Applied Surface Science 305 (2014) 506514

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Applied Surface Science

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

XPS analysis and structural and morphological characterization of

Cu2 ZnSnS4 thin lms grown by sequential evaporation
G. Gordillo a , C. Caldern a, , P. Bartolo-Prez b
a
b

Departamento de Fsica, Universidad Nacional de Colombia, Bogot, Colombia

Departamento de Fsica Aplicada, CINVESTAV-IPN, Mrida, Yuc., Mexico

a r t i c l e

i n f o

Article history:
Received 27 January 2014
Received in revised form 18 March 2014
Accepted 19 March 2014
Available online 27 March 2014
Keywords:
Thin lms
Cu2 ZnSnS4
Raman
XRD
XPS

a b s t r a c t
This work describes a procedure to grow single phase Cu2 ZnSnS4 (CZTS) thin lms with tetragonalkesterite type structure, through sequential evaporation of the elemental metallic precursors under
sulphur vapor supplied from an effusion cell. X-ray diffraction analysis (XRD) is mostly used for phase
identication but cannot clearly distinguish the formation of secondary phases such as Cu2 SnS3 (CTS)
because both compounds have the same diffraction pattern; therefore the use of a complementary
technique is needed. Raman scattering analysis was used to distinguish these phases.
The inuence of the preparation conditions on the morphology and phases present in CZTS thin lms
were investigated through measurements of scanning electron microscopy (SEM) and XRD, respectively.
From transmittance measurements, the energy band gap of the CZTS lms was estimated to be around
1.45 eV. The limitation of XRD to identify some of the remaining phases after the growth process are
investigated and the results of Raman analysis on the phases formed in samples grown by this method
are presented. Further, the inuence of the preparation conditions on the homogeneity of the chemical
composition in the volume was studied by X-ray photoelectron spectroscopy (XPS) analysis.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Recent growth of the thin-lm PV industry and champion cell
efciencies of 20.3% for Cu(In,Ga)Se2 [1], demonstrate that thin lm
photovoltaic (PV) is becoming a viable option for large-scale power
generation. However, due to the limited availability of In, some
concern exists that high material expenses restrict the capacity to
lower production costs, especially in view of the desired industrial
mass production. Kesterites used as thin lm solar cell absorbers
have attracted much attention in the past years [2] due to the
fact that this material has several promising attributes for efcient, inexpensive solar cells made from abundant and nontoxic
elements.
A variety of routes have been undertaken for thin-lm deposition. These include vacuum and solution based deposition
approaches. For each of these deposition approaches one key barrier toward a reliable process is the incompletely understood nature

Corresponding author at: Cra. 30 No. 45-03, Bogot, Colombia.

Tel.: +57 1 3165000x13017; fax: +57 1 3165135.
E-mail address: clcalderont@unal.edu.co (C. Caldern).
http://dx.doi.org/10.1016/j.apsusc.2014.03.124
0169-4332/ 2014 Elsevier B.V. All rights reserved.

of the CuZnSnS phase diagram and control over the phase progression during lm formation [3], which presents a challenge
for preparing single phase lms. A second common limitation
generally encountered during process optimization involves the
volatility upon heating of Sn materials [4], which makes compositional control a challenge during lm fabrication. Despite
these challenges, reasonably successful lm deposition and device
fabrication has been demonstrated for both vacuum and solutionbased deposition approaches. Several groups have reported the
fabrication of CZTS thin lms using a variety of methods such
as sulphurization of stacked metallic layers [5], rf sputtering [6]
and co-evaporation [7]. The highest efciency of 8.4% has been
achieved using the co-evaporation technique [8], demonstrating the potential of CZTS to be effective photovoltaic absorber
layer.
In this work, we report on studies related to the growth
of single phase Cu2 ZnSnS4 thin lms using a procedure consisting in the sequential evaporation of the elemental metallic
precursors in presence of elemental sulphur. The structural and
morphological properties of CZTS thin lms have been investigated through XRD, Raman spectrometry and SEM measurements.
The chemical composition homogeneity was also studied by XPS
analysis.

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507

Fig. 1. Routine to grow single phase Cu2 ZnSnS4 thin lms, following the Cu/Sn/Zn
sequence.

2. Materials and methods

CZTS thin lms were prepared in a physical vapour deposition
(PVD) system equipped with a turbomolecular pump that allows
evaporation at pressures of the order of 2 105 mbar and two
tungsten boats to evaporate Cu and Sn, and two effusion cells used
to evaporate Zn and S, respectively. The temperatures of each effusion cell are controlled using PID temperature controllers and the
deposition rates of both Cu and Sn were monitored with a Maxtec
thickness monitor model TM-400 that uses a quartz oscillator as
sensor.
To grow CZTS lms with kesterite type structure a procedure
was used, consisting in the sequential evaporation of the metallic
precursors in presence of elemental sulphur evaporated from an
effusion cell that provides uncracked sulphur ux. A broad number
of samples were deposited under different sequences (Cu/Zn/Sn,
Cu/Sn/Zn, Sn/Cu/Zn, Sn/Zn/Cu, Zn/Cu/Sn, Zn/Sn/Cu) varying the
main deposition parameters in a wide range. XRD measurements
carried out to each one of the prepared samples, allowed us to nd
the sequence and deposition parameters leading to the growth of
single phase Cu2 ZnSnS4 thin lms. This study revealed that single
phase CZTS lms can be obtained evaporating the metallic precursors under the Cu/Sn/Zn sequence at temperatures as those shown
in Fig. 1. Samples prepared using any other sequence and/or deposition routines different to those displayed in Fig. 1 grow in general
with a mixture of the CZTS phase and secondary phases.
The lm thickness was determined using a Veeco Dektak 150
surface proler and SEM measurements were carried out with a
Jeol JSM-7600F electron microscope in high vacuum mode. Further
characterization involved X-ray diffraction on a Shimadzu-6000
diffractometer and Raman spectroscopy on a Horiba Jobin Yvon
micro-Raman Spectrometer LabRamHR in backscattering conguration with a DPSS laser of 473 nm, 20 mW focused with a 50
objective. The elemental composition analysis of the CZTS thin lms
was measured using an X-ray photoelectron spectrometer K-Alpha
Thermo Scientic.
3. Results and discussion
3.1. Structural properties
The diffraction patterns displayed in Fig. 2 correspond to samples prepared under the sequences Cu/Zn/Sn, Cu/Sn/Zn, Sn/Cu/Zn,
Sn/Zn/Cu, Zn/Cu/Sn and Zn/Sn/Cu, using the same evaporated mass
of Cu, Sn and Zn. It is observed that in general, the diffraction
patterns of the studied samples include reections associated to
both the CZTS phase plus other secondary phases. However, samples deposited under the sequences Cu/Sn/Zn and Zn/Sn/Cu present

Fig. 2. XRD pattern of CZTS thin lms deposited varying the sequence in which
the metallic precursors are evaporated (Cu/Sn/Zn, Cu/Zn/Sn, Sn/Cu/Zn, Sn/Zn/Cu,
Zn/Cu/Sn, Zn/Sn/Cu).

reections corresponding only to the kesterite type Cu2 ZnSnS4

phase oriented preferentially along the (1 1 2) plane (PDF card #00026-0575). The samples prepared using sequences different to the
previously mentioned, present additional reections corresponding to secondary phases such as: ZnO, CuS, SnS2 , Cu0.999 Sn0.501 S1.5 .
Since some binary and ternary compounds that may be present
in the samples studied show reections at the same angles than
those of the reections corresponding to the Cu2 ZnSnS4 phase, is
useful to compare the XRD spectrum of the CZTS lm with those
of thin lms of the binary and ternary compounds, to differentiate with a greater degree of precision the reections associated
to Cu2 ZnSnS4 from those corresponding to secondary phases that
may be present. Fig. 3 compares the XRD spectrum of a sample
containing just the Cu2 ZnSnS4 phase with those of thin lms of copper sulphide, zinc sulphide and tin sulphide prepared separately by
coevaporation of its elemental precursors, as well as with that of a
ternary compound grown by sequential evaporation of copper sulphide and tin sulphide followed by annealing at 550 C in sulphur
ambient.
The following facts can be highlighted from the results of Fig. 3:
(i) Sulphide thin lms of Cu, Sn and Zn deposited separately under
the same conditions, used during the growth of the compound

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Fig. 3. Comparison of the XRD spectrum of a sample deposited on molybdenum

containing just the Cu2 ZnSnS4 phase, with those of thin lms of CuS, SnS and ZnS
deposited on glass by co evaporation of its elemental precursors, as well as with that
of a CTS lm grown by sequential evaporation of CuS and SnS.

Cu2 ZnSnS4 , grow in the CuS (PDF 00-0006-0464), SnS (PDF 01079-2193) and ZnS (PDF 00-001-1280) phases, respectively.
(ii) Evaporation of Cu at 550 C in presence of elemental sulfur followed by co-evaporation of Sn and S at 250 C and subsequent
annealing at 550 C results in the formation of Cu2 SnS3 (PDF
01-089-4714). The subsequent co-evaporation of Zn and S at
550 C converts the ternary compounds formed in the previous stage in Cu2 ZnSnS4 (PDF 00-026-0575), according to the
following reactions.
2CuS + SnS Cu2 SnS3
Cu2 SnS3 + ZnS Cu2 ZnSnS4
(iii) The XRD pattern of the ternary CTS and quaternary CZTS
compounds differ very little from each other. This result indicates that XRD measurements do not allow to know precisely
whether the observed reections in the diffractograms correspond to Cu2 ZnSnS4 or Cu2 SnS3 and thus the use of a
complementary technique is needed.
(iv) Reexions corresponding to CuS and SnS phases are easy
to identify when are present in a phase mixture with CZTS
because its diffraction peaks are clearly distinct from the CZTS
ones. Regarding ZnS, the identication of this phase is very difcult because the most probable ZnS phase to form is the cubic
one with a lattice parameter a of 5.410 A that differs little from
that of CZTS; consequently the XRD peaks of ZnS are very close
to those of the CZTS as is shown in Fig. 3.
A ternary compound can be formed during the growth of
CZTS, such as tetragonal Cu2 SnS3 , cubic Cu2 SnS3 and orthorhombic
Cu3 SnS4 [9,10]. From these, only the orthorhombic Cu3 SnS4 is easy
to identify using XRD. The tetragonal and the cubic have the same
problem as ZnS. The peak proximity for CTZ and CZTS compounds
are also displayed in Fig. 3.
Besides X-ray analysis, Raman spectroscopy study was performed to distinguish the CZTS phase of secondary phases that may
be present in these samples. Fig. 4 compares the Raman spectrum
of a sample grown under the sequence Cu/Sn/Zn (sample O6) with
that of a sample grown under the sequence Zn/Sn/Cu (sample E23).
The Raman spectrum of a CTS sample grown under the sequence
Cu/Sn (sample L5) is also plotted in Fig. 4.

Fig. 4. Raman spectra of CTS (sample L5) and CZTS lms grown under sequences
Cu/Sn/Zn (sample O6) and Zn/Sn/Cu (sample E23).

Raman spectrum of sample O6 shows a single peak at 339 cm1

which has been attributed to Cu2 ZnSnS4 [11]. This peak arises from
the A1 vibrational mode of the lattice, where the group VI atom (S)
vibrates while the rest of atoms remain xed [12]. Raman spectrum
of sample CZTS-E23 shows a strong peak at 317 cm 1 which has
been attributed to orthorhombic Cu3 SnS4 [13] and two additional
small peaks at 339 cm1 and 475 cm1 that have been attributed
to Cu2 ZnSnS4 and Cu2x S, respectively [13]. Sample CTS-L5 has
only a Raman peak at 305 cm1 which has been attributed to cubic
Cu2 SnS3 [13].
It is observed that the results of the Raman analysis are in
agreement with those obtained from XRD measurements only for
CZTS samples deposited under the sequence Cu/Sn/Zn. For samples deposited under the sequence Zn/Sn/Cu the Raman results
do not agree with those obtained by XRD; Raman analysis reveals
that these samples grow with a mixture of the phases Cu3 SnS4
and Cu2 ZnSnS4 , being much larger the contribution of the Cu3 SnS4
phase, whereas the XRD pattern of samples grown under the

Fig. 5. Raman spectra of CZTS thin lms with different Cu/(Sn + Zn) (M) and Zn/(Sn)
(N) ratios.

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509

Fig. 7. SEM images of surfaces for CZTS thin lms deposited under different conditions: (a) Cu/Sn/Zn sequence, M = 0.36, N = 2, (b) Cu/Sn/Zn sequence, M = 0.24, N = 2
and (c) Zn/Sn/Cu sequence, M = 0.36, N = 2.
Fig. 6. (a) Comparison of the transmittance of a typical Cu2 ZnSnS4 thin lms with
those of thin lms of CuS, SnS, ZnS and Cu2 SnS3 and (b) Plot of (h)2 vs h for
Cu2 ZnSnS4 thin lms prepared under the sequence Cu/Sn/Zn.

sequence Zn/Sn/Cu exhibit only reections corresponding to the

Cu2 ZnSnS4 phase. Based on the analysis carried out on CZTS thin
lms deposited by sequential evaporation, using Raman spectroscopy and XRD, it can be concluded that single phase Cu2 ZnSnS4
thin lms can be grown using the sequence Cu/Sn/Zn. It is worth
mentioning that in each studied sample (of about 1 cm2 ) Raman
measurements were made at four different points. The results
revealed that the obtained spectra differ little from each other, indicating that the formation of single phase occurs over a wide area.
As the Raman measurements were made with a laser of 473 nm
(20 mW) that only excites the near-surface region, can not be said
of Raman measurements that the formation of single phase occurs

throughout the volume. However, the atomic concentrations of Zn,

Cu, Sn and S determined from high-resolution XPS core level spectra
integrated peak areas at three different depths, indicated that using
an optimal relationship between the mass of evaporated precursors
and optimized deposition conditions allows depositing CZTS lms
with both, atomic composition close to the stoichiometric one and
reasonably good homogeneity in chemical composition over the
entire volume (see Fig. 10).
Samples deposited under the sequence Zn/Sn/Cu grow predominantly in the Cu3 SnS4 phase, due to the fact that most of the
zinc evaporated onto the glass substrate at 550 C is re-evaporated
resulting in a deciency of Zn and thus to the preferential formation
of the ternary compound.
The inuence of the composition ratio on the Raman spectra of
CZTS thin lms grown under the sequence Cu/Sn/Zn was studied.

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Fig. 8. XPS Spectra of CZTS thin lms grown under the Zn/Sn/Cu sequence (sample E23): (a) typical survey spectra of CZTS thin lms. Survey scan and high resolution core
level spectra measured at three different depths: (b) S 2p, (c) Sn 3d, (d) Cu 2p and (e) Zn 2p.

For this, CZTS samples were prepared varying the ratio of evaporated mass of Cu/(Sn + Zn) (=M) between 0.24 and 0.42 and the
ratio Zn/Sn (=N) between 1.6 and 2.4. In Fig. 5 are compared Raman
spectra of CZTS thin lms prepared with different values of M and
N. This study reveals that all the samples show a single peak which
moves when the composition of the CZTS lms is varied. The sample O6 deposited using compositions ratios M and N of 0.36 and
2, respectively, present a Raman peak at 339 cm1 ; however, the
position peak of samples prepared with composition ratios M and
N above and below of the composition used for the O6 sample is
shifted to lower frequencies apparently caused by some strain produced by compressive stress, which some authors attribute to a
gradient in strain, originated by a gradient of crystal quality in the
layers [14,15]. The variation of the concentration ratio of Cu and Zn

in CZTS lms is frequently used to obtain CZTS lms with electrical

conductivity suitable for use as absorbent layer in solar cells.
3.2. Optical properties
The optical properties of CZTS thin lms were studied by optical
transmission and reection measurements at room temperature.
Fig. 6 shows the spectral transmittance of a typical Cu2 ZnSnS4 thin
lm deposited under the sequence Cu/Sn/Zn as well as the transmittance of thin lms of its binary precursors (CuS, SnS, ZnS) separately
deposited by co-evaporation of its elemental precursors; the transmittance of a Cu2 SnS3 lm grown by sequential evaporation of CuS
and SnS followed by annealing at 550 C in sulphur ambient is also
displayed in Fig. 6.

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511

Fig. 9. XPS spectra of CZTS thin lms grown under the Cu/Sn/Zn sequences (sample O6): (a) typical survey spectra of CZTS thin lms. Survey scan and high resolution core
level spectra measured at three different depths: (b) S 2p, (c) Sn 3d, (d) Cu 2p and (e) Zn 2p.

It is observed that the CuS and CTS lms exhibit low transmittance values, indicating that these lms grow with a high density
of native defects (vacancies, interstitial and antisite). These defects
generate absorption centers within the energy gap which contribute to the photon absorption. In particular, the transmittance of
the CuS lms decreases strongly in the NIR region apparently due
to the formation of a very high density of shallow defects. It is also
observed that the transmittance curve of the CZTS lm has a small
slope: this behavior seems to be caused by absorption of photons
in deep centers generated by structural defects.
The optical band gap of a 800 nm thick CZTS thin lm deposited
under the sequence Cu/Sn/Zn was obtained using the following
equation [16]:
(h) = A(h Eg )

(1)

where is the optical absorption coefcient, A is a constant, Eg

is the optical band gap and n = 1/2 for direct transition. The optical

band gap was obtained by extrapolating the linear region of the plot
(h)2 vs h. was determined from the measured transmittance
(T) and reectance (R) using the formula [16]:

1
(1 R)2
ln
T
d


(2)

where d is the thickness of the lm. The absorption coefcient of the

CZTS lm is larger than 104 cm1 in the visible region. The plot of
(h)2 vs h for CZTS thin lms is presented in Fig. 6b. Therefore the
estimated optical band gaps of the CZTS thin lms is 1.45 eV, which
is in agreement with the previously reported values of 1.41.6 eV
[1719]. The study also revealed that there is a decrease in optical
band gap with increasing Cu/(Zn + Sn) ratio of the CZTS thin lm.
This is in accordance with previous reports [19,20].

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G. Gordillo et al. / Applied Surface Science 305 (2014) 506514

Fig. 10. Atomic concentration at three different depths of CZTS lms grown under the sequence Cu/Sn/Zn using different composition ratios.

3.3. Morphological characterization

The morphology of the CZTS lms was characterized through
SEM. Fig. 7 shows the surface SEM micrograph of samples O6
and E23 prepared under the sequences Cu/Sn/Zn and Zn/Sn/Cu,
respectively, using the same Cu/(Sn + Zn) ratio of 0.36; the SEM
micrograph of sample E25 prepared under the sequence Cu/Sn/Zn
using a Cu/(Sn + Zn) ratio of 0.24 is also displayed in Fig. 7. The
results show that, in general, the CZTS lms consist of compact
grain structures, free of voids with sub-micron size, which is significantly affected by the sequence in which these are deposited. The

samples prepared under the sequence Cu/Sn/Zn (Fig. 7a and b) tend

to grow with grains grouped together in clusters of different size,
while the samples prepared under the sequence Zn/Sn/Cu (Fig. 7c)
show smooth surfaces and closely packed small grains without any
voids. The different morphology observed in CZTS lms deposited
under the sequence Zn/Sn/Cu is due to the fact that these samples
grow with a mixture of the CZTS and CTS phases, the latter being
predominant.
It was also found that in the range of composition studied, the grain size becomes larger with increasing Cu/(Zn + Sn)
ratio. Samples deposited with a Cu/(Sn + Zn) ratio around 0.36

G. Gordillo et al. / Applied Surface Science 305 (2014) 506514

are known to have good crystallinity and a single-phase kesterite

structure.
3.4. XPS analysis
The elemental composition homogeneity in the volume of CZTS
lms grown under different sequences and composition ratios was
studied through XPS measurements carried out at three different
depths (sputter time of 3, 6 and 9 min, respectively). Figs. 8a and 9a
show typical survey spectra of CZTS thin lms deposited under
both, Zn/Sn/Cu (sample E23) and Cu/Sn/Zn (sample O6) sequences.
It is observed that besides the C 1s peak visible at about 284.6 eV,
peaks corresponding to Cu, Zn, Sn and S are identied in both XPS
spectra. High-resolution core level spectra were recorded for the Cu
2p, Zn 2p, Sn 3d and the S 2p regions in order to determine the oxidation state and elemental composition (see Figs. 8be and 9be).
Figs. 8b and 9b show the S 2p core level spectrum which
exhibit two peaks 2p3/2 and 2p1/2 with binding energy at 161.9 and
162.8 eV and a peak splitting of 0.9 eV, which are consistent with
the 160164 eV range expected for S in sulde phases [21,22]. The
Sn 3d5/2 and Sn 3d3/2 peaks shown in Figs. 8c and 9c are present
at 486.4 and 494.5 eV, respectively, with a separation of 8.1 eV,
which conrms Sn(IV) [21,22]. Figs. 8d and 9d show the Cu 2p core
level spectra which exhibit binding energy for the Cu 2p3/2 and Cu
2p1/2 peaks at 932.8 and 952.3 eV, respectively, and a peak splitting
of 19.5 eV, leading to conclude that copper is in the +1 oxidation
state indicating formation of Cu(I) [21,22]. Fig. 9e shows the Zn 2p
core level spectrum of a CZTS lm deposited under the sequence
Cu/Sn/Zn; peaks Zn 2p3/2 and 2p1/2 visible at binding energies of
1021.8 and 1044.6 eV with a peak separation of 22.8 eV suggest
the presence of zinc(II) [21,22]. Fig. 8e shows the Zn 2p core level
spectrum of a CZTS lm deposited under the sequence Zn/Sn/Cu;
this types of samples exhibit only the peak Zn 2p3/2 at 1021.9 eV
being its peak area much smaller than that observed in samples
deposited under the sequence Cu/Sn/Zn, indicating that these samples grow very Zn decient; this unusual result is caused by the
fact that these samples grow predominantly in the Cu2 SnS3 phase
mixed with a small amount of CZTS, as was proven through Raman
measurements (see Fig. 4).
Results depicted in Figs. 8 and 9 show that the peak area of the
core level spectra for elements Cu, Zn, Sn, and S, measured at different depths differ from each other, indicating that the samples
studied are inhomogeneous in chemical composition, being the
inhomogeneity of the sample E23 signicantly greater.
The relative atomic concentrations of Zn, Cu, Sn and S were also
determined from high-resolution XPS core level spectra integrated
peak areas. In Fig. 10 are plotted the atomic concentrations at three
different depths (sputter time of 3, 6 and 9 min, respectively) of
CZTS lms grown under the Cu/Sn/Zn, using different composition
ratios M and N. This study shows that in general the CZTS lms
exhibit inhomogeneity in elemental composition throughout the
volume and it depends on the mass ratio of precursors evaporated.
It was also found that the CZTS lms tend to grow with a stoichiometry inuenced by the mass ratio of the precursors evaporated; the
best result in both, homogeneity and stoichiometry was obtained
with the sample O6 prepared using composition ratios M and N of
0.36 and 2, respectively. The stoichiometry of this sample obtained
by averaging the atomic compositions measured in the three depths
is about S:Sn:Zn:Cu = 4.07:0.97:0.95:2.03.
4. Conclusions
CZTS thin lms with tetragonal-kesterite type structure were
grown using a procedure based on sequential evaporation of the
elemental metallic precursors under sulphur vapour supplied from

513

an effusion cell. XRD and Raman spectroscopy studies gave evidence of the formation of single phase CZTS lms with kesterite
structure using optimized growth parameters. However, the composition ratio and sequence in which the metallic precursors are
evaporated, signicantly affects the phase and the structural and
morphological properties of the CZTS lms. From Raman measurements, evidence was found that, CZTS lms prepared with
composition ratios M and N different than 0.36 and 2, respectively,
present some strain associated to compressive stress, which have
been attributed to a gradient in strain, due to a gradient of crystal quality. Study of surface morphology of CZTS lms made with
SEM revealed that, in general, the CZTS lms consist of compact
grain structures free of voids with sub-micron sizes, which are signicantly affected by the sequence in which these are deposited.
The samples prepared under the sequence Cu/Sn/Zn tend to grow
with grains grouped together in clusters of different sizes, while
the samples prepared under the sequence Zn/Sn/Cu show smooth
surfaces and closely packed small grains without any voids.
Relative atomic concentrations of Zn, Cu, Sn and S, determined
from high-resolution XPS core level spectra integrated peak areas,
revealed that, in general, the CZTS lms exhibit inhomogeneity in
both stoichiometry and elemental composition; however, it was
possible to nd conditions for the preparation of CZTS lms with
reasonable homogeneity in chemical composition and a stoichiometry of S:Sn:Zn:Cu = 4.07:0.97:0.95:2.03 which is close to that of
the Cu2 ZnSnS4 phase. The results also revealed that the Cu2 ZnSnS4
lms are known to get p-type conductivity and an energy band
gap of about 1.45 eV, indicating that this compound is suitable to
perform as absorbent layer in thin lm solar cells.
Acknowledgements
This paper was supported by Colciencias (Cont. #038-2013),
DIB-Universidad Nacional de Colombia, FOMIX-Yucatn 2008108160 and CONACYT LAB-2009-01 # 123913. The authors would
like to thank Eng. Wilian Cauich for his assistance with the XPS and
SEM measurements.
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