Thin Solid Films 551 (2014) 4245

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Thin Solid Films

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

Cu2ZnSnS4 thin lms by simple replacement reaction route for solar

photovoltaic application
Devendra Tiwari a,, Tapas K. Chaudhuri a, Arabinda Ray b, Krishan Dutt Tiwari c
a
b
c

Dr. K. C. Patel Research and Development Centre, Charotar University of Science and Technology, Changa, Anand District, Gujarat 388421, India
P. D. Patel Institute of Applied Sciences, Charotar University of Science and Technology, Changa, Anand District, Gujarat 388421, India
Powerdeal Energy Systems (India) Private Limited, Nashik 422010, Maharashtra, India

a r t i c l e

i n f o

Article history:
Received 7 February 2013
Received in revised form 22 November 2013
Accepted 22 November 2013
Available online 1 December 2013
Keywords:
Replacement reaction
Copper zinc tin sulde
Thin lm solar cells
Solution deposition

a b s t r a c t
A process for deposition of Cu2ZnSnS4 (CZTS) lms using replacement of Zn2+ in ZnS is demonstrated. X-ray
diffraction pattern and Raman spectroscopy conrm the formation of pure CZTS. Atomic force microscopy
shows the lms to be homogeneous and compact with root mean squared roughness of 6 nm. The direct band
gap of CZTS lms as elucidated by UVVis-NIR spectroscopy is 1.45 eV. The CZTS lms exhibit p-type conduction
with electrical conductivity of 4.6 S/cm. The hole concentration and hole mobility is determined to be
3.6 1017 cm3 and 1.4 cm2V1 s1 respectively. Solar cells with structure: graphite/CZTS/CdS/ZnO/SnO2:In/
Soda lime glass are also fabricated, gave photo-conversion efciency of 6.17% with open circuit voltage and
short circuit current density of 521 mV and 19.13 mA/cm2, respectively and a high ll factor of 0.62. The external
quantum efciency of the solar cell lies above 60% in the visible region.
2013 Elsevier B.V. All rights reserved.

1. Introduction
In the search of sustainable and low-cost alternatives for thin lm
solar cells (TFSCs), Cu2ZnSnS4 (CZTS) and its selenide derivatives
based solar cells have taken quantum leap. Unlike, the conventional
TFSC absorber materials such as chalcopyrites like Cu(In,Ga)Se2 and
binary IIVI compounds such as cadmium telluride which are based
on less abundant elements: In, Ga and Te, and toxic element: Cd, CZTS
is based on earth's abundant and environmentally benign elements,
thus, lowers the input material costs, prolongs sustainability, and
saves tomorrow's environment [1,2].
There are ample reports of solar cells based on CZTS, which utilize
vacuum based deposition route such as sputtering, thermal evaporation,
pulse laser deposition etc. [38]. Vacuum based deposition techniques
suffer certain drawbacks like high input capita, low throughput and
difculties of deposition on large areas. These drawbacks, therefore,
will not allow in achieving the ultimate goal of low-cost and sustainable
conversion of energy using TFSC. Thus, It is required to use non-vacuum
based coating techniques. Direct liquid coating techniques offers the
advantage over vacuum based techniques in respect of input capita,
material utilization, throughput and large area deposition [9]. The
workers at IBM and various universities have contributed substantially
in this direction and have demonstrated the huge potential of CZTS
(and its selenides) for low-cost solar photovolatics by fabricating high
efcient TFSCs (highest of which has gone above 10% now), using direct
liquid coating deposition routes [1012].

Corresponding author. Tel.:+91 76982 85145.

E-mail address: devendratiwari.rnd@ecchanga.ac.in (D. Tiwari).
0040-6090/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.tsf.2013.11.095

Presently, the high performance direct liquid coating deposition

routes for deposition of CZTS either utilize (1) colloidal CZTS
nanoparticles, (2) binary metal suldes solution based inks or
(3) sulfurization of metal precursor. However, these necessitate
controlled and tedious synthesis requiring certain costly capping
materials and special conditions or require toxic solvent and long
time for preparation of inks or high temperature and high pressure
sulfurization. Although, these may be sorted out for solar cell production, however it was thought worthwhile to attempt yet another
simpler route based on replacement reaction. Owing to the position
of Zn2 +(aq.) to Zn (s) equilibrium in electrochemical series, Zn2 +
in bivalent compounds of Zn, can be replaced with other metal ions
such Cu 2 +, Sn2 + etc. In this report, a simple route for depositing
CZTS lms by replacement reaction using ZnS lms is demonstrated,
which is easily upscalable for production. Also, using this method, a
solar cell has been fabricated and studied.
2. Experimental
2.1. Synthesis
CZTS layer is deposited by replacement reaction.
Step 1: First ZnS layer is deposited on to a soda lime glass (SLG) substrate
(7.62 2.54 sq. cm) by chemical bath deposition [13]. The bath
consists of zinc acetate and thiourea as zinc and sulfur sources,
respectively. Triethanol amine and trisodium citrate are used
as complexating agents. The pH of the nal bath (before
deposition) is 10.5 and temperature of bath during deposition
is maintained at 353 K.

D. Tiwari et al. / Thin Solid Films 551 (2014) 4245

43

Step 2: In a separate 50 ml beaker, metal salts: cupric chloride (0.2 M),

zinc chloride (0.1 M) and stannous chloride (0.1 M) are dissolved in glycerol.
Step 3: Chemical bath deposited ZnS lm (prepared in step 1) is
immersed in glycerolic metal salt solution (prepared in step
2), for a maximum of 10 min, resulting in black shiny lm.
Deposited lms are then rinsed with distilled water and dried
with jet of dry air. Use of other polar solvents, instead of
glycerol, such as water, alcohol (methanol, ethanol, propanol,
2-propanol) or acetone, although resulted in fast reaction, the
resulting lms are not adherent and sometimes peel off in the
reaction bath.
Solar cell based on replacement reaction route coated CZTS is fabricated on Indium doped Tin Oxide (ITO) coated SLG substrates with
structure: graphite/CZTS/CdS/ZnO/ITO/SLG. First, ITO coated SLG substrate is deposited with ZnO using solgel technique by spin-coating
[14]. The solution for deposition ZnO consists of zinc acetate (0.3 M)
as zinc source, while 2-methoxy ethanol and monoethanol amine
(MEA) are used as solvent and stabilizer, respectively. The molar ratio
of zinc acetate to MEA is maintained to be 1:1. The solution is spin
coated into ITO coated SLG substrate (2.54 2.54 sq. cm) and then
heated at 423 K in air for 10 min. The nal annealing is carried out at
723 K for 2 h in air. CdS buffer layer is deposited by chemical bath
deposition (CBD) method [15]. Chemical bath composes of cadmium
acetate (0.5 mM) and thiourea (5 mM) as Cd and S sources, respectively.
The rate of deposition is controlled by using a buffer of ammonium
acetate (0.03 M) and ammonium hydroxide (0.5 M). During deposition,
the temperature of the bath is maintained at 353 K. Upon this structure:
SLG/ITO/ZnO (solgel)/CdS (CBD), CZTS lm is deposited by the replacement reaction route (as discussed above). Top contacts are obtained by
painting circular pads of colloidal graphite (Ted Pella). The total active
area of the device is 0.35 cm2. All the reagents used during the deposition are of analytical grade procured from Merck.
2.2. Characterization
The structural composition of the lm is determined from X-ray
diffraction (XRD) pattern taken with a Diffractometer (Bruker, D2 Phaser)
using Ni-ltered CuK (1.5418 ) radiation and step size of 0.02o. The
Raman spectrum of the lms is obtained using micro Raman spectrophotometer (Jobin-Yvon, HR 800) in the range of 200450 cm1. The
cross-sectional view of the solar cell is examined by Scanning Electron
Microscopy (FEI, Quanta-200) operating at 20 kV. Prior to analysis
sample is sputter-coated with Au to avoid charging effects. The elemental
composition is determined by an Oxford Link ISIS energy dispersive
analysis of X-rays (EDAX) equipment attached to the Scanning Electron
Microscope (FEI, Quanta-200) and prior to the EDAX analysis, calibration against Cu standard (Cu k, 8.040 keV) is performed. The surface
morphology of the lms is examined by Atomic Force Microscope
(Nanosurf Easyscan2). Optical spectrum is measured with a UVVIS-NIR
Spectrophotometer (PerkinElmer Lambda 9). The Hall Effect measurements are carried out at room temperature on 1 1 cm2 lm sample
with graphite paint electrodes employing standard four-probe technique, data is recorded x. The resistivity measurements are performed
by the standard four-probe technique using a cryostat in the temperature range of 5 to 290 K. The performance of solar cell is evaluated
under standard AM 1.5 illumination.
3. Results and discussion
3.1. Structure and composition
The X-ray diffraction pattern of a typical lm is shown in Fig. 1.
The XRD clearly shows four sharp peaks which match with the standard
CZTS Kesterite XRD data (JCPDS le: 26-0575). On comparison with the

Fig. 1. X-ray diffraction pattern of Cu2ZnSnS4 lm along with quantitative structure

renement t.

standard le, the four peaks at 2Theta values of 28.6, 32.9, 47.5 and
56.4 are assigned to reections from (112), (200), (220) and (312)
planes of kesterite CZTS structure, respectively. Absence of any other
peak due to binary tertiary phases indicates the formation of pure
kesterite CZTS.
For the quantitative phase analysis, full prole Reitveld analysis of
XRD pattern of CZTS powder is performed using Topas 4.2 software.
Thermal parameters are constrained in xed range during renement.
Sum of occupancies have been set to 1. The tted prole of XRD plot
is shown in Fig. 1. The structure belongs to I-42 m space group with
tetragonal structure. The Goodness of Fit and R weighted prole values
for tting are 1.41 and 2.26 respectively. The lattice parameter thus
obtained are a = 0.5423 nm and c = 1.0844 nm. The site occupancies
of ions along with their fractional coordinates are shown in Table 1.
Since the structure of CZTS is similar to other zinc-blende structure
materials such as Cu2SnS3 and ZnS, diffraction pattern of all these phases
have been found to be overlapping [16]. The conrmation of formation
of CZTS is done using Raman spectroscopy. Fig. 2 shows Raman spectrum for CZTS lms along with band tting prole. The deconvoluted
spectrum shows three peaks at 289 cm1, 338 cm1 and 368 cm1,
which matches with the previous report on Raman spectroscopy of
CZTS [16]. The main peak at 338 cm1 is due to A1 vibrational mode,
arising from the vibration of S atoms in CZTS lattice while rest of
the atoms remains stationary. Hence the Raman spectroscopic study
conrms the formation of CZTS only.
Energy dispersive analysis of X-rays (EDAX) depicting the elemental
composition of CZTS lm is shown in Fig. 3. EDAX shows the presence of
Cu, Zn, Sn, S as the major elements, in a relative atomic ratio of about 21,
15, 14 and 50 at.%, respectively. The [Cu]/([Zn] + [Sn]) and [Zn]/[Sn]
ratios being 0.74 and 1.1, respectively indicating a slightly Cu decient
and Zn rich stoichiometry.

3.2. Morphology
The atomic force micrograph of the CZTS lm deposited on glass is
shown in Fig. 4. The micrograph shows formation of nearly spherical
Table 1
Structural parameters of Cu2ZnSnS4 obtained after Rietveld renement.
Site

Occupancy

Cu1A
Cu1B
Sn1A
Sn1B
Cu2
Zn1
S1

0
0.5
0.5
0
0
0.5
0.7667

0
0.5
0.5
0
0.5
0
0.7667

0
0.5
0.5
0
0.25
0.25
0.8786

0.832
0.168
0.832
0.168
1
1
1

44

D. Tiwari et al. / Thin Solid Films 551 (2014) 4245

Fig. 2. Raman spectrum of Cu2ZnSnS4 lm along with band tting prole.

grains with sizes varying between 90 and 130 nm. The root mean
squared (rms) roughness of lms is around 6 nm, indicating deposition
of smooth lms. It is expected that the grain size can be manipulated by
choosing an appropriate solvent to control the rate of replacement
reaction which in turn may constrain the growth of grains on substrate
and to some extent, using ZnS lms with varying grain size. In general,
the deposited lms are compact and devoid of any crack.

Fig. 4. Atomic force micrograph of Cu2ZnSnS4 lm.

be 3.6 1017 cm3 and 1.4 cm2V1 s1 respectively. Fig. 6 shows the
plot of variation of dark conductivity of the lms with temperature as
well its theoretical t to Eq. (1).

3.3. Optical properties

The transmission and reectance spectra of CZTS lm on glass, in
the wavelength range of 1100300 nm are shown in Fig. 5a. The transmission decreases sharply from 1050 nm to 650 nm, forming a low
angle slope near the end of absorption edge. The transmission and
reectance data are used to calculate the absorption coefcient ()
using relation: = 1/d[ln (1-R2)/T], where d is the thickness, R and T
are reectance and transmittance, respectively. The absorption coefcient
is determined to be N 104 cm 1 at the onset of absorption edge. The
tting of optical spectrum data for different possible exponent values
(n = 2, 1/2, 3/2, 3) in Tauc relation (h = (Egh)n),in the studied
wavelength region, suggests direct band gap electronic transition
(i.e. n = 1/2). The value of direct band gap as determined from Tauc
plot of (h)2 versus h (Fig. 5b), is found to be 1.45 eV. The values
of absorption coefcient and the band gap match with literature values
[38].
3.4. Electrical properties
The CZTS lms exhibit p-type conduction with electrical conductivity
of 4.6 S/cm. The hole concentration and hole mobility are determined to

Fig. 3. Energy dispersive analysis of X-rays of the Cu2ZnSnS4 lm showing the elemental
composition.

01 exp

1 = !






4
T
E

E3
02 exp 2 03
o
exp

T
kT
Tn
kT

where, 01 3e2 ph

1 =

NE F
8kT

, ph is the Debye frequency, To kN

E

is the Mott characteristic temperature,NE F is the density of states at Fermi

energy (EF), is a dimensionless constant, is the wavefunction decay
length, 02 is a constant, E2 is nearest activation energy, 03 is a constant
and E3 is grain boundary (GB) barrier energy. The rst, second and third
terms of the Eq. (1) have contributions from Mott variable range hopping
(M-VRH), nearest neighbor hopping (NNH) and thermionic emission
(TE) over GB barriers, respectively. As is seen, the experimental data
ts well to the Eq. (1) over the entire temperature range. The entire
plot can be divided in three regions as apparent from the two distinct
slopes at the extremes of x-axis (b50 K and N150 K) and period of
transition between them. It is found that data below 70 K has prominent
contribution from M-VRH as To/T N N 1, whereas attempt to t an
Arrhenius plot yields insignicant activation energy, in this temperature
range.

Fig. 5. (a) Transmission and reectance spectra of a typical Cu2ZnSnS4 lm and (b) Tauc
plot of (h)2 vs. h plot for determination of energy band gap.

D. Tiwari et al. / Thin Solid Films 551 (2014) 4245

45

Fig. 8. External Quantum Efciency (EQE) of the Cu2ZnSnS4 solar cell.

Fig. 6. Temperature variation of electrical conductivity of a typical Cu2ZnSnS4 lm
(black circles for data points and red line for model t).

Near room temperature, the temperature variation of conductivity

has been explained well using TE over GB, after Seto [17]. In particular,
Seto's model with the exponent n = 0.5 has been used to minimize the
errors due to model assumptions [18]. However, the entire data cannot
be described by M-VRH and TE over GB solely, specically in intermediate temperatures (N50 K and b 150 K) which show a transition
from one transport mechanism to the other. As pointed out by Kosyak
et al. [18], inclusion of an additional mechanism corresponding
to nearest neighbor hopping (NNH) along with the M-VRH and TE
over GB transport mechanisms is required. Thus, in present case also,
a combination of M-VRH, NNH and TE model sufces to explain the
conductivity of CZTS lms over entire temperature range. The NNH
activation energy (E2) and GB barrier energy (E3) for prepared lms
are found to be 143 and 20.5 meV, respectively. These values are close
to that reported in literature [18].

factor. On the other hand, high RS results in low JSC and thus lowering
the PCE of solar cell. The RS can be lowered by annealing the device at
elevated temperatures and using ITO substrate with sheet resistance
(currently at 20 5/sq.).
The external quantum efciency (EQE) of CZTS solar cell thus fabricated is depicted in Fig.8. The plateau EQE maxima lies in visible region
with maximum value of 75.45% at 545 nm. It can be seen that the device
performance is limited up to the onset of Near IR (~ 850 nm). Device
functioning can be extended in Near IR region by lowering the band
gap (currently 1.45 eV) near to ~ 1.1 [1,2]. As reported in literature,
high efcient solar cells are fabricated with CZTSSe systems. These
partial/complete selenized CZTS layer have lower band gap than CZTS
itself (band gap for CZTSe is 0.95 eV) [2]. The band gap of the CZTS
calculated from EQE is 1.51 eV which is similar to the value obtained
from UVVis-NIR spectrum of CZTS lms.
4. Conclusions

3.5. Graphite/CZTS/CdS/ZnO/ITO/SLG solar cell

The JV characteristics of the CZTS based solar cell under illumination is shown in Fig 7. The cross-sectional view of the device along
with demarcations of each layer showing its thickness, is presented
as inset to Fig. 7. The as-fabricated solar cell delivered a power conversion efciency (PCE) of 6.17% with open circuit voltage (Voc) and short
circuit current density (JSC) of 521 mV and 19.13 mA/cm2, respectively
and a high ll factor of 0.62. The series resistance (RS) and shunt resistance (RSH) of solar cell are 5.8 /cm2 and 680 /cm2, respectively.
High RSH/RS (N100) ratio indicates formation of homogeneous potential
barrier devoid of any competing parallel path with different ideality

Fig. 7. JV characteristics of Cu2ZnSnS4 solar cell under illumination (AM 1.5, 100 mA/cm2).
Inset shows cross-sectional scanning electron micrograph of solar cell.

A simple route for deposition of CZTS lms based on metal ion

replacement in ZnS lms is demonstrated. XRD pattern and Raman
spectroscopy conrm the formation pure CZTS. Band gap of CZTS lms
is determined to be 1.45 eV from optical spectroscopy. The solar cell
fabricated using this method yields Power Conversion Efciency of
6.17% with open circuit voltage (Voc) and short circuit current density
(JSC) of 521 mV and 19.13 mA/cm2, respectively and a high ll factor
of 0.62.
References
[1] C. Wadia, A.P. Alivisatos, D.M. Kammen, Environ. Sci. Technol. 43 (2009) 2072.
[2] D.B. Mitzi, O. Gunawan, T.K. Todorov, K. Wang, S. Guha, Solar Energy Mater
Solar Cells 95 (2011) 1421.
[3] H. Katagiri, N. Sasaguchi, S. Hando, S. Hoshino, J. Ohashi, T. Yokota, Solar Energy
Mater Solar Cells 49 (1997) 407.
[4] J. Seol, S. Lee, J. Lee, H. Nam, K. Kim, Solar Energy Mater Solar Cells 75 (2003) 155.
[5] T. Tanaka, T. Nagatomo, D. Kawasaki, M. Nishio, Q. Guo, A. Wakahara, A. Yoshida, H.
Ogawa, J. Phys, Chem. Solids 66 (2005) 1978.
[6] J. Zhang, L. Shao, Y. Fu, E. Xie, Rare Metals 25 (2006) 315.
[7] K. Moriya, K. Tanaka, H. Uchiki, Jpn. J. Appl. Phys. 46 (2007) 5780.
[8] B. Schubert, B. Marsen, S. Cinque, T. Unold, R. Klenk, S. Schorr, H. Schock,
Prog. Photovolt. Res. Appl. 19 (2011) 93.
[9] T.K. Todorov, D.B. Mitzi, Eur. J. Inorg. Chem. 2010 (1) (2009) 17.
[10] N. Moritake, Y. Fukui, M. Oonuki, K. Tanaka, H. Uchiki, Phys. Status Solidi C 6 (2009)
1233.
[11] Q. Guo, G.M. Ford, W. Yang, B.C. Walker, E.A. Stach, H.W. Hillhouse, R. Agawal,
J. Am. Chem. Soc. 132 (2010) 17384.
[12] D.A.R. Barkhouse, O. Gunawan, T. Gokeman, T.K. Todorov, D.B. Mitz, Prog. Photovoltaics
Res. Appl. 20 (2012) 611.
[13] F. Gde, C.J. Gm, Crystal Growth 299 (2007) 136.
[14] M. Ohyama, H. Kozuka, T. Yoko, Thin Solid Films 306 (1997) 78.
[15] J. Britt, C. Ferekides, Appl. Phys. Lett. 62 (1993) 2851.
[16] A.-J. Cheng, M. Manno, A. Khare, C. Leighton, S.A. Campbell, E.S. Aydil, J. Vac.
Sci. Technol. A 29 (5) (2011)(051203-1-11).
[17] J.Y.W. Seto, J. Appl. Phys. 46 (1975) 5247.
[18] V. Kosyak, M.A. Karmarkar, M.A. Scarpulla, Appl. Phys. Lett. 100 (2012) 263903.