Journal of Alloys and Compounds 680 (2016) 446e451

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Heating rate tuning in structure, morphology and electricity

properties of Cu2FeSnS4 thin films prepared by sulfurization of
metallic precursors
Xiankuan Meng a, Hongmei Deng b, Jiahua Tao a, Huiyi Cao a, Xinran Li a, Lin Sun a,
Pingxiong Yang a, *, 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

a r t i c l e i n f o a b s t r a c t

Article history: Cu2FeSnS4 (CFTS) thin films have been synthesized by sulfurization of the sputtered metallic layers. The
Received 8 January 2016 disappeared coexistence phase (Cu2FeSn3S8) and reduced strain have been observed in CFTS thin films
Received in revised form accompanying the ritardando heating rate of sulfurization, and no impurity phase is detected in the
27 February 2016
samples. It is found that the S content at the bottom of CFTS thin films turns out to be very sensitive to
Accepted 18 April 2016
Available online 19 April 2016
the heating rate. The CFTS thin film sulfurized under faster heating rate has S-poor state with a bilayer
structure and lots of micro-grains occupy the bottom of the CFTS thin film, while it has been obviously
improved by reducing the heating rate. The optical transmission spectrum reveals that valence band
Keywords:
Cu2FeSnS4
maximum and conduction band minimum of CFTS are away from one another gradually with the
Sputtering decreasing heating rate, corresponding to the enhanced band gap energy of CFTS from 1.42 to 1.47 eV. As
Thin films for these four CFTS devices, the highest open circuit voltage is 129 mV with short circuit current of
Sulfurization 3.25 mA/cm2, which increased by 17.3% and 30.0%, respectively, compared to the previous work.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction vacuum deposition process, namely radio frequency (RF) magne-

Cu2FeSnS4 (CFTS) has recently attracted increasing attention as a
promising photovoltaic material for scalable production of thin film
solar cells because of its non-toxic and earth abundant elements,
and a tunable direct band gap of 1.2e1.8 eV [1e10]. Recently, dye-
sensitized solar cells (DSSC) with CFTS thin film as a photo-
cathode have been fabricated which indicates its potential for solar
energy harvesting [11]. Various deposition methods have been
employed for the fabrication of Cu2FeSnS(Se)4 [CFTS(Se)] absorber
layer such as hot-injection method [12] and aerosol assisted
chemical vapor deposition method [13]. However, the control of the
high-quality CFTS(Se) absorber layer with large grain size and
dense, smooth surface which is very important in producing
CFTS(Se) solar cell is an extremely challenging task, moreover, the
above methods for synthesizing CFTS(Se) are usually not suitable
for mass-production and time-consuming. A typical two-stage
* Corresponding author.
E-mail address: pxyang@ee.ecnu.edu.cn (P. Yang).
tron sputtering and post-sulfurization at high temperature in the
presence of S vapor and/or H2S gas, is enjoy great popularity due to
its obvious advantages in achieving uniform deposition and good
control of grain growth. Besides, the rapid thermal processing (RTP)
system can provide well-defined hold temperatures for the
annealing of thin films which will help us to better regulate the
experimental conditions of annealing and guarantee the credibility
of the experiment. To date, the reported highest power conversion
efficiency (PCE) for CFTS and Cu2FeSnSe4 (CFTSe) thin film solar cell
is 0.07% and 0.02% [10,14], respectively. The PCE of CFTS is still lower
compared with Cu(In, Ga)Se2 and Cu2ZnSnS(Se)4 [15,16]. It is
probably caused by the existence of bilayer structure with nano-
crystalline and phase purity issues of CFTS, which is urgent need to
solve to improve the PCE of CFTS device. Nevertheless, in terms of a
typical two-step process, the quality of thin film is strongly de-
pends on the post-annealing process [17e20], moreover, there has
no investigation on the impact of heating rate on CFTS was re-
ported. Hence, the different heating rates are put forward by au-
thors to optimize the grain growth and the micro-structure of CFTS

http://dx.doi.org/10.1016/j.jallcom.2016.04.166
0925-8388/© 2016 Elsevier B.V. All rights reserved.
 X. Meng et al. / Journal of Alloys and Compounds 680 (2016) 446e451
thin films.
In this paper, we report that CFTS thin films have been synthe-
sized by using a two-stage process and four different heating rates
used in the experiments. Here, we choose sulfur powder as a sulfur
donor, which can effectively avoid the environmental and health
risks compared to using H2S gas as the sulfur source to fabricate
such composites. The calculations and mechanisms associated with
specific tuning in crystal lattice, morphology and the band gap have
been discussed, in order to study the structure, surface/section
profile and optical properties of polycrystalline CFTS thin films in
detail. Furthermore, based on the research results, the open circuit
voltage (Voc) and short circuit current (Jsc) of CFTS device have been
enhanced 17.3% and 30.0%, respectively, compared to the previous
work [10], and these results may offer the possibility to realize the
Cu-Fe-Sn-S system materials for low-cost thin film solar cells.
2. Experimental
CFTS thin films were formed by sulfurized the sandwich struc-
ture Sn/Fe/Cu metallic precursors on glass/Mo-glass substrates
using RF magnetron sputtering. The deposition order of metal layer
was substrate/Sn/Fe/Cu, which can effectively prevent the oxida-
tion of iron during the post-annealing process. All precursors were
done under a high purity Ar gas atmosphere which flow rate is 20
sccm and with background pressure of 5
104 Pa pumped by
turbo molecular pump. In this paper, the precursors were grown at
room temperature on glass substrates (25
25 mm2) using the Sn,
Fe and Cu targets with high pure of 4 N and the sputtering pressures
were set to 1.2 Pa, 1.6 Pa and 1.6 Pa for Sn, Fe and Cu, respectively.
Formation of the CFTS thin film was performed in RTP tubular
furnace. Precursors were placed in graphite box with sulfur powder
(0.5 g) and the annealing temperature was held at 550  C using
different heating rates ranging from 10 to 40  C/min. The whole
annealing process was performed in an atmosphere of N2 with a
constant working pressure of 1300 Pa. The four samples were
designated as S10, S20, S30 and S40, respectively, where the
numbers represent the heating rate of sulfurization. To investigate
the electrical properties of CFTS, thin films were synthesized on
Mo-coated glass (25
25 mm2) using the above-mentioned
experimental parameters. CdS thin films as buffer layer were
deposited by chemical bath deposition (CBD) under standard at-
mospheric pressure using CdSO4, ammonia and (NH2)2SC mixed
aqueous solution at 72  C for around 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 device. Finally, the CFTS device
with the layer-structure as shown in Fig. 1(a) has been prepared,
and Fig. 1(b) presents a typical schematic of band alignment of the
Fig. 1. (a) Schematic diagram of device structure for Cu2FeSnS4; (b) Simulated schematic diagram of band alignment for Cu2FeSnS4 device.
447
CFTS device [21,22]. The winder band gaps of ZnO and buffer layer
allow the majority of photons to be absorbed in the narrow-gap
absorber (CFTS). Electron-hole pairs generated by the photons in
the CFTS absorber are separated by the built-in electric field in the
p-n junction and contribute to cell’s photocurrent. Electron-affinity
difference at the buffer/absorber heterointerface results in a con-
duction band discontinuity △Ec.
X-ray diffraction (XRD; D/MAX-2200, Rigaku Co.) was used to
analyze the crystalline structures of CFTS thin films by using Cu Ka
radiation. Raman scattering experiment was performed with a
micro-Raman spectrometer (Jobin Yvon Lab RAM HR 800UV Micro
PL, 488 nm lasers). The surface/section profile and the composition
of CFTS thin films were analyzed by scanning electronic microscopy
(SEM, FEI, S-4700) with an energy dispersive X-ray spectroscopy
(EDX) compositional analyzer. X-ray photoelectron spectroscopy
(XPS) technique was carried out by WSCALAB X-ray photoelectron
spectrometer instrument using a source of Al Ka radiation to
confirm elemental oxidation states for CFTS. Optical properties of
CFTS thin films were measured by UVeviseNIR spectroscopy
(Perkin-Elmer Lambda 950), and the current density-voltage (J-V)
characteristics of the CFTS devices was obtained under AM1.5
global spectrum with their radiance set at 1000 W m2 (ABET
Technologies, Sun 2000). All measurements were performed at
room temperature.
3. Results and discussion
Fig. 2 shows the XRD patterns and relevant calculation param-
eters of CFTS thin films sulfurized with different heating rates. As
Fig. 2. (a) XRD patterns of Cu2FeSnS4 thin films sulfurized at different heating rates.
Inset shows position and full width at half maximum (FWHM) of (112), (220) and (312/
116) diffraction peaks; (b) Cell volume of Cu2FeSnS4 and inset is lattice constant (a and
c); (c) Williamson-Hall method plots, and ε represents the strain in the thin films.
448 X. Meng et al. / Journal of Alloys and Compounds 680 (2016) 446e451
shown in Fig. 2(a), the main diffraction peaks of all as-synthesized
CFTS thin films match well with the stannite CFTS structure (JCPDS
74-1025), apart from the weak and disappearing peaks (in S40 and
S30) arising from the Cu2FeSn3S8 phase (JCPDS 85-0378) which has
been confirmed as the transitional product in the grain growth
process of CFTS [19]. All thin films have strong preferential orien-
tation in (112) direction, as reported, the grains may coalesce and
grow in preferred direction when the interfacial energy is mini-
mum one [23]. It indicates that the interfacial energy of the others
plane is bigger than that of (112)-orientation. At the same time, the
consequence of XRD patterns reveals that the faster heating rate
results in coexistence-phase in CFTS thin film which is inconsistent
with the purpose of the preparation of target products with pure
phase. Based on the XRD data, not only the phase purity but also the
growth of grain can be obtained. As presents in the inset of Fig. 2(a),
the full width at half maximum (FWHM) of (112) peak decreases
with the heating rate, demonstrating the enhancement in the
crystallinity of CFTS thin films, which can presumably be attributed
to the increase in the predicted grain size as observed in the surface
and section profile images of CFTS thin films in Fig. 5. The FWHM of
(220) and (312/316) shows a non-linear relationship with the
heating rate, which both display a minimum when the heating rate
was set as 20  C/min, namely, maximum grain growth along (220)
and (312/116) in S20 compared with that of the others samples. It is
reported that larger grain growth orientation along (220) will show
better structural and electrical properties [20]. Furthermore, the
inset of Fig. 2(a) shows that the 2q position of (112) slightly moves
to higher angles regularly with increasing heating rate, which is
mainly caused by the shrinking cell volume as presents in Fig. 2(b)
[14].
Fig. 2(b) shows the cell volume of sulfurized CFTS with different
heating rates and inset is the lattice constants (a and c) which are
calculated using the formula: 1/d2hkl ¼ (h2 þ k2)/a2 þ l2/c2 for
tetragonal unit cell, where d is the lattice plane space and (hkl) are
the miller indices corresponding to XRD peaks. Based on the lattice
constants, we can better understand the degree of cell structure
distortion (c/2a) for S10, S20, S30 and S40, which are all deviate
from 1, meaning the strain may exist in the CFTS thin films during
the grain growth process. The strain (ε) can be estimated by the
Williamson-Hall (W-H) equation [10],
Kl
bhkl cos qhkl ¼ þ 4ε sin qhkl
D
where K is the shape factor (K ¼ 0.89); l is the wave length of the X-
rays (l ¼ 0.154056 nm); qhkl is Bragg diffraction angle and bhkl is the
full width at half maximum of hkl diffraction peak; D is the crys-
tallite size. As shown in Fig. 2(c), the plot is drawn by taking 4
sinqhkl along X-axis and bhkl cosqhkl along Y-axis and the strain
present in the material is extracted from the slope of the linear fit
made to the plot. The values of strain are estimated to be 3.7
103,
1.2
103, 4.6
103 and 4.8
103 for S10, S20, S30 and S40,
respectively, revealing the heating rate of 20  C/min can effectively
reduce the strain in CFTS thin films in our experiment, which means
the improvement of the quality of CFTS thin films. This result is
consistent with the statement of grain growth along (220) always
show better structural properties.
Although XRD is commonly used to determine the crystalline
structure of phases, they cannot be distinguished clearly here due
to the most intensive peaks of Cu2SnS3 and SnSx coincide with those
of CFTS. Therefore, Raman scattering spectra with 488 nm excita-
tion wavelength was used to confirm the presence of stannite CFTS
and/or impurity phases. Raman peaks around at 252, 315e319, and
354 cm1 as shown in Fig. 3, agree well with the reported charac-
teristic CFTS vibration modes [1,10] and no impurity phases can be
Fig. 3. Raman scattering results of Cu2FeSnS4 thin films sulfurized at different heating
rates. Inset gives the cell structure model of Cu2FeSnS4.
discovered, of which, peaks located from 315 cm1 to 319 cm1
have been identified with the A1 mode, and the others two peaks
(252 and 354 cm1) have been defined as the B/E modes for stan-
nite structure CFTS. From the vibrational point of view, the optical
modes of stannite structure can be written as:
G ¼ 2A1 þ A2 þ 2B1 þ 4B2 þ 6E [24]. Here, the A1 and A2 modes
include the motion of the anions only. For the B1 modes, half of the
Cu atoms are displaced toward the positive z axis and the other half
are displaced toward the opposite direction, while the Fe and Sn
atoms remain stationary, in the meantime, anions move only in the
xy plane. In the B2 modes of the stannite CFTS, the cations only
move along the z direction, whereas these cations move only
within the xy place in the E modes. Moreover, Raman spectra re-
veals the absence of Cu2FeSn3S8 phase, which appeared in XRD
patterns, hence, we speculate that the crystalline grain of
Cu2FeSn3S8 exists in the bottom of the as-synthesized thin films
due to the about 150 nm penetration depth of this measurement,
considering the excitation wavelength (488 nm) used. Besides, the
A1 modes of CFTS shift towards lower frequency with decreasing
heating rate of sulfurization as shown in Fig. 3. According to the
extended Keating’s mode, the frequency of the A1 mode can be
expressed by equation [25],
(1)
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2aCuS þ aFeS þ aSnS
n¼ (2)
MS
where aX-VI (i.e. X ¼ Cu, Fe, Sn and VI ¼ S) are the bond-stretching
force constants which depend on the interaction between the
nearest neighbors, MS is the mass of S-anion. In addition, the bond-
stretching force constants aX-VI rely on the bond length of the
nearest neighbor cation-anion, and the relationship between the
bond-stretching force constants and the bond length is obtained
from the formula: a ¼ Adn [26], where A and n are constants, and
d is the bond length. According to the discussion of XRD part as
shown in Fig. 2(b), the cell volume of CFTS is shrinkage with the
heating rates vary from 10 to 40  C/min corresponds to the
decreasing value of bond length. Therefore, in terms of the above
formula, the bond-stretching force constants of CFTS will be
decrease with the decreasing heating rate, and then the A1 mode of
CFTS shows a red shift phenomenon in consideration of the Eq. (2).
In order to confirm the elemental oxidation states for the as-
obtained CFTS, XPS measurement was employed and sample
(S20) with pure phase was identified as the test object as shown in
Fig. 4. Fig. 4(a) shows the Cu binding energy peaks which located at
 X. Meng et al. / Journal of Alloys and Compounds 680 (2016) 446e451
Fig. 4. XPS analysis of Cu2FeSnS4 thin film sulfurized under 20  C/min: (a) Cu 2p; (b) Fe
2p; (c) Sn 3d and (d) S 2p.
931.5 and 952.1 eV corresponding to the 2p3/2 and 2p1/2 states,
respectively, and a peak splitting of 20.6 eV indicating a Cu(I)
configuration. The typical Fe 2p3/2 and 2p1/2 peaks appeared at
712.0 and 725.3 eV, respectively, were given by Fig. 4(b), and the
splitting of 13.3 eV reveals a Fe(II) configuration. No other valence
states of Fe were discovered in the XPS measurement, which is
consistent with the result of XRD and Raman (i.e. pure phase). In
addition, the peaks located at 486.1 and 495.4 eV with peak split-
ting of 9.3 eV corresponding to the Sn(IV) 3d5/2 and 3d3/2 state
shown in Fig. 4(c). The S 2P core-level spectrum in Fig. 4(d) shows
two peaks located at 160.9 eV and 162.3 eV, i.e. S 2P3/2 and S 2P1/2,
severally, with the peak separation of 1.4 eV, which is consistent
with the 160e164 eV range of S in the sulfide phase. The values of
binding energy for all peaks further demonstrate the formation of
CFTS phase and it matches well with the reported binding energy
for CFTS [6].
Fig. 5 shows surface and section profile images of CFTS thin films
sulfurized by different heating rates. Clearly, when the heating rate
decreases from 40 to 20  C/min, the grain size of the CFTS thin film
becomes larger, and isolated grains with large size and well-defined
boundaries are formed, as evident in Fig. 5(a, c and e). This may be
due to the fact that the slower heating rate provides more enough
time and energy to guide the precursor alloying and crystallization,
in accordance with the results also obtained in Cu2ZnSnS4 and
Cu(In, Ga)Se2 thin films [27,28]. Nevertheless, further lower the
heating rate didn’t bring much improvement in thin film crystal-
line. The section profile images of CFTS (S40, S30, S20 and S10) thin
films are shown in Fig. 5(b, d, f and h), respectively. The thicknesses
of these four samples are all around 1.2 mm. Furthermore, it is found
that the increase in heating rate results in a growth in the fine-
grained nanocrystalline bottom layer, meanwhile, the grain size
of whole cross-section becomes smaller. The small grain size can
promote the contact area of boundaries resulting in the more ex-
istence of recombination centers and decreased carrier mobility,
which is harmful to improve the optoelectronic properties of
polycrystalline semiconductors, according to the classic grain-
boundary model concludes [29,30]. So as to confirm the distinc-
tion of chemical compositions between the large-grained and the
nanocrystalline, EDX has been utilized.
Table 1 shows the element composition values of CFTS thin films
determined from cross-sectional EDX measurement. From
449
composition analysis, it is found that the top, namely large-grained,
layer is slightly dependent on the heating rate of sulfurization, and
all sample’s composition close to the stoichiometric ratio 2:1:1:4.
However, thin films sulfurized at fast heating rate (S40 and S30) are
in S-poor and Sn-rich states as presented in the bottom-
composition, which partly verifies the above conjecture in XRD
analysis in Fig. 2(a), i.e. Cu2FeSn3S8 may exists in the bottom of the
thin film. When further slow down the heating rate (S20 and S10),
the element composition ratio is almost the same and all of them
are in close proximity to that of the top layer, indicating the heating
rate of 20  C/min is good enough for the films to be well crystal-
lized. Finally, we can draw conclusion that the optimal heating rate
is 20  C/min, considering cost-effectiveness and the corresponding
S20 thin film has the best crystal quality combined the results of
XRD, Raman and SEM.
The optical transmission spectra of CFTS thin films have been
measured for determination of the band gap (Eg) at various heating
rates of sulfurization as shown in Fig. 6. The corresponding Eg can
be estimated from the tangent lines in the plot of the Tauc’s law
ðahnÞ2 versus hn for the direct band-gap material. The optical ab-
sorption coefficient can be calculated by the equation:
a ¼ ðlnðTÞ=tÞ, where T is the transmittance of CFTS thin films and t
is the thickness of thin films, and hn is photo energy [31]. As pre-
sented in Fig. 6, the values of Eg are estimated as 1.47, 1.45, 1.44, and
1.42 eV for S10, S20, S30 and S40, respectively, which lie in the
range of the values of most previous reports [1e10] and close to the
ideal band gap (~1.4 eV) of photovoltaic semiconductors according
to the Shockley-Queisser limit [32]. On the basis of first-principles
calculation, the Eg evolution of multiternary semiconductors is
generally explained in terms of consequence of hybridizations in
valence band maximum (VBM) and conduction band minimum
(CBM) [2]. For CFTS, it has the crystal structural descendant from
CuInSe2 by the substitution of Fe and Sn for In and S for Se. Hence,
the CBM of CFTS should consist of Fe ns or Sn ns and S p orbitals and
the VBM of CFTS is a consequence of hybridization of Cu d and S p
orbital. Furthermore, the degree of hybridization depends on the
bond length of the nearest neighbor cation-anion, namely the de-
gree of hybridization increases with the shortening of the bond
length, and when the degree of hybridization increases, the cor-
responding band tail (VBM or CBM) will shifts into the band gap
[33]. As discussed in the XRD and Raman part, the value of bond
length decreases with the heating rate elevated from 10 to 40  C/
min, meaning VBM and CBM draw closer to one another gradually.
In order to further verify this conclusion, the variation tendency of
energy band have been simulated, as shown in the inset of Fig. 6,
using the software “wxAMPS” combined with the as-obtained de-
vice parameters in this paper [34,35]. The simulation result shows
that the above explanation for the decrease of Eg with the increases
of heat rate from 10 to 40  C/min is valid.
Devices with structure of Al:ZnO/ZnO/CdS/CFTS/Mo/glass as
shown in the inset of Fig. 7 were prepared to investigate the effect
of different heating rates on electrical properties of CFTS thin films,
and J-V characteristics have been employed under simulated AM 1.5
illumination as provided in Fig. 7. The Voc, Jsc and the fill factor (FF)
for S10, S20, S30 and S40 is 120, 129, 90 and 83 mV, and 2.54, 3.25,
1.96 and 1.77 mA/cm2, and 24.3%, 26.6%, 26.7% and 27.9%, corre-
sponding to the PCE of 0.07%, 0.11%, 0.05% and 0.04%, respectively. It
can be clearly seen that the devices based on CFTS thin films
derived from faster heating rate show relatively poor performance.
As discussed above shown in Figs. 2 and 5, faster heating rate (S30
and S40) during the CFTS grain growth process may induce the
more formation of structural defects and more effective recombi-
nation centers for photon-generated electrons, which would result
in significant cell leakage, corresponding to the sample with low Voc
and Jsc. However, the improvement of performance can be
450 X. Meng et al. / Journal of Alloys and Compounds 680 (2016) 446e451

Fig. 5. Surface and section profile images of Cu2FeSnS4 thin films sulfurized by different heating rates: (a, b) 40  C/min; (c, d) 30  C/min; (e, f) 20  C/min and (g, h) 40  C/min.

Table 1
Element composition values of Cu2FeSnS4 thin films determined from EDX analysis.

Sample ID Top Bottom

Cu/(Fe þ Sn) Fe/Sn S/Metals Cu/(Fe þ Sn) Fe/Sn S/metals

S40 1.02 1.02 1.01 0.84 0.73 0.83

S30 1.01 1.00 1.01 0.89 0.82 0.86
S20 1.04 0.99 1.00 0.93 0.98 0.91
S10 1.01 1.01 1.00 0.92 1.00 0.91

discovered with the heating rate decreases to 20  C/min, which

attribute to the modified crystallinity and the less strain in the S20.
As for lower heating rate condition, the device derived from S20
exhibits better performance than that of the device obtained from
S10 due to the fact that the increasing strain and enhanced
roughness caused by overgrowth of grains in S10 which would
decrease the shunt resistant and open circuit voltage. In general, Fig. 6. Plot of (ahv)2 vs hv for the estimation of the band gap energy of Cu2FeSnS4 thin
films. Inset shows the simulated variation tendency of energy band, where abscissa
the Voc and Jsc of these four devices with the above mentioned
represents the thickness of Cu2FeSnS4 thin films and ordinate is energy.
structure are relatively low may also due to the too thin absorbed
 X. Meng et al. / Journal of Alloys and Compounds 680 (2016) 446e451
Fig. 7. J-V characteristics of Cu2FeSnS4 thin films sulfurized using different heating
rates and inset is the cross-section SEM image of Cu2FeSnS4 device.
layer, as shown in Fig. 5, to absorb a significant portion of the
incident light and no metallic grid electrode was prepared on the
top of CFTS devices as shown in the inset of Fig. 7 [36].
4. Conclusions
In this paper, the effects of different heating rates on micro-
structure, morphology, composition and photology of quaternary
CFTS thin films obtained by sulfurization of the metallic layers have
been investigated. XRD patterns indicate faster heating rates during
the CFTS grain growth can induce the coexistence phase, bigger
strain and shrinking crystal cell in thin films. The results of SEM and
EDX indicate that the composition in the bottom of CFTS thin films
sulfurized under faster heating rate has S-poor and Sn-rich states
with an obvious bilayer structure, however, the quality of crystal-
lization improved significantly with the lower heating rate. The
optical transmission spectrum reveals that the VBM and the CBM of
CFTS draw closer to one another gradually with the increasing
heating rate, corresponding to the reducing band gap energy of
CFTS. Finally, as for CFTS device, the sample S20 shows a relatively
ideal performance with Voc ¼ 129 mV and Jsc ¼ 3.25 mA/cm2 which
have been enhanced 17.3% and 30.0%, respectively, compared to the
previous work. More work, including optimizes the sulfurization
parameters or adjusts the thickness and so on, should be done to
improve the electrical properties of CFTS thin films, but these above
results can help us have a deeper understanding for CFTS-system
materials.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (61474045), the State Key Basic Research
451
Program of China (2013CB922300).
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