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Microstructural and optical characterization of CZTS thin films deposited in one

step by spray pyrolysis

Conference Paper · June 2015

DOI: 10.1109/PVSC.2015.7356087

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 Microestructural and optical characterization of CZTS thin films
deposited in one step by spray pyrolysis
E. A. Ramirez, , M. F. Hurtado-Morales, A. A. Ramírez, G. Gordillo.
National University of Colombia, Bogotá, edaramirezpe@unal.edu.co, Colombia
Abstract — Thin films of Cu2ZnSnS4 (CZTS) have been
deposited on top of glass substrates using spray pyrolysis. The
precursor solution of CZTS was prepared in one step, dissolving
metallic salts and thiourea in dimethyl sulfoxide (DMSO). The
solution was deposited under flow nitrogen on a hot plate at 623K
and afterwards all samples were annealed at 773K in nitrogen-
atmosphere. The effect of film thickness and the annealing
process on the structural and optical properties of CZTS films
have been studied. X-ray diffractograms revealed the formation
of polycrystalline CZTS films and was used Raman spectroscopy
for identify possible secondary phases. The grain size of the films
was calculated using the Scherrer´s formula and the optical
reflectance and transmittance were measured to determine the
absorption coefficient, Urbach energy and the optical band gap.
This studies reveal that the transition is direct band gap energy
and the value is inversely to the thickness. The films of 1µm
showed single phase CZTS and low Urbach energy, indicating a
decrease in the density of localized states in the band gap by
increasing the crystallinity.
Index Terms — Spray pyrolysis, thin films, CZTS, solar cells.
I. INTRODUCTION
Cu2ZnSnS4 (CZTS) is a quaternary semiconductor that has
emerged as a potential absorber substitute for CuInGaSe2 in
photovoltaic devices. This material has excellent optical
properties (α ~ 104cm-1) and a direct band gap value that
matches well the solar spectrum (1.46 ≤ Eg ≤ 1.5 eV) [1].
Various approaches have been reported to fabricate CZT(S,Se)
absorber layers, including vacuum-deposition technologies
(e.g., thermal coevaporation, sputtering, and pulsed-laser
deposition) and non-vacuum-deposition technologies (e.g.,
electrodeposition and solution process) [2]. Recently, a world-
record efficiency of 12.0% was reported for CZTSSe solar
cells by IBM group using zinc particles dispersed in a
precursor slurry between hydrazine and metal chalcogenide
nanoparticles [3]. However, hydrazine-based solutions have
some limitations for large-scale production because of their
toxicity; therefore, it is highly desirable to develop a low-
toxicity and facile solution. Recently, was reported a novel
method in which metal salts and thiourea are dissolved in
dimethyl sulfoxide (DMSO). With this method 7.5%
efficiency was reached [4].
In this contribution, we presented a process for fabrication
of CZTS thin films, from metal chlorides and thiourea
dissolved in DMSO. We use the spray pyrolysis method for
the deposition process and films of different thicknesses was
obtained depending on the number of layers. The effect of
annealing process and the films thickness was evaluated.
Further, results are reported related to structural, optical and
morphological properties determined from XRD, Raman
spectroscopy, transmittance and reflectance measurements.
II. EXPERIMENTAL SETUP
In the synthesis of CZTS solution, Dimethyl sulfoxide
(DMSO) was used as a solvent due to its very low toxicity and
its suitable boiling point and surface tension. Cupric chloride
(0.01 M), zinc chloride (0.005 M), stannic chloride (0.005 M)
and thiourea (0.04 M), were used like a source of metals and
sulfur, respectively. We diluted the DMSO solution with
acetone to decrease viscosity and improve the wetting
behavior.
A spray pyrolysis deposition system operated in open air
conditions was used to produce the CZTS thin films. The
system used a pneumatic spray nozzle that employed nitrogen
as the carrier gas a pressure of 200 kPa of compressed N2,
using a dissolution flow rate of 15L.min−1. Films were
deposited on ultrasonically cleaned soda lime glass substrates
held at a substrate temperature of 623 K, which could be
maintained to an accuracy of ±10K using analog temperature
controller. Each layer was grow with 5 spray pulses and 1 min
of time between pulses in all cases. Films of different
thicknesses were deposited: K13 (0,5µm), K15 (0.75µm) and
K17 (1µm).
Crystallization process was carried out in the temperature of
773K during 30 min at a constant working pressure of 20 mbar
and a N2 flow rate. The furnace temperature was ramped up at
10 K/min until the maximum temperature was attained. The
films annealed are denoted by letter A.
The transmittance and reflectance measurements were done
using a Varian – Cary 5000 spectrophotometer between 350-
1600nm and the film thickness was determined using a Veeco
Dektak 150 surface profiler. The phase identification was
performed using X-ray diffraction with a Shimadzu-6000
diffractometer and Raman spectroscopy with a Thermo Scientific
DXR Raman microscope with a DPSS laser of 780nm, 15 mW
focused with a 50X objective.
II. RESULTS AND DISCUSSIONS
A. Optical properties
The influence of thickness and annealing on the optical
properties of CZTS thin films was studied. From
measurements of spectral reflectance and transmittance was
calculated the absorption coefficient (α), using the next for identify ternary and other secondary phases, such as,
relation. Cu2SnS3-t and c-ZnS, was used Raman spectroscopy. The
other films, corresponding to 0.5µm and 0.75µm thick showed
1  T ( )  a shift in the diffraction pattern, this due to internal tensions
   ln( ) (1)
d  1  R( )  between planes that generate macroscopic deformation. This
was quantified by measuring the lattice strain (see Table 2).
Where d is the film thickness, T(λ) and R(λ) are the
transmittance and reflectance, respectively.
Using the equation 2 was calculated the band gap (Eg). Values
for the three samples are presented in Table 1. The Eg
decreases with increasing thickness, from 1.75 to 1.55 eV for
k13 and k17 films, respectively, approaching the optimal value
(~1.5 eV).

(hv)  B(hv  Eg )1/ 2 (2)

Where hν is photon energy B is a constant between 107 and

108m-1 and Eg is the energy between the valence and the
conduction band
In semiconductor materials the Urbach energy (Eu) is a direct
measurement of temperature induced disorder, including too
structural disorder (tension and dislocations) [5]. The Eu is
related with the absorption coefficient and Eg according the
following equation.

 hv  Eg  Fig. 1. X-ray diffractions patterns obtained for annealed and

   0 exp   (3)
 Eu  unannealed CZTS thin films
The full width at half maximum (FWHM) of CZTS thin films
Where Eu is the Urbach energy which corresponds to the
for (112) plane are given in Table 2. FWHM of thin films
width of the band tail, EI and αo are constant. This energy is
shows an increase with decreasing thickness. The grain size D
related to the density of localized states in the band gap. In
of crystallites was calculated using the Scherrer’s Formula [6].
Table 1 shown that increasing the thickness leads to a decrease
of Eu due to reduced localized states by increasing the
4 K
crystallinity. D (4)
3 B1/ 2.cos( B )
TABLE I
Were the shape factor (4/3) refers to a geometrical correction
Eg AND Eu OF CZTS FILMS OF DIFFERENT THICKNESSES
assuming spherical crystallite shapes, λ is the radiation
Sample Eg (eV) Eu (meV) wavelength, K is an unit cell geometry dependent constant,
k17A 1.55 655.10 which was set to be equal to 0.99,  B is the XRD peak
K17 1.55 1206.85
position and B1 / 2 is the corrected FWHM of the main XRD.
K15A 1.65 8613.26
K15 1.65 - The larger D values indicate better crystallization of the film.
K13A 1.75 11933.17 It was observed that the grain size values decrease with the
K13 1.75 16051,36 film thickness, which clearly reveals the deterioration in the
crystallinity. The results for k17 and k17A films, shows that
the annealing process can increase about 9.3 times the size of
crystallite and Urbach energy decrease by half.
B. Structural properties
The correct FWHM was estimate according the expression
The X-ray diffraction patterns of K17 and K17A showed
diffraction in planes corresponding to the structure Kesterite,
diffraction peaks (112) (220) (312) and was not found B1 / 2  FWHM 2  corr 2 (5)
secondary phases type Cu2-xS and SnxSy (see Fig. 2). However,
Where corr is the correction parameters related to the
equipment's peak broadening.

TABLE II
CRYSTALLITE SIZE MEASURED USING THE FWHL
D - Crystallite
Sample FWHM Ratio
size (nm)
k17A 0.157 144.0
9.3
K17 0.630 15.5
K15A 0276 46.6
6.0
K15 1.152 7.8
K13A 0.576 17.2
2.3
K13 1.179 7.6

C. phase identification
Because of the similarity between the diffraction peaks of
CZTS phase and Cu2SnS3-t and c-ZnS, was used Raman
spectroscopy in order to unambiguously identify the
corresponding peaks using the symmetric vibrational modes.
CZTS is known to have the following strong peaks: 288-289
cm-1 and 337-339 cm-1. The spectra showed a dominant Raman
shift peak in 333 cm-1, this signal is associated to CZTS
structure with local structure inhomogenities caused by a
highly disordered distribution of Cu and Zn atoms. Other less
intense peaks also were identified and assigned to Cu2SnS3-t
and c-ZnS secondary phases. These peaks are shown in the
Raman spectra of annealed films (Fig. 2 and 3). defects and
increased crystallite size.
Was observed a relationship between increased crystal size
and shift in the bands Raman after annealing. The films k17
increase the crystallite size around 9 times after annealing and
the shift of the Raman bands was 18 cm-1, while k13 film that
only increased about 2.3 times the size of the crystal after
annealing, had a Raman shift of 9 cm-1 in the main peak (see
Fig 2 and 3).
Fig. 2. Raman spectrum of unannealed CZTS thin films.
Fig. 3. Raman spectrum of annealed CZTS thin films.
III. CONCLUSIONS
Best crystallographic characteristics as well as an increase in
crystallite size and reduced the Urbach energy are achieved
with an increase in film thickness. This can be attributed to
diffusive effects that generate structural failures when the films
are very thin.
Particles formed before annealing are similar size. However,
the increase in thickness promotes the growth of crystals.
would be interesting in future studies to evaluate these results
with electrical measurements.
REFERENCES
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Cu2ZnSnS4 thin films. Journal of Alloys and Compounds, vol.
585, pp. 776–782, 2014
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Pan, Fabrication of a Cu2ZnSn(S,Se)4 photovoltaic device by a
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[3] T. M. Winkler, W. Wang, O. Gunawan, H. J. Hovel, T. K.
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[4] T Schnabel, M. Löw and E. Ahlswede, "Vacuum-free
preparation of 7.5% efficient Cu2ZnSn(S,Se)4 solar cells based
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[5] M.V. Kurik, Review of Urbach´s tail. Phys. Status Solidi A, vol.
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