210 oC, the composition is slightly iron deficient. This is
improved by increasing the reaction temperature, as seen in
Table 1 b-d. This may be due to the low reactivity of the iron
precursor at the lower reaction temperatures.
TABLE I
Composition (from EDX Analysis) and band gaps (from UV-Vis
absorption spectra) of CFTS nanocrystals synthesized at different
temperatures
Temp. Cu: Fe: Sn: S Band gap
(oC) (eV)
a 210 30.81: 8.24: 13.39: 47.55 1.54
b 240 33.21: 10.51: 12.85: 43.44 1.53
c 280 30.68: 11.41: 13.10: 44.81 1.51
d 310 26.67: 11.91: 14.42: 47.00 1.49
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Fig. 3 Room temperature absorption spectra of CFTS nanocrystals
synthesized at: a) 210, b) 240, c) 280, and d) 310 oC. Inset shows
extrapolation of the spectra in the band edge region for
determination of the band gap.
The as-prepared CFTS nanocrystals dissolved in hexane
display a dark brown color due to strong absorption at visible
wavelengths. The optical properties of the nanocrystals have
been studied using UV-Vis spectroscopy. Fig. 3 shows the
UV-Vis absorption spectra of CFTS nanocrystals synthesized
from 210 oC (Figure 1a) to 310 oC (Figure 1d). The band gaps
have been obtained by plotting (Ahν)2 versus hν (A =
absorbance, h = Planck’s constant and ν = frequency) and
extrapolating the linear portion of the spectrum in the band
edge region. For CFTS nanocrystals prepared at different
temperatures, the band gap varies between 1.54 eV for
nanocrystals synthesized at 210 °C (Figure 3a) to 1.49 eV for
the those synthesized at 310 °C (Figure 3d). Besides phase
transformation, the variations can be partly attributed to small
changes in the composition as determined using EDX (Table
1). There are no reported band gap values in the literature for
bulk CFTS, and our values for the wurtzite and zinc blende
nanocrystals are somewhat higher than that reported recently
for tetragonal CFTS nanocrystals (1.28 ± 0.02 eV).5
IV. CONCLUSION
In conclusion, we have developed a simple solution-based
route for the synthesis of wurtzite Cu2FeSnS4 (CFTS)
nanocrystals. It involves the thermal decomposition of metal-
acetylacetonate precursors and their reaction with a mixture of
sulfur source. Low temperature (~210 °C) is observed to be
favorable for the formation of the wurtzite phase, while the
more stable zinc blende phase is observed at higher
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temperatures (~310 °C). As-synthesized wurtzite CFTS
nanocrystals exhibit oblate spheroid morphology with a small
size distribution. Depending on the reaction temperature, the
band gaps of the CFTS nanocrystals are determined to be in
the range of 1.54 - 1.49 eV. The nanocrystals, which are well
dispersed in organic solvents such as hexane, appear attractive
for use in thin film solar cells.
ACKNOWLEDGEMENT
This work was supported by the U.S. Department of Energy,
Office of Basic Energy Sciences, Division of Materials
Sciences and Engineering under Award No. DE-FG02-
08ER46537 (X.Z. and A.G.), the National Science Foundation
under Grant No. CHE-1012850 (K.R.), the Natural Science
Foundation of China under Award No. 21006044, and the Key
Laboratory of Material-Oriented Chemical Engineering of
China under Grant No. KL10-02. As a visiting graduate
student from Southeast University, X.Z. was also partially
supported by the China Scholarship Council.
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