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Thermal treatments and characterization of CZTS thin films deposited using

nanoparticle ink 1

Article  in  Canadian Journal of Physics · July 2014

DOI: 10.1139/cjp-2013-0572

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 875

ARTICLE
Thermal treatments and characterization of CZTS thin films
deposited using nanoparticle ink1
A. Martinez-Ayala, Mou Pal, N.R. Mathews, and X. Mathew
Can. J. Phys. Downloaded from www.nrcresearchpress.com by University of Saskatchewan on 07/13/14

Abstract: The structural, optical, and optoelectronic properties of copper zinc tin sulfide (CZTS) films, deposited by a non-
vacuum nanoparticle based approach were studied as a function of different annealing temperatures. The CZTS films for
photovoltaic applications were deposited using the doctor blading method using an ink prepared with nanoparticles synthesized
using the solvothermal method. Deposited films were annealed at different temperatures in N2–S atmosphere. The films were
characterized using different tools such as X-ray diffraction, scanning electron microscopy (SEM), energy dispersive X-ray
spectroscopy (EDXS), ultraviolet–visible spectroscopy, Raman spectroscopy, and photoconductivity. The results showed that the
kesterite phase was formed in the temperature range between 400 and 550 °C. At temperatures beyond 500 °C, many peaks of
binary and ternary phases were detected, probably because of the decomposition of the kesterite layer. The cross section SEM
images showed that the film is compact; however, there are isolated voids. The EDXS estimated chemical composition was found
to vary with annealing temperature; the nearly stoichiometric film was obtained when annealed at 450 °C. The optical band gap
of the stoichiometric film was 1.6 eV, and it showed photoconductivity.

PACS Nos.: 73.61.Cw, 78.30.Hv, 72.40.+w.

Résumé : Nous étudions, à différentes températures de recuit, les propriétés structurales, optiques et optoélectroniques de
films de sulfure de cuivre, zinc et étain (CZTS), déposés dans une approche à nanoparticules sans faire le vide. Les films CZTS
For personal use only.

pour des applications photovoltaïques sont déposés et égalisés par tige de verre (doctor blade) utilisant une encre préparée
avec des nanoparticules synthétisées par méthode solvo-thermale. Les films déposés sont soumis à un recuit à différentes
températures dans une atmosphère de N2–S. Les films sont caractérisés à l’aide de différentes techniques, comme la
diffraction X, la microscopie électronique à balayage (SEM), la spectroscopie X dispersive (EDXS), la spectroscopie Raman et
la photoconductivité. Les résultats montrent que la phase kësterite se forme entre 400 et 550 °C. Au delà de 500 °C, nous
détectons plusieurs raies de phases binaires et tertiaires. Les images de la section efficace SEM montrent que le film est
compact; cependant il y a des vides isolés. L’estimé de la composition chimique par EDXS varie avec la température de recuit;
nous obtenons un film pratiquement stœchiométrique pour une température de recuit de 450 °C. La bande interdite optique du
film stœchiométrique est de 1.6 eV et montre de la photoconductivité. [Traduit par la Rédaction]

1. Introduction solution-based techniques. Vacuum-based deposition methods

Cu2ZnSnS4 (CZTS), a copper-based quaternary chalcogenide has
drawn much attention as a low-cost absorber material for thin
film solar cells. It has a direct band gap of 1.4–1.5 eV [1, 2] with a
high optical absorption coefficient (of the order 104 cm−1) [3, 4],
which make it suitable for application in solar cells. In addition,
the material availability and nontoxicity of the constituent ele-
ments are important considerations for large scale production of
CZTS based photovoltaic devices. Although thin film solar cells
based on cadmium telluride (CdTe) and copper indium gallium
diselenide (CIGS) have reached excellent power conversion effi-
ciencies of about 18% and 20%, respectively, the toxicity issue of
heavy metal cadmium and limited availability of indium (In) and
tellurium (Te) restrict the massive production of CdTe and CIGS-
based photovoltaic panels. Compared to CdTe and CIGS technol-
ogies, the CZTS based solar cells yielded efficiency as high as 11% as
reported by Todorov et al. [5]. However, theoretical considerations
predict maximum power conversion efficiency of about 32%,
which means there is enough room for further improvement [6].
CZTS thin films have been deposited by various techniques,
broadly classified into two major categories: vacuum-based, and
(i.e., sputtering and thermal evaporation) have the advantages of
producing thin films with controllable chemical composition,
high uniformity, and good reproducibility [7]. However, these
techniques are relatively slow and suffer from low material utili-
zation and high energy consumption. In comparison to vacuum-
based techniques, solution-based approaches are low-cost and
high throughput printing or spraying techniques are being exten-
sively pursued as alternative to the expensive vacuum based tech-
niques. Some of the nonvacuum techniques that are explored
widely in recent years are electrochemical deposition [8], sol-gel
technique [9], spray pyrolysis [10], and ink-printing approaches
[11–13]. In particular, the strategy of depositing thin film using
nanoparticle ink/paste under atmospheric condition and subse-
quent thermal processing to make high quality absorber layers is
becoming more popular due to the process simplicity and low
cost. The key step in this approach is to formulate nanoparticle
based ink or paste with suitable viscosity and substrate wetting
capacity to produce smooth, uniform thin film layer. Subsequent
thermal processing must allow the removal of organic solvents or
additives used in ink formulation leaving minimal carbon

Received 16 October 2013. Accepted 9 December 2013.

A. Martinez-Ayala, M. Pal, N.R. Mathews, and X. Mathew. Instituto de Energías Renovables, Universidad Nacional Autónoma de México, Temixco,
Morelos 62580, México.
Corresponding author: X. Mathew (e-mail: xm@ier.unam.mx).
1This paper was presented at the 25th International Conference on Amorphous and Nanocrystalline Semiconductors (ICANS25).

Can. J. Phys. 92: 875–878 (2014) dx.doi.org/10.1139/cjp-2013-0572 Published at www.nrcresearchpress.com/cjp on 21 January 2014.
 876 Can. J. Phys. Vol. 92, 2014

impurities in the film. The primary objective of the present study Fig. 1. XRD patterns of Cu2ZnSnS4 films annealed at different
is to explore the feasibility of depositing CZTS films using a temperatures.
nanoparticle-based paste prepared with an organic solvent, fol-
lowed by thermal annealing process that lead to the formation of 550 ºC CZTS
dense and compact film. The structural, optical, compositional Cu2SnS3

Cu2SnS3
Cu2SnS3
Cu2SnS3
Cu2SnS3
and photo-response properties of the films have been evaluated. SnO2

Sn3S4
ZnS

Sn

+
Intensity (arb.units)
2. Experimental
In this work CZTS layer was deposited on conducting glass sub- 500 ºC
strate using a nanoparticle-based ink by non-vacuum doctor blad-

(112)
ing method. Ink was made by dispersing 10 mg of solvothermally

(220)
(200)

(224)
synthetized CZTS nanoparticles [14] in a mixture containing

(211)

(332)
(008)
Can. J. Phys. Downloaded from www.nrcresearchpress.com by University of Saskatchewan on 07/13/14

250 ␮L of oleic acid and 200 ␮L of dilute acetic acid (1 mL of glacial

acetic acid in 50 mL of deionized water). This mixture was thor-

(112)
450 ºC
oughly agitated to obtain a homogeneous paste. The paste was

(220)
(211)
applied on cleaned glass substrate (TEC 15) and was spread by

(224)
sliding a glass rod over 50 ␮m thick scotch tape spacers, forming

(200)
(101)

(332)
(008)
a uniform film between the spacers. The deposited film was pre-
heated to 200 °C for 1 min on a hot plate and then subjected to
thermal treatment at 400, 450, 500, and 550 °C for 30 min in N2–S 400 ºC

(112)
atmosphere. The structural and optical properties of the films

(220)
were characterized by X-ray diffraction (XRD), Raman scattering,

(224)
(200)

(211)

(332)
(008)
scanning electron microscopy (SEM), energy dispersive X-ray spec-
troscopy (EDXS), and ultraviolet–visible absorption spectroscopy.
The photoresponse of the film with adequate stoichiometry was 10 20 30 40 50 60 70
evaluated to check their suitability in photovoltaic application. To
measure the photo response, carbon contacts were painted on the 2 (degrees)
film surface in a coplanar configuration and the film was illumi-
For personal use only.

nated using a tungsten halogen lamp. The illumination intensity Fig. 2. Raman spectra of CZTS films annealed at different
was approximately 45 mW/cm2. temperatures. (*) indicates the position of 356 cm−1 band
corresponding to Cu2SnS3 phase.
3. Results and discussion

338
288
Figure 1 shows the XRD patterns of the CZTS films annealed at
297

368
different temperatures (400, 450, 500, and 550 °C) in N2–S atmo-
sphere. The sulfur atmosphere was maintained during the ther-
Intensity (arb.units)

mal treatment to compensate for any loss of sulfur from the films 346
during the process. The characteristic peaks of CZTS correspond- 550 º C
ing to the tetragonal phase (Kesterite JCPDS No. 26-0575) along the
303

planes (112), (200), (211), (220), (224), (008), and (332) were observed.
267

The films showed a preferential orientation towards (112) plane.

The possible presence of ZnS phases can be detected for the films *
500 º C
annealed at 500 °C. The peaks of SnO2 can be attributed to the
substrate. At an annealing temperature of 550 °C, the films were
found to undergo decomposition to binary and ternary phases, *
such as Sn3S4, ZnS, and Cu2SnS3 as indicated in the figure. The 450 º C
average crystal size was estimated using the Debye Scherrer for-
mula; the calculated values were 12, 22, and 24 nm for the films
400 º C
annealed at 400, 450, and 500 °C, respectively. The films annealed
at 450 °C showed better recrystallization, and also a decrease in
the intensity of the binary and ternary phases, which was other-
wise observed for the films annealed at 500 °C and above. 200 300 400 500 600
To confirm that the films are CZTS, the samples were further -1
analyzed using Raman spectroscopic techniques as shown in Raman shift (cm )
Fig. 2. In the spectra of CZTS films annealed at 400, 450, and
500 °C, the major Raman modes at 288, 338, and 368 cm−1 corre-
sponding to the CZTS phase was observed [15–18]. Although an
increase in annealing temperature up to 500 °C has improved the Table 1 summarizes the composition ratios of CZTS films an-
crystalline quality of the CZTS films, a few weak bands began to nealed at different temperatures. The Cu/(Zn + Sn) and Zn/Sn ra-
appear at 267, 303, and 356 cm−1 corresponding to the cubic tios were not calculated for the film annealed at 550 °C as the
Cu2SnS3 phase. This result indicates that the decomposition of crystal structure of the film did not correspond to the kesterite
CZTS into binary and ternary phases is evident at higher anneal- phase as evidenced by XRD and Raman results. In all cases, the
ing temperature. When the film was annealed at 550 °C, the kes- CZTS films show the tendency towards copper poor and Zn rich
terite phase did not exist anymore, which is evident from the composition, which is similar to the desired stoichiometry of
absence of the characteristic CZTS Raman bands. Instead, two CZTS films to achieve improved device performance [19]. The film
bands corresponding to cubic Cu2SnS3 and ZnS phases were ap- annealed at 450 °C has shown the closest composition to the
peared at 297 and 346 cm−1, respectively. desired stoichiometry.

Published by NRC Research Press

 Martinez-Ayala et al. 877

Table 1. Chemical composition of CZTS films annealed at different temperatures.

Temperature (°C) Cu (% atom) Zn (% atom) Sn (% atom) S (% atom) Cu/(Zn+Sn) Zn/Sn
400 20 16 14 50 0.66 1.14
450 24 14 12 50 0.92 1.16
500 25 14 14 47 0.89 1.0
550 31 30 19 20 − −

Fig. 3. Surface morphology of the CZTS films annealed at (A) 400 °C, (B) 450 °C, and (C) 500 °C for 30 min. (D) Cross section view of CZTS layer
annealed at 450 °C for 30 min (TCO, transparent conducting oxide layer). (E) The SEM image of a film annealed at 450 °C for 60 min.
Can. J. Phys. Downloaded from www.nrcresearchpress.com by University of Saskatchewan on 07/13/14

Fig. 4. EDXS spectra of the CZTS film annealed at 450 °C: (a) At a spot on a grain; and (b) over an area of 1.0 ␮m2 on a large grain.
For personal use only.

Figure 3 shows SEM micrographs of morphology of the films Table 2. EDXS estimated chemical composition at different regions of
annealed at 400, 450, and 500 °C for 30 min. In general, the films the film (Fig. 3E).
are porous and consist of irregular shaped crystallites assembled Area
from stacked nanoparticles. With increasing annealing tempera-
ture, the films show improved crystallinity and compactness. The Spot analysis on 1 ␮m2 area over Away from
cross-sectional view of the film annealed at 450 °C (Fig. 3D) illus- Element the grain (%) the grain (%) the grain (%)
trates the formation of a continuous layer free of cracks but with Cu 25 26 22
voids. As we can see, the thickness is approximately 2–2.5 ␮m. The Zn 17 14 17
image shown in Fig. 3E corresponds to a film annealed at 450 °C Sn 15.5 12 13
for 60 min. It is clear that longer annealing duration significantly S 42.5 48 48
enhances the grain growth; the film contains large, well-defined Cu/(Zn+Sn) 0.77 1.0 0.73
crystallites with grain dimensions about 1 ␮m. Zn/Sn 1.1 1.16 1.3
EDXS analysis was performed specifically on the larger grains
seen in Fig. 3E as well as at regions away from these grains, and
found that in both cases the material stoichiometry corresponds
to the CZTS phase. Figure 4 shows the EDXS spectra obtained at a including that over the larger grains is very similar to each other
spot (Fig. 4a) on one of the large grains, and over an area of 1.0 ␮m2 and close to the desired stoichiometry of CZTS; which indicates
(Fig. 4b) on a large grain shown in Fig. 3E. Table 2 summarizes the that the larger grains are not the segregation of different phases,
atomic percentage of the elements in different regions of the film. but because the recrystallization occurred at higher temperature.
As can be seen, the chemical composition at different regions In general, the films show Cu poor and Zn rich composition,

Published by NRC Research Press

 878
Fig. 5. (␣h␯)2 versus (h␯) of CZTS film annealed at 400 and 450 °C.
8
3x10
400 °C
9
1.2x10
2
( hv) (cm ev)
8
2x10
-1
8
8.0x10
2
Can. J. Phys. Downloaded from www.nrcresearchpress.com by University of Saskatchewan on 07/13/14
8
1x10
8
4.0x10
E =1.56 eV
g g
0 0.0
1.5 1.8 2.1 2.4
Photon energy (eV)
which is similar to the desired stoichiometry of CZTS films for
achieving optimal device performance [20]. Even though longer
annealing duration resulted in larger grains with adequate stoi-
chiometry, we were unable to obtain pinhole-free films for
photoconductivity measurements. Hence in this paper we are dis-
cussing films annealed for 30 min duration. Because the films
For personal use only.
annealed at temperatures higher than 450 °C showed deviation
from desired stoichiometry and phase purity, we used only those
films annealed at 400 and 450 °C to estimate the band gap and
photoconductivity.
The absorption coefficient (␣) was extracted from the transmit-
tance (T) data using the formula ␣ = ln(1/T)/t, where t is the film
thickness. The average absorption coefficient of the film was
higher than 104 cm−1 in the visible region. Figure 5 shows the
(␣h␯)2 versus (h␯) plot for the CZTS film annealed at 400 and 450 °C
for 30 min. The band gap energy was estimated by extrapolating
the linear part of the plot to meet the photon energy axis, and the
obtained values are 1.56 and 1.6 eV for films annealed at 400 and
450 °C, respectively, which are in the range of values reported in
the literature [21].
Photocurrent response of the films annealed at 400 and 450 °C
was measured as described in Sect. 2. The response of the film
annealed at 400 °C was very poor and we discarded the data be-
cause of poor signal-to-noise ratio. The photocurrent response of a
film of approximately 3 ␮m thickness and annealed at 450 °C for
30 min is shown in Fig. 6. The current was measured in dark and
under illumination with an applied potential of 1 V. Prior to the
measurement, the film was kept in the dark for 30 min for stabi-
lization. After the stabilization period the current was monitored
at fixed intervals in the following sequence: 20 s dark, 20 s under
illumination, 20 s dark. The sharp rise and fall of the photore-
sponse with respect the illuminating pulse can be taken as an
indication of low level or near-absence of trap states in the band
gap of the material. The estimated value of the conductivity in
dark was 5.94 × 10−8 (⍀cm)−1.
4. Conclusion
CZTS films were successfully deposited on glass substrates by a
simplified doctor blading method using a nanoparticle-based ink.
Annealing temperature in the range of 450 °C was identified as
adequate for the postdeposition thermal treatments of CZTS film
in ambient N2 and S. The formation of the kesterite phase was
confirmed by XRD and Raman studies. The annealed film was
near-stoichiometric, with copper poor and zinc rich composition,
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Can. J. Phys. Vol. 92, 2014
Fig. 6. Photocurrent response of a typical CZTS thin film developed
from the nanoparticle ink and annealed at 450 °C for 30 min in N2–S
atmosphere.
450 °C
E =1.6 eV
1.5 1.8 2.1 2.4 which is recommended to obtain CZTS solar cells with higher
efficiency. The absorption coefficient of the CZTS layer was higher
than 104 cm−1 in the visible region and a direct optical band gap
approximately 1.67 eV. The film showed photoresponse indicating
that the developed films are quite promising for the fabrication of
solar cells.
Acknowledgements
This work at IER–UNAM was supported by the project CONACyT
129169. Authors acknowledge the support of M.L.R. Garcia in XRD
analysis, G.C. Segura for SEM measurements and central labora-
tory of IFUAP, BUAP for Raman analysis.
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