Journal of Analytical and Applied Pyrolysis 122 (2016) 209–215

Contents lists available at ScienceDirect

Journal of Analytical and Applied Pyrolysis

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

Preparation and characterization of Cu2 FeSnS4 quaternary

semiconductor thin films via the spray pyrolysis technique for
photovoltaic applications
M. Adelifard
School of Physics, Damghan University, Damghan, Iran

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

Article history: The Cu2 FeSnS4 (CFTS) nanostructured thin films have been spray deposited onto glass substrates without
Received 5 July 2016 any post-sulfurization in toxic atmosphere such as H2 S or ‘S’ vapor. The influence of substrate tempera-
Received in revised form tures on the structural, morphological, compositional, optical, electrical and photoconductivity properties
25 September 2016
of the CFTS thin films have been studied. These properties are found to be strongly dependent on the sub-
Accepted 25 September 2016
Available online 27 September 2016
strate temperature. XRD spectra analysis revealed that all CFTS thin films showing pure stannite structure.
The improved crystallinity of the CFTS with a (112) orientation was observed with increasing the sub-
strate temperature. The spray synthesized CFTS films exhibit a smooth, uniform and dense topography.
Keywords:
CFTS EDS study reveals that the deposited thin films are nearly stoichiometric. The direct band gap energy
Thin film for the CFTS thin films is found to be about 1.50 eV, which is close to the ideal band gap for the high-
Spray pyrolysis est theoretical conversion efficiency of solar cell. Electrical conductivity and hole mobility of the CFTS
Optical properties films increases with increasing substrate temperatures. The films were p-type and shows photoconduc-
Electrical properties tivity. Electrical measurements (I–V curves) were registered in dark and under light exposure and were
correlated with the films composition and structure, as obtained from the EDS analysis and XRD patterns.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction Recently, several techniques including physical and chemical

Currently, researches on low-cost thin film solar cells are
increasing significantly. Various types of well-known solar cell
materials such as CdTe and CuIn(Ga)Se2 (CIGS) have been exten-
sively investigated [1–5]. These materials have the toxicity of
cadmium, expensive and scarce elements like indium and gallium,
respectively, which affects large-scale production. To achieve the
goal of cost-effective photovoltaic technology, it is necessary to
explore new materials contains less toxic material S instead of Se
and more abundant elements, Fe, Sn, than In, like Cu2 FeSnS4 (CFTS)
and other quaternaries of these chalcopyrite-like semiconductors.
CFTS is reported to have a band gap between 1.2 and 1.5 eV (ideal
for a single junction solar cell) [6–12] and a band edge absorption
coefficient above 104 cm−1 . A thorough understanding of material
properties is very much essential for the successful utilization of
this compound in solar cells.
E-mail address: adelifard@du.ac.ir
methods have been employed for preparing CFTS thin films namely:
sputtering [11] and successive ionic layer absorption and reac-
tion [12]. Generally these techniques are multi steps processes,
they are based on sequential or co-deposition of precursor metal-
lic stacked layers followed by a subsequent sulfurization. Also,
other techniques such as hot injection and the ultrasound-assisted
microwave irradiation for the deposition of CFTS layer were utilized
[7,8]. However, the above methods for synthesizing CFTS are usu-
ally complex and time-consuming. Considering these problems, for
a large scale solar cell production a single step and facile deposition
process is more economic and well suitable.
Chemical spray pyrolysis (CSP) technique is low-cost, non-
vacuum and eco-friendly, and can be used for cost-effective
large-area deposition, with no need of any sophisticated instru-
mentation. However, to the best of our knowledge, spray deposition
of CFTS thin films has rarely been reported. Prabhakar et al. [10]
reported deposition of CFTS thin films by spray pyrolysis followed
by sulfurization at different temperatures of 400, 500 and 600 ◦ C.
The effect of sulfurization temperature on the properties of CFTS
thin films was studied.

http://dx.doi.org/10.1016/j.jaap.2016.09.022
0165-2370/© 2016 Elsevier B.V. All rights reserved.
210 M. Adelifard / Journal of Analytical and Applied Pyrolysis 122 (2016) 209–215

In this study, we report a simple method to prepare CFTS thin

films by spray pyrolysis technique on the glass substrate without
sulfurization in toxic atmosphere such as H2 S or ‘S’ vapor. Differ-
ent substrate temperature conditions (250–370 ◦ C) were used to
study the effect of substrate temperature on the structural, com-
positional, morphological, optical, electrical and photoconductivity
properties of CFTS thin films.

2. Experimental

2.1. Synthesis of CFTS thin films

Cu2 FeSnS4 (CFTS) thin films were deposited by spray pyroly-

sis method on glass substrate. The CFTS precursor solution was
prepared by mixing CuCl2 . 2H2 O (0.1 M), FeCl3 . 6H2 O (0.05 M) and
SnCl4 ·5H2 O (0.05 M) in 50 ml double-distilled water. Tin (IV) chlo-
ride react with water to produce tin (IV) hydroxide and hydrogen
chloride (hydrolysis of SnCl4 ) as follows:

SnCl4 + 4H2 O  Sn(OH)4 + 4HCl (1)

Therefore, In order to enhance the solubility of tin chloride, a few

drops of hydrochloric acid (typically of the same or greater molarity
as the stannic chloride) was also added to the solution to maintain
the equilibrium towards the left-hand side.
Then 0.4 M of thiourea (CS(NH2 )2 ) was dissolved into the mix-
ture. The excess quantity of thiourea was added to prevent any
deficiency of sulfur in the prepared films because sulfur is a very
volatile element, especially at elevated temperatures. Since the
thiourea can be decomposed in air upon heating to generate H2 S,
the our spraying system and furnace was kept inside an airtight
metallic chamber of size 60 × 60 × 60 cm3 and the outlet of the box
was fitted with an exhaust fan to remove the toxic gases produced
during the decomposition of the spray solution. However, because
of the acute health hazard associated with H2 S vapor that could be
accidentally released from a spray pyrolysis unit, operator is also
needed to protect his health. Some safety precautions when work-
ing with system are: do not breathe mist/vapors/spray, and also
do not eat, drink or smoke when working with system. The final
solution was stirred for 30 min. CFTS thin films were deposited
at different substrate temperatures from 250 ◦ C to 370 ◦ C at the
step of 40 ◦ C with an accuracy of ±5 ◦ C using a digital tempera-
ture controller to investigate substrate temperature effect. Other
deposition parameters such as spray deposition rate, the distance
between nozzle and substrate and hot plate rotation speed were
set at: 10 ml/min, 30 cm and 50 rpm, respectively. The samples are
denoted as ‘CFTS250 , ‘CFTS290 , ‘CFTS330 , and ‘CFTS370 .
2.2. Characterization techniques
The structure confirmation of films were performed by using
X-ray Diffractometer (D8 Advance Bruker system) with Cu−K␣
radiation (␭ = 1.5406 Å) operated in the 2␪ range from 10 to 70◦ . The
elemental composition was determined using an energy-dispersive
spectrometer (EDS) system attached to VEGA2 SEM. Field emis-
sion scanning electron microscope (FE-SEM, S-8000, Hitachi), and
Atomic Force Microscope (AFM, 95-50-E, DME) are used to study
the surface morphology of the CFTS film. Optical characterization
was done using Shimadzu-UV1800 spectrophotometer.
The film thickness was measured using a Taly step profilome-
ter (roughness detector with a stylus-Taylor Hobson model). Taly
profile (a dedicated software package designed for use with labora-
tory instruments) has complete laboratory analysis functions such
as: roughness parameters and Step height measurement etc.; and
the information can be displayed graphically and numerically. By
step height measurement between coated glass and uncoated part
Fig. 1. XRD patterns of CFTS thin films deposited at various substrate temperature.
of glass we could determine the thickness of the studied samples
with a precision of about 10 nm.
Electrical resistivity and Hall effect data (magnetic field
strength = 240 mT) of the samples were measured in the Van der
Pauw configuration [13]. To study the photoconductive proper-
ties of prepared films, samples were exposed to light radiation
with fixed intensity (3500 lx) at a fixed distance (20 cm). Then,
the resistance of films were recorded under lighting at specified
time intervals at room temperature. The electrical measurements
(I–V curves) of the films were investigated by using the two-point-
probe method. To this purpose, two ends of samples were coated
with aluminum by thermal evaporation in vacuum using Edwards
E-306 coating system. The distance between two electrode and
instrument was set at 25 cm.
3. Results and discussion
3.1. Structural characterization
Fig. 1 presents the X-ray diffraction patterns of CFTS films
deposited at different substrate temperatures (250, 290, 330 and
370 ◦ C). All thin films are polycrystalline irrespective of substrate
temperature. The data analysis show the single stannite structure
of Cu2 FeSnS4 (JCPDS No. 44-1476) in the tetragonal space group
I-42m, with the major diffraction peaks (112), (200), (220), and
(116) in all the studied samples [10–12]. Also, with increasing the
substrate temperature, the presence of other orientations along
(101) and (110) which belong to Cu2 FeSnS4 tetragonal phase was
also detected. Except for these peaks, no characteristic peaks were
detected for other phases/impurities such as FeS, CuS or Cu2 S,
which indicates that the as-prepared films might have a com-
plete synthesization without post-annealed. It can be seen that
(112)-oriented texture is dominant for all CFTS thin films, and the
intensity and full width at half maximum (FWHM) of (112) peak
become strong and narrow with increasing the substrate temper-
ature, which indicates that the films have good crystallinity.
The crystallite size of the films, calculated using Scherrer’s for-
mula:
k
D= (2)
ˇ cos 
 M. Adelifard / Journal of Analytical and Applied Pyrolysis 122 (2016) 209–215 211

Table 1
Chemical composition of different CFTS films measured by EDS.

Reference Composition of elements in thin films (at.%) Cu/(Zn+Sn) Fe/Sn S/metal

Cu Fe Sn S

CFTS250 24.84 12.99 12.67 49.5 0.96 1.02 0.98

CFTS290 25.02 13.46 12.49 49.03 0.96 1.07 0.96
CFTS330 25.36 13.62 12.31 48.18 0.97 1.11 0.93
CFTS370 25.72 13.72 12.14 48.66 0.99 1.13 0.94

These ratios calculated from semi-quantitative EDS data may contain 5% error.

Fig. 2. FESEM images of CFTS thin films (a) CFTS250, (b) CFTS290, (c) CFTS330, and (d) CFTS370 (inset: low magnification image).

where D is the crystallite size,  is the wavelength of the x-ray
source, ˇ is full-width at half-maximum (FWHM) of the main peak,
k is a constant (close to unity) and  is the Bragg angle. The calcu-
lated crystallite sizes are found to be 11.48 nm, 18.84 nm, 23.15 nm
and 29.80 nm for CFTS250, CFTS290, CFTS330 and CFTS370, respec-
tively. The variation of the crystallite size has major influence on
optical and electrical properties of the samples, as described in the
following.
3.2. Composition characterization
The composition variation of spray deposited CFTS thin films
prepared at different substrate temperatures is presented in
Table 1. EDS shows the presence of Cu, Fe, Sn and S as major ele-
ments. All CFTS thin films deposited at substrate temperatures
between 250 ◦ C to 370 ◦ C were close to the stoichiometric one
in composition. In these films, excess metals and deficient sul-
fur are observed. Indeed, with increasing substrate temperature
the compositional ratios of sulfur slightly decrease in all CFTS thin
films due to the evaporation of sulfur during deposition process.
All thin films deposited at different substrate temperatures are
of Cu-poor and Fe-rich states (i.e. Cu/(Fe + Sn) < 1 and Fe/Sn > 1).
According to reported studies for efficient Cu2 ZnSnS4 (CZTS) solar
cells, zinc rich & copper poor combination with composition ratio
Cu/[Zn + Sn] = 0.85 to 0.9 and Zn/Sn > 1, is preferred [14]. Therefore,
analysis of Table 1 for our studied CFTS samples reveals that there is
no significant loss of any of the four elements and the compositional
ratios are nearly optimal for solar cell application.
3.3. Morphological study
In order to study the surface morphology, the produced films
were examined by FESEM, Fig. 2. It is observed that the homogene-
ity of the films increases with increasing substrate temperatures.
Increment in the substrate temperatures resulted in larger inter-
connected grains which lead to a reduction of the inherent defects
that are present in the materials. The low magnification images
(Fig. 3a–d inset) show that all samples are uniformly covered with
hierarchical spherical particles. The average grain size visualized by
FESEM, which corresponds to the grain size parallel to the substrate,
are around 20–40 nm. These particle sizes are fairly well matched
with those obtained by XRD analysis.
To establish the role of substrate temperature, further study
using atomic force microscopy was done. The AFM images are
shown in Fig. 3. The surface roughness decreases with increasing
substrate temperatures (CFTS250, CFTS290, CFTS330 and CFTS370
are ∼94, 81, 72 and 66 nm, respectively). As seen in section 3.1, as
the substrate temperature increases, the sharpness and intensity
of (112) diffraction peak increases. Further, the value of roughness
212 M. Adelifard / Journal of Analytical and Applied Pyrolysis 122 (2016) 209–215
Fig. 3. 3-D AFM micrographs of CFTS thin films (a) CFTS250, (b) CFTS290, (c) CFTS330, and (d) CFTS370.
decreases from 94 to 66 nm. Thus, the AFM study is consistent with
XRD analysis of the studies samples.
3.4. Optical study
The optical transmission spectra of the CFTS films are shown in
Fig. 4. According to these data, while the studied samples have a low
transmission in the visible wavelength range, it raises sharply to
about 20–32% in the near infrared wavelength region. It is also clear
that while the substrate temperature of the samples increases, the
absorption edges exhibit a slight blue-shift and it seems to stabilize
for radiation wavelengths below 600 nm.
It is also mentioned that the variations of transmission of the
films are consistent with the variations of crystallite size of the
layers, section 3.1; the greater the crystallite sizes, the higher the
optical transmittance of the films as a result of lower photon scat-
tering by the crystallite boundaries [15].
In addition to transmittance spectra, the reflectance of the thin
films can also reveal some other physical properties of the samples,
Fig. 4 inset. According to these data, reflectance of the samples has
a very low spectral dependence. This graph shows that all films
have a low (∼3–10%) reflectivity through all the visible and near
infrared wavelengths. This property accompanied by the transmit-
tance data indicates the high absorbance of these films in the visible
wavelength range.
The optical absorption coefficient spectrum of the CFTS film
is shown in Fig. 5(a). ˛() is estimated using the data presented
in Fig. 4, i.e. the transmittance measurements, T(), and the
reflectance measurements, R():
 
1 (1 − R)2
˛= ln (3)
d T
where d is the thickness of the layers (CFTS250, CFTS290, CFTS330
and CFTS370 are ∼350, 320, 280 and 260 nm, respectively). It
was found that the samples present a large absorption coefficient
(>104 cm−1 ) in the visible region, indicating it is suitable for thin
film solar cell applications. As shown in Fig. 5(b), the optical band
gap energy can be determined by extrapolating the straight portion
to the energy axis, i.e. (˛h)2 = 0. The direct optical band gap values
are found to be 1.42 eV, 1.46 eV, 1.49 eV and 1.55 eV for correspond-
ing CFTS250, CFTS290, CFTS330 and CFTS370; which are similar to
the band gaps of CFTS reported in literature [9,10]. In fact, the dis-
crepancy of band gap due to variation of substrate temperature is
a result of Mosse–Burstein (MB) effect [16,17], in which the band
gap can be presented as Eg = Eg0 + EMB , where Eg0 is the intrinsic
band gap and EMB is the amount of band gap change (a func-
tion of electron or hole concentration (n2/3 or p2/3 )), which tend to
increase the band gap as a result of degeneracy effect due to high
carrier concentration in the valance band. In regard to the present
case, the observed increase in the band gap values associated with
the increase in the hole carrier concentration (See Table 2). These
 M. Adelifard / Journal of Analytical and Applied Pyrolysis 122 (2016) 209–215
Fig. 4. Optical transmittance spectra of CFTS films (inset: reflectance spectra of CFTS films).
Fig. 5. (a) The variations of absorption coefficient versus wavelength, and (b) Plots
of (˛h)2 versus h for deposited CFTS films.
band gap values suggest that CFTS is a promising material as a light
absorber in solar cell devices.
213
Table 2
Electrical measurement results of the CFTS films for various substrate temperature.
Resistivity,  Carrier concentration, Mobility, 
(×10−3  cm) p (cm−3 ) (cm2 /V s)
CFTS250 7.04 9.01 × 1018 98.5
CFTS290 3.95 1.51 × 1019 104.7
CFTS330 3.24 1.63 × 1019 118.3
CFTS370 2.48 1.74 × 1019 144.8
The accuracy of measurements by using the van der Pauw method depends on
sample geometry, type of contacts and etc., and may contain 5–10% error.
3.5. Electrical and photoconductivity studies
Table 2 presents electrical properties of the CFTS films for vari-
ous substrate temperature. Through the Hall data acquisitions we
found out that all the studied samples exhibited p-type conductiv-
ity, well-matched with other reports [9,10]. It is clear that, while
the substrate temperature of the samples increases: (1) the hole
mobility increases from 98.5 cm2 /V.s to about 144.8 cm2 /V.s; (2) the
resistivity decreases from 7.04 × 10−3 .cm to 2.48 × 10−3 .cm
in CFTS thin films.; and (3)The degenerate hole density gradually
increases from ∼9.01 × 1018 cm−3 to about 1.74 × 1019 cm−3 . These
variations are compatible with the shifts in the transmittance and
reflectance spectra shown in Fig. 4 in relation with their poor/rich
metallic-like behavior. High carrier concentrations and mobility of
the films are higher than those found by Prabhakar et. al [10]. It is a
well-known fact that the various factors, such as crystallinity, mor-
phology, roughness, porosity, stress, composition, film-substrate
interface, etc., play a crucial role in determining the electrical prop-
erties of the films. In polycrystalline semiconductor thin films the
increase of the crystallite size produces an increase in the charge
carrier mobility and therefore decrease in the resistivity [18]. In
addition, the reduction of electrical resistivity can be motivated
also by an increase in the density of charge carriers. In regard to the
present case, the observed decrease in the electrical resistivity can
be associated with the increase in the crystallite size, grain size, and
also the loss of sulfur (See section 3.1, Fig. 2 and Table 1, respec-
tively). On the other hand, the sulfur deficiencies also contribute
to the increase in free carrier concentration of the films, which
reduces the resistivity of the films. Other authors also reported a
214 M. Adelifard / Journal of Analytical and Applied Pyrolysis 122 (2016) 209–215
Fig. 6. Variations of sheet resistance versus temperature in the studied samples.
Fig. 7. The relative reduction of resistance versus exposure time for CFTS thin films.
similar behavior for role of sulfur vacancies in improving electrical
properties of chalcogenide thin films [19–21].
The variation of resistivity versus temperature is a reliable
method for investigating the level of degeneracy in a material. Fig. 6
shows the experimental data for the variation of sheet resistance
(Rs = /d) versus temperature (in the range of 300–425 K) in our
studied samples. As it is evident the sheet resistances in all samples
are almost constant in the entire temperature range confirming the
studied layers, CFTS250–CFTS370, can be considered as degenerate
materials.
The relative reduction of resistance of the CFTS thin films versus
exposure time is shown in Fig. 7. It can be seen that the photocon-
ductivity properties of the films increase with increasing substrate
temperature. The best photoconductivity properties were obtained
for CFTS370 film.
Fig. 8 shows the light effect in dark and under100, 300 and
500Wcm−2 light exposure on the I–V behavior for the two typical
as-grown CFTS290 and CFTS370 films. As can be seen in Fig. 8, irra-
diation causes an increase in the current values of these films. The
maximum increase is observed under illumination at 500Wcm−2 .
It is also mentioned that the CFTS370 film is found to be more con-
ductive than the CFTS290 film. This higher conductivity could be
attributed to two processes, the improvement of the crystalliza-
tion with increasing substrate temperature from 290 to 370 ◦ C in
agreement with the XRD patterns (Fig. 1); and loss of S and Sn
Fig. 8. The I–V behavior for CFTS290 and CFTS370 thin films under dark and light
exposure.
and formation of Cu-rich components with increasing substrate
temperature (Table 1).
In addition to, this loss of S with increasing substrate tem-
perature creates intrinsic defects (intrinsic acceptors and intrinsic
donors). These defects are playing a major role affecting the con-
ductivity [22–24].
4. Conclusions
Quaternary CFTS films were deposited on heated glass at differ-
ent substrate temperatures
(250–370 ◦ C) by spray pyrolysis technique without sulfurization
under a non-vacuum condition. The effects of substrate tempera-
ture on the structure, morphology, composition, optical, electrical
and photoconductivity properties of CFTS thin films were inves-
tigated. XRD results reveal that the CFTS formation starts at a
low temperature as 250 ◦ C and continues till 370 ◦ C. At low depo-
sition temperatures the CFTS films are nearly poor crystallinity.
As the deposition temperature is increased to 370 ◦ C, the crys-
tallinity and the grain size increases. However, with increasing
substrate temperature from 300 to 375 0C, the surface morpholo-
gies of films became uniform in gradual and large grains size were
obtained. All thin films have high absorption coefficient values
close to 105 cm−1 in the visible region and the direct optical band
gap in the layers increases from 1.42 to 1.55 eV, which proves
them as promising candidate for the fabrication of high efficiency
solar cells. The photoconductivity properties of the films increase
with increasing substrate temperature. Finally the Hall experi-
 M. Adelifard / Journal of Analytical and Applied Pyrolysis 122 (2016) 209–215
ment data show that all the studied samples are p-type degenerate
(p > 9 × 1018 cm−3 ) films. Irradiation effect on the I–V behavior of
the CFTS290 and CFTS370 films have also been investigated. Current
values increased with increasing light intensity.
References
[1] M.A. Contreras, K. Ramanathan, J.A. Shama, F. Hasoon, D.L. Young, B. Egass, R.
Noufi, Prog. Photovolt. 13 (2005) 209.
[2] B.A. Anderson, C. Azar, J. Holmberg, S. Karlsson, Energy 23 (5) (1998) 407.
[3] J.L. Vossen, W. Kern, Thin Film Processes, New York Academic Press, 1978, pp.
104–107.
[4] K. Taretto, U. Rau, J. Werner, Thin Solid Films 8 (2005) 480–481.
[5] I. Luck, J. Kneisel, K. Siemer, J. Bruns, R. Scheer, R. Klenk, N. Janke, D. Braunig,
Sol. Energy Mater. Sol. Cells 67 (2001) 151.
[6] Y.E. Romanyuk, L.P. Marushko, L.V. Piskach, I.V. Kityk, A.O. Fedorchuk, V.I.
Pekhnyo, Cryst. Eng. Comm. 15 (2013) 4838–4843.
[7] W. Wang, H.L. Shen, H.Y. Yao, J.Z. Li, Mater 125 (2014) 183–186.
[8] C. Yan, C. Huang, J. Yang, F.Y. Liu, J. Liu, Y.Q. Lai, Chem. Commun. 48 (2012)
2603–2605.
[9] X.Y. Zhang, N.Z. Bao, K. Ramasamy, A. Yu-Hsiang, Y.F. Wang, B.P. Lin, Chem.
Commun. 48 (2012) 4956–4958.
[10] R.R. Prabhakar, N.H. Loc, M.H. Kumar, P.P. Boix, S. Juan, R.A. John, S.K. Batabyal,
L.H. Wong, ACS Appl. Mater. Interfaces 6 (2014) 17661–17667.
215
[11] X. Meng, H. Deng, J.H.L. Sun, P. Yan, J. Chu, Mater. Lett. 151 (2015) 61–63.
[12] H. Guan, H. Shen, B. Jia, X. Wang, Mater. Sci. Semicon. Process. 25 (2014)
159–162.
[13] L.J. Van der Pauw, A. method of measuring specific resistivity and Hall effect
of discs of arbitrary shape, Philips. Res. Rep. 13 (1958) 1–9.
[14] H. Katagiri, K. Jimbo, W.S. Maw, K. Oishi, M. Yamazaki, H. Araki, A. Takeuchi,
Thin Solid Films 517 (2009) 2455–2460.
[15] P.K. Manoj, B. Joseph, V.K. Vaidyan, D. Sumangala Devi Amma, Ceram. Int. 33
(2007) 273.
[16] E. Burstein, Phys. Rev. 93 (1954) 632.
[17] T.S. Moss, Proc. Phys. Soc. Lond. Ser. B 67 (1954) 775.
[18] J.W. Orton, B.J. Goldsmith, J.A. Chapman, M.J. Powell, J. Appl. Phys. 53 (1982)
1602.
[19] Y. Rodriguez-Lazcano, H. Martinez, M. Calixto-Rodriguez, A. Nunez Rodriguez,
Thin Solid Films 517 (2009) 5951.
[20] O. De Melo, L. Herandez, O. Zelaya-Angel, R. Lozada-Morales, M. Becerril, E.
Vasco, Appl. Phys. Lett. 65 (1994) 1278.
[21] V. Narasimman, V.S. Nagarethinam, K. Usharani, A.R. Balu, Int. J. Thin Film Sci.
Technol. 5 (1) (2016) 17.
[22] J. Cardoso, O. Gomezdaza, L. Ixtlilco, M.T.S. Nair, P.K. Nair, Semicond. Sci.
Technol. 16 (2001) 123.
[23] J. Johansson, M. Kostamo, L. Karppinen, J. Mater. Chem. 12 (2002) 1022.
[24] W. Jeong, G. Park, Sol. Energy Mater. Sol. Cells 75 (2003) 93.