Journal of Alloys and Compounds 542 (2012) 22–27

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Journal of Alloys and Compounds

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Cu2ZnSnS4 thin films deposition by ultrasonic spray pyrolysis

W. Daranfed a, M.S. Aida a,⇑, N. Attaf a, J. Bougdira b, H. Rinnert b
a
Université de Constantine, Laboratoire de Couches Minces et Interfaces, Faculté des Sciences, Algeria
b
Université de Lorraine, Institut Jean Lamour, UMR 7198, Vandoeuvre 54506, France

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

Article history: Cu2ZnSnS4 (CZTS) thin films were deposited by ultrasonic spray pyrolysis technique. The substrate tem-
Received 24 May 2012 perature was varied from 280 to 360 °C in order to investigate its influence on CZTS films properties. The
Received in revised form 29 June 2012 deposition rate shows two activation energies 0.16 and 0.53 eV, respectively at low and high substrate
Accepted 15 July 2012
temperatures. This indicates that CZTS deposition by spray pyrolysis passes by two different processes
Available online 23 July 2012
with increasing temperature substrate. The temperature 320 °C corresponds to the transition between
these two processes. The X rays diffraction (XRD) analysis indicated that the deposited films have a keste-
Keywords:
rite hexagonal structure with (1 1 2) preferential orientation and a crystalline size, ranged from 30 to
CZTS
Thin film
52 nm with increasing substrate temperature. Stannate ZnSnO3 is present as a secondary phase. The pres-
Spray technique ence of this secondary phase causes films optical band broadening. Broad emissions at around 1.27 eV
Solar cells was observed in the photoluminescence spectrum measured at 77 K, it is accompanied with a small peak
located at 1.75 eV due the presence of zinc stannate phase ZnSnO3.
Ó 2012 Elsevier B.V. All rights reserved.

1. Introduction [15]. Generally these techniques are multi steps processes, they
are based on sequential or co-deposition of precursor metallic
Solar cells based on CuIn(Ga)Se2(CIGS) and CdTe have attained stacked layers followed by a subsequent sulfurization or annealing
efficiency of 19.8% and 16.5%, respectively [1]. Nevertheless, issues in H2S atmosphere. However for a large scale solar cell production a
are encountered with these absorbing materials such as scares of In single step deposition process is more economic and well suitable.
and Ga and toxicity of Cd. This may limit the mass production of This can be achieved by co-sputtering technique [16] co-evapora-
solar cells based on these materials. These problems have stimu- tion [17] or by vacuum free chemistry methods such as spray-pyro-
lated the research for an alternative absorber layer that can be pre- lysis [18,19], photochemical deposition [20,21] and sol–gel [22].
pared with abundant and environmental friendly materials. Among these techniques, spray pyrolysis is a versatile and low-
Recently quaternary Cu2ZnSnS4 (CZTS), which is composed of cost one. This technique is very attractive; it has been largely used
abundant and safety materials, has emerged as CIGS and CdTe to produce oxide and sulfide II–VI semiconductors. However, few
alternative. It becomes a promising material for thin films solar cell studies have been devoted to CZTS deposition by spray pyrolysis
absorber layer. CZTS is derived from CuInSe material by replacing [19,23,24]. To our knowledge ultrasonic spray pyrolysis has not
scarce In(III) by abundant elements Zn(II) and Sn(IV) in the ratio been tested in CZTS deposition.
50:50, and toxic selenium by sulfur. In the present work, CZTS thin films have been deposited by
CZTS has a band gap ranged from 1.4 to 1.6 eV, which is close to ultrasonic spray pyrolysis. The effect of substrate temperature on
the optimal value required as solar cell absorber layer [2–4], a high structural, chemical composition, optical and electrical properties
absorption coefficient in the visible solar spectrum wavelengths [1] of CZTS films has been investigated. It is well known that aqueous
and a p-type conductivity. Therefore, these properties promote precursor synthesis route leads to oxide contamination [25]. In
CZTS as potential candidate for photovoltaic materials. The theo- order to minimize contamination with oxide and hydroxide spe-
retical predicted efficiency of CZTS based solar cell is larger than cies a non-aqueous precursor material is used.
30% [5–7]. Efficiency up to 6.77% has been already reached in solar
cells produced with CZTS as absorber layer [8].
2. Experimental details
Several techniques have been employed for preparing CZTS thin
films namely: sputtering [2,9,10], thermal evaporation [11,12], CZTS Thin films were deposited by spray ultrasonic in air. The initial solution is
electron-beam-evaporated precursors [13,14], electrodeposition prepared from copper chloride CuCl2 (0.01 M), zinc acetate (0.005 M), tin chloride
SnCl2 (0.005 M) and thiourea SC(NH2)2 (0.04 M). These salts, used as sources of
different elements (Cu, Zn, Sn and S), are diluted in methanol. In order to optimize
⇑ Corresponding author. Tel.: +21 3663146426. the temperature deposition, the substrate temperature was changed from T = 280 to
E-mail address: [email protected] (M.S. Aida). 360 °C with a step of 20 °C and the spraying duration was fixed at 45 min. The struc-

0925-8388/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jallcom.2012.07.063
 W. Daranfed et al. / Journal of Alloys and Compounds 542 (2012) 22–27 23

tural properties were determined by XRD using Philips X’Pert system with CuKa

(112)
radiation (CuKa = 1.5418 Å). Films morphology and composition were analyzed

(ZnSnO3)
12000 ____CZTS

(ZnSnO3)
using scanning electron microscope equipped with energy dispersive X-rays

(ZnSnO3)
(EDX) microanalysis system. The optical transmission in the UV–visible range ____ZnSnO3

(200)

(204)
(114)

(312)
(300–2400 nm) measurements were performed using Shimadzu UV–3101 PC spec- 10000
trophotometer. The electrical conductivity was achieved in dark at room tempera-
360°C

Intensity (a.u)
ture in a coplanar structure with two evaporated gold stripes contacts onto film
surface. Films morphology and composition were analyzed using scanning electron 8000
340°C
microscope (Hitachi FEG S4800) equipped with energy dispersive X-rays (EDX)
microanalysis system.
6000
For photoluminescence (PL) measurements, samples were excited by a 60 mW
laser diode emitting at 488 nm. The PL signal was analyzed by a monochromator 320°C
(equipped with a 600 grooves/mm grating) and by a photomultiplier tube cooled
4000 300°C
at 190 K. For measurements at low temperature, the samples were inserted in a
cryostat equipped with fused silica windows.
2000 280°C
3. Results and discussion
0
20 30 40 50 60
3.1. Deposition rate
2Theta (degree)
The deposited films are well adherent to the substrates and
Fig. 2. XRD diffraction patterns of CZTS thin films deposited at various substrate
have a dark color; their thicknesses are increased with increasing temperatures.
the deposition substrate temperature as reported in Fig. 1. The lar-
ger measured film thickness is 3 lm, it is obtained after 45 min
deposition at 360 °C substrate temperature. This corresponds to a
55
deposition rate of 66 nm/min. The deposition rate has two activa-
tion energies (as shown in insert Fig. 1): in temperature range 260–
320 °C the activation energy is equal to 0.16 eV, while, in temper-
50
ature range between 320 and 360 °C, it is equal to 0.53 eV. This
indicates that films deposition passes by two processes or by two
kinds of chemical reactions with increasing the deposition temper-
45
Grain Size (nm)

ature. It is hard to further discus these processes due to the lack

about the reactions involved during the spray pyrolysis CZTS depo-
sition. According to insert Fig. 1 three hundred and twenty degree
40
centigrade corresponds to the transition temperature from one
process to the second one.
35
3.2. Structural properties

The X-ray diffraction patterns of CZTS films synthesized at var- 30

ious substrate temperatures are shown in Fig. 2. As can be seen,
peaks assigned to (1 1 2), (2 0 0), (2 0 4) and (3 1 2) planes of CZTS 280 300 320 340 360
are presents in the whole diffraction patterns. These peaks are as- o
Substrate Temperature ( C)

3.5 Fig. 3. Variation of the grain size as a function of substrate temperature.

1.2

1.0 EA2=0.53 eV

3.0 0.8 signed to the kesterite phase (according to the card JCPDS 26-
Ln(T)

0.6 0575). Several authors have mentioned the formation of kesterite

EA1=0.16 eV
0.4
phase with (1 1 2) as preferential orientation [12,16,23]. This phase
Film thickness ( μm)

0.2
is more stable than the possible stannite one [26].
2.5 1.55 1.60 1.65 1.70 1.75 1.80 1.85
1000/T (K)
-1 In a quaternary compound, such as CZTS, it is hard to avoid sec-
ondary phases formation regardless the deposition method. The
quasi-totality of authors have reported the presence of secondary
2.0 phases. The most met ones are CuxS in Cu-rich and ZnS in Zn-rich.
However, at high deposition temperature the secondary phases
disappear. Kamoun et al. [19] have observed the presence of CuS
1.5 and Cu2S as secondary phase in spray deposited CZTS films in the
same substrate temperature then the present study. Kishor et al.
[23] have used larger temperatures ranged from 290 to 450 °C in
order to produce a single phase CZTS by spray pyrolysis technique.
1.0
280 300 320 340 360 They noticed the presence of CuxS and Cu2SnS3 secondary phases
o when low temperature is used. However they succeeded in single
Substrate temperature ( C) phase production only above 370 °C. In our films, the only detected
Fig. 1. Variation of the CZTS thin films thickness as a function of substrate
secondary phase is zinc stannate ZnSnO3 phase, as can be seen in
temperature. Inset figure variation of deposition rate as a function of reverse XRD diffraction patterns (Fig. 2). The difference between our result
temperature used to deduce the deposition activation energy. and Kamoun et al. [19] and Kishor et al. [23] results may originates
24 W. Daranfed et al. / Journal of Alloys and Compounds 542 (2012) 22–27

Fig. 5. Typical EDX spectra obtained in film prepared at 320 °C.

80

70

60 280°C
300°C
Transmittance (%)

50 340°C

40
320°C
30 360°C

20

10

0
500 1000 1500 2000
Wavelenght (nm)

Fig. 6. Transmittance in the visible range of CZTS thin films deposited at various
substrate temperatures.

to the transition from one to another deposition process as sug-

gested from the deposition rate variation.
The crystalline size (D) has been determined from (1 1 2) peak
by using the Scherrer’s formula [27]
Kk
D¼
bcosh
Fig. 4. SEM images of CZTS thin films prepared at substrate temperature: (a)
280 °C; (b) 320 °C and (c) 360 °C. where K is the Scherer constant corresponding to the quality factor
of the apparatus measured with a reference single crystal, k is the
wavelength of the X-ray used; b is the full width at half maximum
from the fact that these author have used an aqueous solution; of the peak and h is the Bragg angle.
however in our case we have used methanol as solvent solution. The crystallite size calculated in different films is ranged from
Nakayama et al. [18] have found a trace of zinc stannate phase in 30 to 52 nm. This is comparable to the reported values in the liter-
sprayed CZTS film deposited by spray with ethanol solution fol- ature [23]. The grain size is enlarged with increasing substrate
lowed by sulfirization. temperature (Fig. 3). This suggests that the films crystallinity is im-
According to the peak intensity located at 33.9°, assigned to the proved with increasing the substrate temperature.
zinc stannate phase (Fig. 2), films prepared with 320 and 360 °C
contain less ZnSnO3 than the other ones. The reduction of the 3.3. Morphology and composition
secondary phase in film prepared at 360 °C may originate from
the increase in the deposition temperature. However, in the case Fig. 4(a–c) show surface SEM images of CZTS films prepared at
of film prepared at 320 °C, we speculate that the reduction in the different substrate temperatures. As can be seen, films are com-
secondary phase may due to that this temperature corresponds posed with granular structure and rough surface. Voids and small
 W. Daranfed et al. / Journal of Alloys and Compounds 542 (2012) 22–27 25

8
8.0x10

(α hν ) (cm eV )
2
-2
2
8
4.0x10

Eg=1.41 eV

0.0
0 1 2 3
Photon Energy (eV)
2
Fig. 7. Typical variation of the quantity (ahv) as a function of photon energy, for the sample prepared at 300 °C, used for the determination of the optical gap.

cavities can be observed in films micrograph deposited at low tem-

1.7
perature (Fig. 4a). However, films become compact with densely
packed grains with increasing substrate temperature (Fig. 4b and
c) This is consistent with crystallinity improvement as deduced
from XRD analysis.
The elemental composition of CZTS films is determined by 1.6
means of EDX. There is a deviation from the stochiometry in the
Optical gap (eV)

whole deposited films. The same conclusion has been reported

by several authors [18–23]. The obtained films are Zn-rich, Cu-poor
and sulfur deficient as can be seen in Fig. 5 showing a typical re- 1.5
corded EDX spectrum. It is generally reported that CZTS films are
sulfur deficient due to its volatility [22]. Since our films are Cu-
poor, this explains then the absence of Cu based secondary phases
and the densely compact structure [12]. 1.4

3.4. Optical properties

In Fig. 6 is reported the transmittance spectra of films deposited 1.3

280 300 320 340 360
with various substrate temperatures. The optical band gap of CZTS
o
films is estimated, as shown in Fig. 7 from the plot of (ahv)2 as a Substrate temperature ( C)
function of photon energy hv, according to Tauc formula for direct
Fig. 8. Variation of the optical band gap of CZTS films as a function of substrate
bang gap semiconductor [28]:
temperature.

ðahvÞ2 ¼ Bðhv  Eg Þ
have reported in Cu-poor CZTSe [33–35] where optical gap ranged
where a is the absorption coefficient, B is a constant, Eg is the optical
from 1.6 to 1.35 eV are reported.
gap energy, v is incident photon frequency and h is the Planck’s
The refractive index of CZTS films were measured by ellipsom-
constant.
etry, at 628 nm laser radiation, using film deposited on Si sub-
The variation of the deduced optical gaps with substrate tem-
strate. In Fig. 9 we have reported the variation of the measured
perature is reported in Fig. 8. The obtained optical gaps are within
refractive index as a function of substrate temperature. As can be
the range from 1.4–1.6 eV which is in good agreement with CZTS
seen the refractive index is enhanced with increasing substrate
band gap values reported by other authors [18,29]. The presence
temperature. The increase in the refractive index is a signature of
of ZnSnO3 phase causes the enlargement of the optical band gap
the film densification and crystallinity improvement, which is in
since this phase has a large band gap 2.42 eV. As can be seen, films
good agreement with SEM observations and XRD analysis results.
prepared at 320 and 360 °C have the lowest band gap 1.4 eV which
is close the stoichiometric value of CZTS [30]. This is due to the
reduction of ZnSnO3 in these films as deduced from XRD analysis. 3.5. Electrical conductivity
The same observation of optical broadening due to the incorpora-
tion of ZnS as secondary phase (optical gap of ZnS is equal to In Fig. 10 we have reported the variation of CZTS dark conduc-
3.5 eV) has been observed in CuInS2 [31]. tivity as a function of substrate temperature. The obtained films
The large optical band gap measured in our films (1.6–1.4 eV) have large conductivity, it varies from 0.8 to 6 (X cm)1. Our films
can be due also to their composition. It has been claimed that conductivities are relatively higher than the reported ones in the
Cu-poor CZTS film has a large optical band gap [32]. Similar trend literature. Nakayama et al. [18] have prepared, CZTS films using
26 W. Daranfed et al. / Journal of Alloys and Compounds 542 (2012) 22–27

2.8 10
Experimental data points
Fitted curve

2.6 8

PL Intensity
Refractive index

6
2.4

4
2.2

2
2.0

0
0.75 0.90 1.05 1.20 1.35 1.50 1.65 1.80 1.95
1.8
280 300 320 340 360 Photon energy, eV
o
Substrate temperature ( C) Fig. 11. PL spectra of the CZTS thin films grown at substrate temperatures of 320 °C.

Fig. 9. Variation of the refractive index measured at 628 nm in CZTS films as a

function of substrate temperature. 3.6. Photoluminescence

Fig. 11 shows the photoluminescence spectrum measured at

77 K in CZTS film prepared at 320 °C. As seen, a large and symmet-
6 rical peak of emission localized at 1.27 eV was observed. This peak
was observed by several authors [36,37]. It is assigned to the do-
nor-acceptor pair (DAP) emission. The small peak located at
5
-1

1.75 eV originates from the zinc stannate phase ZnSnO3, since the
Electrical conductivity ( Ω .cm)

energy of this emission is larger than the optical gap of CZTS.

4

4. Conclusion
3
Cu2ZnSnS4 thin films have been successfully deposited by ultra-
sonic spray pyrolysis technique. The effect of substrate tempera-
2 ture on film growth was investigated. The deposition rate have
two activation energies: 0.16 eV at low deposition temperature
1
and 0.53 eV at high temperature suggesting that CZTS thin films
deposition by spray pyrolysis passes by two processes when
increasing substrate temperature. XRD analysis indicates that the
0 deposited films have nanocrystalline keserite structure, the crys-
280 300 320 340 360
talline sizes varies in the range 30–52 nm with increasing sub-
o
Substrate temperature ( C) strate. The films optical band gap was ranged from 1.45 to
1.6 eV. XRD analysis, SEM observation and refractive index mea-
Fig. 10. Variation of the dark conductivity in CZTS thin films as a function of surements indicate that the film crystallinity is improved with
substrate temperature.
increasing substrate temperature. The deposited films are Cu-poor
and contain zinc stannate ZnSnO3 as a secondary phase. All the
deposited films exhibit a p-type conductivity with a relatively high
the spray deposition technique followed by a sulfurization at conductivity by comparison to the literature. Film deposited at
550 °C. Their films have a kesterite structure and exhibit a conduc- 320 °C seems to have a suitable optical and electrical properties
tivity of about 5  103 (X cm)1. Recently Liu et al. [16] have re- for efficient thin film solar cell fabrication.
ported a conductivity value of 0.18 (X cm)1 in CZTS film
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