Determination of the optimal conditions for
the deposition ofCu2ZnSnS4 (CZTS) thinjilms
by Spray Pyrolysis using Taguchi method
Youssef Arba*, Joel Herve Nkuissi Tchognia,
Bouchaib Hartiti, AbderraoufRidah
Department of Physics
FST, Hassan II Mohammedia University
Mohammedia, Morocco
youssefarba080@gmail.com
*
Abstract-Thin films of Copper zinc tin sulfide (Cu2ZnSnS4'
CZTS) is one of the promising semiconductor materials used in
over recent years as a next generation of absorber materials in
thin film solar cells thanks to its tunable direct band gap energy,
large absorption coefficient, cost effective and eco-friendly
nature. The aim of this present study is to investigate the
influence of parameters deposition of CZTS thin films using the
L27 orthogonal array of the Taguchi's design of experiments.
CZTS thin films were deposited on ordinary glass substrate by
spray pyrolysis technique. The Taguchi design was used to
evaluate the effects of seven deposition parameters called factors
namely the ratios ICuIfOZnl+ISnl), IZnlflSnl and ISIfIMetall,
solution rate, air-compression, time of deposition, substrate
temperatures on optical properties of as-sprayed films. The
identification of the most influent factors of the deposition
process on the band gap energy of as-sprayed films is also done.
Under the optimized configuration, the CZTS films showed
optimal gap energy of 1.56 eV. The Taguchi analysis employed in
the present investigation led to optimize process parameters for
the most optimal deposition conditions.
Keywords: Spray Pyrolysis, Taguchi method, Design
experiment, CU2ZnSnS4, Solar cell, thin film, optical
characterization.
I. [NTRODUCTION
Nowadays the solar cell market is dominated by wafer­
based crystalline silicon technology. Due to the indirect band
gap of Si,the thickness of the cells is about 200 11m [1,2] and
this increases significantly the total cost of the module. A
number of alternative materials have been investigated for the
development of next generation of cost-effective and high
efficiency solar cells. Among them polycrystalline cadmium
telluride (CdTe), copper indium diselenide (C[S) and its
combinations with gallium and/or sulfur (Cu(In,Ga)(S,Se)2)
have been well synthesized [3-7] and have reached the
commercialization stage. These materials, belonging to the
family of chalcopyrite-type are currently considered to be the
most promising thin film solar cell materials because of their
very favorable electronic properties that have recently led to
solar cell efficiencies surpassing 20%. They have a band gap
978-1-4799-7336-1/14/$31.00 ©2014 IEEE
Philippe Thevenin
Department of Physics
Supelec, University of Lorraine
Metz, France
close of that of silicon but which is associated to a photon
absorption mechanism of direct type. This results to an
absorption process very efficient leading to very high
absorption coefficients ( 105 cm·l) well matched to the solar
�
spectrum and compatible with the use of thickness of 1 to 2
microns about 100 to 200 times lower than that of crystalline
silicon. CIS and its alloys with gallium and/or sulfur is
therefore a semiconductor whose intrinsic optical
characteristics are better adapted than those of silicon to the
photovoltaic conversion.
However, limitations in supply for In, Ga and Te and
environmental pollution surrounding Cd and Se have raised
concern about limitations on production capacity of the PV
devices. [t is necessary to solve this issue by developing
alternative light absorber materials that are both non toxic and
easily available. In this context, CU2ZnSn(S, Se)4 (CZTS)
compound has gained more attention as one of the promising
candidates. All the components in CZTS are earth abundant
of
and environment benign. It is a compound whose intrinsic
point defects lead to p-type semiconductor behavior. It has an
4
absorption coefficient> [0 cm'! which is suitable for thin
film photovoltaic applications [8-10] and a direct band gap
which has been predicted [11] to be 1.0 eV for CU2ZnSnSe4
and 1.5 eV for CuZZnSnS4. The band gap of CZTS can also be
tuned by incorporation of Ge because Ge-containing materials
have smaller band gap than Ge-free counterparts [12]. This
tunability is of particular interest for the manufacturing of
absorbers with a band gap between 1.1 eV and l.5eV which
allow theoretical efficiencies higher than 30% [13]. CZTS is a
mineral found in nature [[4] and sharing the similar structure
with CIS except that half of [n is replaced with Zn and another
half with Sn. It has two principal crystallographic structures
known as stannite-type and kesterite-type which are similar
except the different arrangement of Cu and Zn atoms [[5].
However it usually appears in kesterite phase because it is
more stable thermodynamically compared to the stannite
phase [15]. CZTS can be synthesized through solid state
chemical reactions between ZnS, CU2S and SnSz. The study of
the phase diagram of the system has shown that a single phase
CZTS material can be formed only in a very small region [16].
Impurities including ternary and quaternary compounds are
easier to form than CZTS. The single phase composition
region is much smaller for CZTS than for CIS. Therefore it is
very challenging to make pure CZTS compounds. Until now,
only Cu-poor and Zn-rich materials gave high efficiency as
was already noted Nagaoka team [17]. In Zn-rich growth
conditions, the kesterite structure is tolerant to stoichiometry
deviations by zinc excess and copper lacking [17-19], but high
Zn content also leads to structural disorder [20]. That is why it
is important to find an optimal range for values of the rations
[Cu]/([Zn]+[Sn]), [Zn]/[Sn] and [S]/[Metal]. Considering the
above parameters and other, CZTS thin films have been
synthesized by various deposition techniques which are
Thermal evaporation [21], E-Beam evaporation with post
sulfurization process [22], RF co-sputtering of binary
compounds [23]. Routes using co-evaporated elements [24].
Non vacuum methods have also been developed namely
sulfurization of sol-gel deposited precursors and spray­
pyrolysis [25, 26 and 27]. In this work we have used spray
pyrolysis for the synthesis of CZTS thin films. The main
advantages of spray pyrolysis technique are related to easy
control of roughness leading to light scattering which is a
useful tool in solar cells and ease of tailoring of film properties
for desired application by changing deposition conditions [28].
It is a simple technique, low cost and can be used effectively
for the deposition of large area thin films.
In this work, we have introduced the design of experiments
method to organize our experiments and to determine with a
minimum of tests and a maximum of precision the effect of
various deposition parameters on the optimization of optical
properties of CZTS films. We have selected seven process
parameters for the synthesis of CZTS films, and each of them
II. EXPERIMENTAL DETAILS
The CU2ZnSnS4 (CZTS) thin films were synthesized by
spray pyrolysis according to parameters shown in TABLE I. The
levels of factors were selected basing on the best preparation
conditions of this material found in the literature [25, 31 and
32]. Each experiment was repeated three times for taking into
account the dispersion of result in order to evaluate the
average of the three values for calculation of the signal on
noise (SIN) ratio. The energy band gap of the synthesized
films was used for the calculation of the SIN ratio where the
smaller value the better; see (1). After the selection of factors,
the L27 orthogonal array of the Taguchi's design of
experiments has been constructed which contains seven
columns and twenty seven rows; see TABLE II. Each parameter
was assigned to a column and twenty seven deposition
parameter combinations giving the higher precision and
information on the system have been available. Only twenty
seven experiments were therefore required to study the whole
system with the L27 (37) orthogonal array. In each experiment,
an aqueous solution containing cupric chloride, zinc acetate,
stannic chloride and thiourea was sprayed, using a
pneumatically controlled air-atomizing spray nozzle (14JAU,
Spraying systems Co., USA), onto heated glass substrates.
Compressed air was used as the carrier gas. TABLE I shows the
parameters and their levels used in this study and TABLE II
shows the combinations between these parameters where the
rows represent experiments.
TABLE I. Parameters and levels used in this experiment
Parameters levels
Symbol Parameters
Levell Level 2 Level 3
Temperature of
A 300 375 450
deposition (KO)
B [Cu] /([Zn] + [Sn]) 0.55 1 1.3
C [Zn] / [Sn] 0.38 0.88 1.2

has three different possible values. In order to obtain a full D [S] / [Metal] 0.8 1 1.2
characterization, one would be required to carry out all
factorial design combinations 37 i.e., 2187 experiments. E Pressure (mbar) 2 3 4

However, by applying Taguchi's design, one reduces F Spray rate 0.93 2.25 8
significantly the number of experiments and the time required
for an experimental investigation obtaining similar and in G spray time (min) 10 30 60

principle equivalent information by some approximations. In

our case, this allowed to perform only 27 sets of experiments TABLE II. L27 (37) Taguchi orthogonal array
instead of the whole set of 2187 required by a full factorial
design. The Taguchi method is also effective in investigating Tests A B C D E F G

the effects of multiple factors on performances of the final 1 Al BI CI DI EI FI GI

product as well as in study the influence of individual factors
2 Al BI CI DI E2 F2 G2
in order to know which factor is more influent than others [29,
30]. The main goal of this study is to apply the Taguchi 3 Al BI CI DI E3 F3 G3
method in order to determine the optimal experimental
4 Al B2 C2 D2 EI FI GI
configuration which leads to best optical properties (band gap
energy) of CZTS thin films. 5 Al B2 C2 D2 E2 F2 G2

6 Al 82 C2 D2 EJ F1 G1
 7 A, BJ CJ OJ E, F, G, band gap. The CZTS is a material with an energy band gap
ranging from 1.4 eV to 1.6 eV [22]. The theoretical optimal
8 A, B, C, 0, E, F2 G2 gap of this material is around 1.5eV [11, 37] with which this
material exhibits very good optoelectronic properties. In this
9 A, B, C, 0, EJ F, G,
work the performance criteria used to have informations about
10 A2 B, C2 0, E, F2 G, optical properties of films is given by the following formula:

11 A2 B, C2 0, E, F, G,

12 A2 B, C2 0, EJ F, G2 (2)

13 A2 B2 C, 0, E, F2 G,

14 A, B, CJ 0, E2 FJ G, Where /::"Eg is the difference between the theoretical value

and the experimental value of CZTS energy band gap obtained
15 A, B, CJ 0, EJ F, G,
from the experiments of the Taguchi table. The value /::"Eg ° =

16 A, BJ C, 0, E, F, GJ represents films with very good optical properties of an

absorber while higher values can indicate the presence of
17 A, BJ C, 0, E2 FJ G, secondary phases like ZnS, SnS, CuS or CuZSnS3 which have
18 A, BJ C, 0, EJ F, G,
a detrimental effect on CZTS performance. On TABLE 111 are
listed the experimental data of performance criteria (/::"Eg) and
19 AJ B, CJ 0, E, FJ G, the corresponding SIN ratio calculated by the above equation
(1). The mean of SIN ratio for each level of the parameters is
20 A, B, C, O2 E, F, G,
also calaculated and summarized in TABLE IV. Besides, the
21 A, B, C, O2 EJ F2 G, graphical representation of means of the SIN ratios of all
factors at all levels allowed to determine graphically the
22 A, B2 C, 0, E, F, G2 factors having more effects on film properties than others. The
23 A, B2 C, 0, E, F, G, graphical representation of the SIN response for the energy
gap is shown of Fig.l.
24 A, B2 C, 0, EJ F2 G,
TABLE III. The performance criteria value and the corresponding SIN ratio.
25 A, B, C2 0, E, F, G2
Ml I1E2 I1E3
Tests SIN ratio (db)
26 AJ BJ C, 0, E2 F, GJ (eV) (eV) (eV)
1 0 0,6 0,2 8,7506126
27 AJ BJ C, 0, EJ F, G,
2 0,1 0,07 0 23,03935

3 0,83 0,5 0,38 4,4237251

III. RESULTS AND DISCUSSION 4 0,14 0,5 0,6 6,7805654

The characterization of samples was done by the optical 5 0,3 0,4 0,1 10,621479
transmittance measurements. All the 27 experiments were
conducted with the same procedure as mentioned above. The 6 0,5 0,2 0,3 8,9733766
SIN ratio in Taguchi method is used to measure the
7 0,02 0,07 0,05 25,850267
performance criteria including: "Smaller-the-better",
"Nominal-the-better" and "Larger-the-better" [30, 33 and 34]. 8 0,1 0,2 0 17,781513
In this study, we have chosen "Smaller-the-better" as our
performance criteria. The corresponding SIN ratio proposed by 9 0,8 0,7 0,9 1,8931952

Taguchi in this case is given by the following equation [35, 10 0,5 0,53 0,4 6,3770606
36]:
II 0,2 0,2 0,565 8,7590353

12 0,911 0,53 0,5 3,4332025

(1)
13 0,3 0,102 0,2 13,297418

14 0,2 0,07 0,07 17,798919

Where i is the number of an experiment, n the number of 15 0,19 0,04 0,23 15,199931
repeated experiments and Y; represents the primary response 16 0,5 0,54 0,3 6,7667913
i.e the measured experimental value in our case the energy
 17 0,19 0,28 0,43 10,008695 According to Table IV and Fig.l, it appears clearly that
factors show different effects on optical band gap. The effect
18 0,5 0,43 0,1 8,2885885 of factors is classified according to the mean of the SIN ratio.
Fig.1 shows that, if the difference between the extreme points
19 0,839 0,4 0,64 3,7211514
is big, the factor has more effect on response. In this case one
20 0,093 0,54 0,1 9,8541086 can classify the intensity of effects of parameters according to
the mean their SIN ratios as follows: spray time, pressure,
21 0,1 0,13 0,4 12,05512
[Zn ]/[Sn] ratio, [S]/[metal] ratio, deposition temperature,
22 0,19 0,2 0,17 14,55932 [Cu]/[Zn]+[Sn] ratio and spray rate. The greater is the mean of
SIN ratio, the smaller is the value of energy band gap.
23 0,5 0,63 0,39 5,7457448 According to this, the better (optimal) combination of
parameters for preparing CZTS thin films leading to good
24 0,5 0,5 0,61 5,3655497
optoelectronic properties is then A\B3C3D\E2F2Gz. After the
25 0,17 0,2 0,04 16,289321 determination of the optimal condition, a confirmation
experiment was done and the result is shown on Fig.2. Fig.2
26 0,5 0,7 0,3 5,5804316
shows the variation of (ahu)2 as a function of photon energy
27 0,5 0,3 0,6 6,3202321 (hu) for as-deposited CZTS thin film under optimal condition.
Based on the direct allowed inter band transition theory, the
optical band gap of CZTS is determined by extrapolating the
TABLE IV. The mean of SIN response of performance criteria
linear part of the curve to the zero absorption coefficient
Mean of SIN ratio (dB) Optimal
(a 0) as shown in Fig.2. The film exhibits an energy gap of
=

Symbol 1.56 eV under this condition not far of theoretical value of

Levell Level 2 Level 3 parameters
A 12.01 9.99 8.83 Al 1.5eV [37] and similar to the band gap of bulk CZTS in
B 8.93 10.93 10.98 B3
comparison with those reported by others (1.54 and 1.56 eV
respectively) [18, 38].
C 9.66 8.13 13.05 C3
D 12.30 8.56 9.97 Dl
E 11.38 12.13 7.33 E2
F 9.94 11.29 9.60 F2
G 11.30 12.55 6.99 G2

14 1-- SIN ratio grapH

13 1500

12 �1250
iii'
'0 ";"E
to)
0' 11 > 100)

r
� �
en
z 10
en s: 750
N;;
'0
c: 9
.t:500
Sl �
:!:
8
250

1,50 1,65 1,80 1,95 Z10

A1A2.A3 - 81B283 - C1C2C3 - D1D2D3 - E1E2E3 - F1 F2F3 - G1G2G3
Photon Energy, hv (eV)
Deposition parameters

Figure 1. Graph of the SIN ratio for energy band gap Figure 2. Variation of (ahu)2 with the incident photon energy hu for
the sample prepared at optimal condition

IV. CONCLUSION
In this study, we used the Taguchi method to determine the
optimal configuration for growing CZTS thin films with good
optical properties. The L27(37) orthogonal array was used to
optimize the deposition parameters of films by spray pyrolysis
technique. The results showed that this method can greatly
simplify the optimization of multiple parameters and can
considerably reduce the cost and the time of experiments. It
has been showed that the Zn/Sn ratio and the spray time are
the most influent parameters on the optical band gap of CZTS
films. The film exhibits an optical band gap of l.56 eV under
optimal configuration which is quite close to the optimum
band gap energy for thin film solar cells.
ACKNOWLEDGMENT
The authors thank the ICTP (The Abdus Salam
International Centre for Theoretical Physics) and ANSOLE
(African Networkfor Solar Energy) for financial support in the
framework of the Intra-African Exchange (INEX) program.
REFERENCES
[1] K.L. Chopra, P.D. Paulson, V. Dutta, 'Thin-film solar cells: an overview,"
Progress in Photovoltaics: Research and Applications Vol. 12, 2004, pp. 69-
92.
[2] A Goetzberger, J. Knobloch, B. Voss, "Crystalline silicon solar cells:
technology and systems," Wiley, New York, 1998.
[3] C.B. Murray, D.J. Norris, M.G. Bawendi, "Synthesis and characterization
of nearly monodisperse CdE (E=S, Se, Te) semiconductor monocrystallites,"
Journal of the American Chemical Society, Vol. 115, 1993, pp. 8706-8715.
[4] AK. Iwahori, R. Takagi, N. Kishimoto, 1. Yamashita, "A size controlled
synthesis of CuS nano-particles in the protein cage, apoferrin," Materials
Latters, Vol. 65, 2011, pp. 3245-3247.
[5] 1. Tang, S. Hinds, S.O. Kelley, E.H. Sargent, "Synthesis of Colloidal
CuGaSe2, CulnSe2, and Cu(lnGa)Se-, Nanoparticles," Chem. Mater. Vol. 20,
2008, pp. 6906-6910.
[6] D.P. Dutta, G. Sharma, "A facile route to the synthesis of
CulnS2 nanoparticles," Materials Letters, Vol. 60, 2006, pp. 2395-2398.
[7] M. Jeon, T. Shimizu, S. Shingubara, "Cu,ZnSnS4 thin films and nanowires
prepared by different single-step electrodeposition method in quaternary
electrolyte," Materials Letters, Vol. 65,2011, pp. 2364-2367.
[8] K. Ito, T. Nakazawa, "Electrical and optical properties of stannite-type
quaternary semiconductor thin films," Jpn J Appl Phys. Vol. 27, 1988, pp.
2094-2097.
[9] c.P. Chan, H. Lam, C. Surya, "Preparation of Cu,ZnSnS4 films by
electrodeposition using ionic liquids," Solar Energy Materials and Solar
Cel/s, Vol. 94, 2010, pp. 207-2II.
[10] W. Xinkun, L. Wei, C. Shuying, L. Yunfeng, 1. Hongjie, "Photoelectric
properties of Cu2ZnSnS4 thin films deposited by thermal evaporation," J
Semicond. Vol. 33, 2012, pp. 0220021-02202224.
[II] S. Chen, X.G. Gong, A Walsh, S.H. Wei, "Crystal and electronic band
structure of Cu2ZnSnX4 (X=S and Se) photovoltaic absorbers: First-principles
insights," Appl. Phys. Lett. Vol. 94, 2009, pp. 041903-041908.
[12] G.M. Ford, Q. Guo, R. Agrawal, H.W. Hillhouse, "Earth Abundant
Element Cu,Zn(Snl-,Ge,)S4 Nanocrystals for Tunable Band Gap Solar Cells:
6.8% Efficient Device Fabrication," Chem. Mater., Vol. 23, 2011, pp 2626-
2629.
[13] W. Shockley, H.J. Queisser, "Detailed Balance Limit of Efficiency of p­
n. Junction Solar Cells," J Appl Phys, Vol. 32, 1961, pp. 510-519.
[14] S. A Kissin, "A Reinvestigation of the stannite (Cu2FeSnS4)-kesterite
(Cu2ZnSnS4) pseudobinary system," Canadian Mineralogist, Vol. 27. 1989.
pp. 689-697.
[15] S. Schorr, "Structural aspects of adamantine like multinary
chalcogenides," Thin Solid Films, Vol. 515, 2007, pp. 5985-5991.
[16] 1. D. Olekseyuk, 1. V. Dudchak, and L. V. Piskach, "Phase equilibria in
the Cu,S-ZnS-SnS2 system," Journal of Alloys and Compounds, Vol. 368,
2004, pp. 135-143.
[17] H. Katagiri, K. Jimbo, M. Tahara, H. Araki, K. Oishi, "The influence of
the composition ratio on CZTS-based thin film solar cells," in Materials
Research Society Symposium Proceedings, 2009, p. 1165.
[18] A Ennaoui, M. Lux-Steiner, A Weber, D. Abou-Ras, 1. Kiitschau, H.-W.
Schock, R. Schurr, A Hiilzing, S. Jost, R. Hock, T. VoB, J. Schulze, A Kirbs,
"Cu2ZnSnS4 thin film solar cells from electroplated precursors: Novel low­
cost perspective" Thin Solid Films, Vol.517, 2009, pp.2511-2514.
[19] P.A. Fernandes, PM.P. Salome, AF. da Cunha, "Growth and Raman
scattering characterization of Cu,ZnSnS4 thin films," Thin Solid Films, Vol.
517, 2009, pp. 2519-2523.
[20] M. Valentini, C. Malerba, F. Biccari, R. Chierchia, P. Mangiapane, E.
Salza, A Mittiga, "Growth and characterization of Cu,ZnSnS4 thin films
prepared by sulfiuization of evaporated precursors," in 26th EUPVSEC
(Hamburg, 2011).
[21] T.K. Todorov, K.B. Reuter, D.B. Mitzi, "High-Efficiency Solar Cell with
Earth-Abundant Liquid-Processed Absorber," Adv Mater. Vol.22, 2010, pp.
E156-E159.
[22] H. Katagiri, K. Saitoh, T. Washio, H. Shinohara, T. Kurumadani, S.
Miyajima, "Development of thin film solar cell based on Cu,ZnSnS4 thin
films," Solar Energy Materials and Solar Cells, Vol. 65, 2001, pp.141-148.
[23] K.K. Jimbo, R. Kimura, T. Kamimura, S. Yamada, W. Maw, H. Araki,
K. Oishi, H. Katagiri, "Cu2ZnSnS4-type thin film solar cells using abundant
materials," Thin Solid Films, Vol.515, 2007, pp.5997-5999.
[24] T. Tanaka, D. Kawasaki, M. Nishio, Q. Guo, H. Ogawa, "Fabrication of
CU2ZnSnS4 thin films by co-evaporation," Phys Stat Sol (c), Vol.3. 2006.
pp.2844-2847.
[25] N. Kamoun, H. Bouzouita, "Fabrication and characterization of
Cu,ZnSnS4 thin films deposited by spray pyrolysis technique," Thin Solid
Films, Vol.515, 2007,pp.5949-5952.
[26] K. Tanaka, N. Moritake, H. Uchiki, "Preparation of Cu,ZnSnS4 thin films
by sulfurizing sol-gel deposited precursors," Solar Energy Materials and
Solar Cells, Vol.91, 2007, pp.1199-1201.
[27] N. Nakayama, K. Ito, "Sprayed films of stannite CU2ZnSnS4," Appl Surf
Sci, Vol.92, 1996,pp.171-175.

[28] CM. Muiva, T.S. Sathiaraj, K. Maabong, "Eflect of doping

concentration on the properties of aluminium doped zinc oxide thin films
prepared by spray pyrolysis for transparent electrode applications," Ceramics
International, Vo1.37, 2011, pp.555-560.

[29] G. Taguchi, "Introduction to Quality Engineering," Asian Productivity

Organization, Tokyo, 1986.

[30] W.H. Yang, Y.S. Tamg, J. Mater, "Design optimization of cutting

parameters for turning operations based on the Taguchi method," Journal of
Materials Processing Technology Vol.84, 1998, pp. 122-129.

[31] Y Arba, M. Rafi, H. Tchognia, B. Hartiti, A. Ridah, P. Thevenin, "Effect

of substrate temperature on physical properties of CZTS thin films," Journal
of Optoelectronics and Advanced Materials, Vol. 15, 2013, pp. 1200 - 1203.

[32] S. Thiruvenkadam, D. lovina, A. Leo Rajesh, "The influence of

deposition temperature in the photovoltaic properties of spray deposited CZTS
thin films," Solar Energy, Vol.l06,2014, pp.166-170.

[33] JA. Ghani, I.A. Choudhury, H.H. Hassan, "Application of Taguchi

method in the optimization of end milling parameters," Journal ofMaterials
Processing Technology, Vol.J 45, 2004, pp. 84-92.

[34] K.D. Kim, D.W. Choi, YH. Cho, H.T. Kim, "Optimization of parameters
for the synthesis of zinc oxide nanoparticies by Taguchi robust design
method," Colloids and Surfaces A: Physicochemical and Engineering
Aspects, Vo1.311, 2007,pp. 170-173.

[35] Y M. Chiang, H.-H. Hsieh, 'The use of the Taguchi method with grey
relational analysis to optimize the thin-film sputtering process with multiple
quality characteristic in color filter manufacturing," Computers & Industrial
Engineering, Vo1.56, 2009, pp. 648-661.

[36] L.-I. Tong, C.-I. Su, "Optimizing multi-response problems in the

Taguchi method by fuzzy multiple attribute decision making," Quality and
Reliability International, Vol.J 3, 1997, pp.25-34.

[37] L.-J. Chen, Y-J. Chuang, "Quaternary semiconductor derived and

formation mechanism by non-vacuum route from solvothermal nanostructures
for high-performance application," Materials Letters, Vol.91, 2013, pp.372-
375.

[38] H. Park, Y H. Hwang, B-S. Bae, "Sol-gel processed CU2ZnSnS4 thin

films for a photovoltaic absorber layer without sulfurization," J Sol-Gel Sci
Technol., (2012) doi: 1O.1007/sI0971-012-2703-0.