28th European Photovoltaic Solar Energy Conference and Exhibition

CZTS THIN FILMS GROWN USING A NOVEL SOLUTION BASED DEPOSITION APPROACH

R. Becerra1, J. M. Correa1, J.S. Oyola2, M. Botero3 and G. Gordillo2

1
Departamento de Química, Universidad Nacional de Colombia, Bogotá, Colombia
2
Departamento de Física, Universidad Nacional de Colombia, Bogotá, Colombia
3
Facultad de Ingeniería Ambiental, Universidad Santo Tomas, Bogotá, Colombia

ABSTRACT: This paper present a method for growing thin films of Cu2ZnSnS4 (CZTS) using a new solution-based
chemical route consisting in sequential deposition of Cu2SnS3 (CTS) and ZnS films followed by annealing in sulfur
atmosphere. The CTS compound is prepared in one step using a novel procedure consisting of simultaneous
precipitation of Cu2-xS and SnS performed by diffusion membranes assisted CBD technique. Diffusion membranes
are used to optimize the kinetic growth through a moderate control of the release of metal into the solution by
osmosis. The conditions in terms of concentration of metal species, sulphide anion and temperature required for the
precipitation of the Cu2SnS3 compound were determined through a study of chemical equilibrium of the systems
(SnCl2 + Na3C6H5O7·2H2O) , CuCl2 and Na2S2O3·5H2O. These conditions were obtained solving the chemical
equilibrium equation using the Visual MINTEQ 3.0 package, supported on the program MINTEQA2.

X-ray diffraction (XRD) and Raman spectroscopy were used to characterize the structural properties of the CZTS
films. Optical and morphological properties were also studied by spectral transmittance, AFM (Atomic Force
Microscopy) and SEM (Scanning Electron Microscopy) measurements. XRD and Raman measurements showed that
films deposited using this new route present only the Cu2ZnSnS4 phase.
Keywords: Thin films, Cu2ZnSnS4, diffusion membranes assisted CBD, chemical equilibrium, optical and structural
properties.

1 INTRODUCTION determined from XRD, Raman spectroscopy,

Thin film photovoltaics 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. Cu2ZnSnS4 has been
considered as the alternative absorber layer to
Cu(In,Ga)Se2 due to its earth abundant and
environmental friendly constituents, optimal direct band
gap of 1.45eV and high absorption coefficient in the
visible range [1,2]. In recent years, great efforts have
been focusing on the preparation of CZTS thin films and
exploration their potential application in thin film solar
cells [2-4].
A variety of routes have been undertaken for thin-
film deposition. These include vacuum and solution
based deposition approaches. For each of these
deposition routes, the compositional control and growth
of single phase CZTS films are the main barriers toward
a reliable process. These barriers are attributed to the
incompletely understood nature of the Cu–Zn–Sn–S
phase diagram [5] and to the volatility upon heating of Sn
materials [6]. Despite these limitations reasonably
successful film deposition and device fabrication has
been demonstrated for both vacuum and solution-based
deposition approaches. Cu2ZnSnSe4 and Cu2ZnSn(S,Se)4-
based solar cells using hydrazine-based solution process
have already reached an energy conversion efficiency as
high as 11.1 % [4], demonstrating the effectiveness of the
solution process in CZTSSe-based solar cells.
In this work, we propose a novel solution based
chemical route for preparation of CZTS thin film from
Cu2SnS3 and ZnS precursors, where the Cu2SnS3
compound was formed by co-precipitation of Cu2-xS and
SnS performed by diffusion membranes assisted CBD
technique. Further, results are reported related to
structural, optical and morphological properties
transmission, SEM and AFM measurements. These are
compared with those of reference CZTS films prepared
by sequential evaporation of metallic precursors in
presence of elemental sulfur.
2 EXPERIMENTAL
CZTS thin films were prepared using a novel solution
based deposition technique; this consist in sequential
deposition of Cu2SnS3 and ZnS thin films followed by
annealing at 450 C in nitrogen atmosphere.
The ZnS films are deposited by conventional CBD
method, whereas the Cu2SnS3 compound was prepared in
one step using a novel procedure consisted of
simultaneous precipitation of Cu2-xS and SnS. The co-
precipitation of Cu2-xS and SnS was achieved introducing
initially aqueous solutions of (SnCl2·2H2O +
Na3C6H5O7·2H2O) and (CuCl2·2H2O) into two spatially
separate diffusion membranes and then, both membranes
are introduced into a solution containing (Na2S2O3·5H2O
+ glucose) dissolved in water. The role of the diffusion
membranes is to optimize the kinetic growth through a
moderate control of releasing metal into the solution by
osmosis and glucose is added to promote the reduction of
Cu2+ to Cu+. The sodium citrate act as complexing agent
and as a pH regulator.
Reference parameter values for the reagents
constituting the work solution (concentration of metal
species, sulfide anion and temperature), required to
obtain the Cu2SnS3 compound from co-precipitation of
Cu2-xS and SnS were found by means of a study of the
equilibrium conditions of the systems (SnCl2 +
Na3C6H5O7·2H2O) , CuCl2 and Na2S2O3·5H2O. For this
we constructed a matrix of concentrations and
equilibrium constants representing the chemical
equilibrium equations that define each system. The
concentrations and equilibrium constants allow building

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chemical equilibrium equations present in the system

which were solved using the Visual MINTEQ 3.0
package, supported on the program MINTEQA2. Using
as input data the values determined through the solution
of the chemical equilibrium equation, a parameter study
was done for finding suitable conditions to grow the
compound CTS. The following chemical bath
composition led to good results: [CuCl2]=50mM,
[SnCl2]=100mM, [Na2S2O3]=250mM, [glucose]=345mM
and [Na3C6H5O7]=237mM. During the deposition the
bath temperature was maintained at 70 oC and the final
solution pH around 5.
The ZnS thin films were grown in a solution
containing thiourea (CSN2H4) as sources of S2- ions, zinc
acetate (ZnC4H6O4·2H2O) as source of Zn2+ ions, sodium
citrate (Na3C6H5O7·2H2O) as complexing agent and
ammonia (NH3) for pH adjustment. The following
chemical bath composition led to good results: [zinc
acetate]=150mM; [thiourea]=150mM; [sodium
citrate]=30mM. During the deposition the bath
temperature was maintained at 80C and the solution pH
around 10.
The transmittance measurements were done using a
Varian–Cary 5000 spectrophotometer and the film
thickness was determined using a Veeco Dektak 150
surface profiler. Further characterization involved X-ray
diffraction on a Shimadzu-6000 diffractometer and
Raman spectroscopy on a Horiba JobinYvon micro-
Raman Spectrometer LabRamHR in backscattering
configuration with a DPSS laser of 473 nm, 20 mW
focused with a 50X objective. Morphological studies
were also done through AFM and SEM measurements
carried out with a PSI AP-0100 Scanning Probe
Microscope and a FEI-Nova nanosem 200 microscope
respectively.
The optical, structural and morphological properties
of the CBD grown CZTS samples were compared with
those of reference CZTS films prepared by sequential
deposition of CuS/SnS/ZnS thin films grown by co-
evaporation of the elemental precursors [see details in
Ref. 7].
3 RESULTS AND DISCUSSION
3.1 Optical properties
In Fig.1 are compared transmission spectra of CZTS
and CTS films deposited by sequential evaporation with
those of samples prepared by sequential deposition of
Cu2SnS3 and ZnS films using the CBD method. The
results of Fig. 1 show that both, the CZTS and CTS films
exhibit low transmittance values. This behavior is
apparently caused by the presence of a high density of
native defects (vacancies, interstitial and anti-site), which
generate absorption centers within the energy gap that
contribute to the photon absorption mainly in the VIS and
NIR region.
Figure 1: Comparison of the spectral transmittance of
CZTS and CTS thin films deposited by sequential
evaporation with those of samples deposited using a
solution based chemical route.
The absorption coefficient α of the reference CZTS
film prepared by evaporation was determined from
spectral transmittance and reflectance measurements and
using the following relationship:
T() =[1-R()]exp(-d) (1)
Where T() is the spectral transmittance, R() the
spectral reflectance and d the sample thickness.
The CZTS thin films we have grown in this work by
evaporation and by CBD have a value of Eg = 1.42 eV
and 1,5 eV respectivelly, indicating that they are suitable
for use as the absorber layer in solar cell. These values
coincide with those reported in the literature [8].
3.2 Structural characterization
In this work we were able to prepare CZTS thin films
containing only the Cu2ZnSnS4 phase using both, vacuum
and solution based deposition methods. XRD and Raman
spectroscopy measurements confirmed the formation of
single phase Cu2ZnSnS4 films in samples prepared by
both methods (see Fig. 2 and 3).
Fig. 2 compares the XRD pattern of a reference
CZTS thin films prepared by evaporation with the
diffractogram of a sample grown by CBD.
The XRD measurements reveal that CZTS thin films
grown by both methods present reflexions corresponding
only to the kesterite type Cu2ZnSnS4 phase oriented
preferentially along the (112) plane (AMC card #99-100-
5143). It is also observed that the FWHM (full width at
half maximum) of the peaks corresponding to thin films
of CZTS grown by CBD is less than that of samples
deposited by evaporation, indicating that these last have
poorer crystallographic quality.
Besides X-ray analysis, Raman spectroscopy
measurements were done on thin films of CZTS prepared
by both, CBD and sequential evaporation. In Fig. 3 the
Raman spectra of a CZTS grown by sequential

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evaporation (Fig. 3c) is compared with those of samples
prepared by CBD under: a) the sequence Cu2SnS3/ZnS +
annealing at 450°C and b) the sequence
Cu2SnS3/SnS/ZnS + annealing at 450°C.
neighborhood. The shift of the peak toward a higher
value of wave length could be associated with an
enrichment of S. This behavior has been observed by
other authors through study of [A1] Raman mode
wavenumber dependency on the sulfur concentration in
Cu2ZnSn(SexS1−x)4 solid solutions [11].

3.3 Morphological characterization

Fig. 4 compares AFM and SEM images of CZTS thin
films prepared by sequential deposition of CBD grown
CTS and ZnS films with those prepared by sequential
deposition of CuS, SnS and ZnS grown by co-evaporation
of elemental precursors.

a) AFM
CZTS(CBD)

Figure 2. Comparison of XRD pattern of a reference

CZTS thin film prepared by evaporation with that of a
sample prepared by CBD.

b) AFM
CZTS (Evap.)

Figure 3: Raman spectra of CZTS thin films: a) grown

by CBD under the sequence Cu2SnS3/ZnS + annealing at
450C, b) grown by CBD under the sequence
c) SEM
Cu2SnS3/SnS/ZnS + annealing at 450C c) grown by
CZTS(CBD)
sequential evaporation

It is observed that in general the Raman spectra of the

CZTS films show a single peak around 334 cm−1 which
has been attributed to the Cu2ZnSnS4 phase [9]. This
peak arises from the [A1] vibration mode of the lattice,
where the group VI atom (S) vibrate while the rest of
atoms remain fixed. However the Raman spectrum of
CZTS films deposited by CBD under the sequence
d) SEM
Cu2SnS3/ZnS followed by annealing at 450°C present an
CZTS (Evap.)
additional peak around 560 cm-1 which has been
associated with the Cu2-xS phase [10]. It is also observed
that the peak associated with the [A1] mode of the sample
deposited by evaporation is wider than that of the sample
deposited by CBD under the sequence Cu2SnS3/SnS/ZnS
(Fig. 3b) and it occurs at a higher wavenumber. The peak
broadening in the samples deposited by evaporation is Figure 4: Typical AFM and SEM images of CZTS thin
correlated with the increasing structural disorder due to films prepared by both, sequential CBD and sequential
the random distribution of S atom in the lattice that leads evaporation respectively.
to fluctuations in the masses and force constants in the

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The AFM and SEM measurements revealed that the
morphology of the CZTS films deposited by CBD is quite
different from that of the samples prepared by sequential
evaporation. The samples prepared by evaporation tend to
grow with grains grouped together in big clusters (size of
about 0.7 x1 µm). CBD deposited CZTS films grow in
general with a morphology characterized by small grains
with sizes varying in the range of 190x 80 nm and 260x140
nm; however in this types of samples, clusters with sizes of
the order of 0.6 x 0.3 µm are formed in some regions.
4 CONCLUSIONS
Cu2ZnSnS4 thin films were grown from Cu2SnS3 and
ZnS precursors deposited sequentially by both, vacuum
and solution based deposition techniques. The vacuum
based Cu2SnS3 compound was obtained by sequential
evaporation of Cu and Sn in presence of elemental sulfur
and the solution based Cu2SnS3 compound was prepared
in one step using a novel procedure consisting of
simultaneous precipitation of Cu2-xS and SnS. The co-
precipitation of Cu2-xS and SnS was performed by
diffusion membranes assisted CBD technique. XRD and
Raman spectroscopy studies gave evidence of the
formation of single phase CZTS films using both, the
vacuum and solution based deposition techniques under
optimized growth conditions.
Optical characterization performed by spectral
transmittance measurements revealed that in general, the
CZTS films grow with poor crystallographic quality,
probably associated to structural and native defects,
indicating that further studies must be done to improve
the properties of the CZTS films. CZTS thin films we
have grown in this work by evaporation and by CBD
have a value of Eg = 1.42 eV and 1.5 eV respectively,
indicating that these compound are suitable for use as
absorber layer in solar cells.
AFM and SEM studies revealed that the morphology
of the solution based CZTS films is quite different from
that of the samples prepared using vacuum based
technique. The samples prepared by evaporation tend to
grow with grains grouped together in clusters, while the
CBD deposited CZTS films grow in general with a
morphology characterized by small grains.
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ACKNOWLEDGEMENTS: This paper was

supported by Colciencias (Cont. #038-2013), DIB-
Universidad Nacional de Colombia and FODEIN-
Universidad Santo Tomás. Also to IREC, Barcelona
Spain.

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