Journal of Materials Science: Materials in Electronics

https://doi.org/10.1007/s10854-018-00630-0

Physical and optical properties of sprayed ­Cu2ZnSnS4 (CZTS) thin film:

effect of Cu concentration
R. J. Deokate1   · R. S. Kate1 · S. C. Bulakhe1

Received: 20 October 2018 / Accepted: 21 December 2018

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Abstract
The crystallographic microstructural and optical properties of CZTS thin film have been investigated with influence of copper
concentration in spray solution. The X-ray and Raman study carried out to the prepared CZTS thin films and attained pure
kesterite phase. The results of microstructural properties such as crystallite size, d-spacing, microstrain, texture coefficient
and standard deviation investigated. The prepared CZTS thin film shows very high optical absorption of the order of ­105 cm−1
in the visible region and the optical band gap energy varied between 1.45 and 1.47 eV. This optical band gap tuning is most
applicable for solar cells. By using the Wemple–DiDomenico (WDD) single oscillator model, the optical parameters were
calculated such as single oscillator energy (­ E0), dispersion energy (­ Ed), static refractive index (­ n0), etc. Large values of opti-
cal conductivity (σ) give the promise to the solar cell application.

1 Introduction variation is necessary. Numbers of articles are available on

the structural properties of the CZTS thin films, also on the
The overpriced CIGS and CdTe solar cells are substituted elemental composition variation. Via sequential electrodep-
that adopt rare earth elements such as In, Ga, Te and toxic osition method, CZTS based solar cells synthesized using
Cd with the earth-abundant and non-toxic solar cell materi- different copper salt concentration in which sulfurization
als, the serious research is being worked out [1, 2]. Qua- was carried out in elemental sulfur vapor atmosphere by
ternary kesterite copper zinc tin chalcogenide ­Cu2ZnSnS4 Mkawi et al. and they found that there was increase in the
(CZTS) thin film solar cells have been very fascinated mate- grain size with the increase in copper concentration [16].
rial from last 10 years due to its optical direct band gap Bhosale et al. studied the variation of copper concentra-
(~ 1.5 eV), which is closer to the required optical band gap tion on the structural and phase purity of the CZTS [17].
for solar cell and large absorption coefficient (> 104 cm−1) Kumar et al. [18] reported the increase in optical band gap
[3, 4]. The CZTS thin films have been prepared and studied with decrease in copper salt concentration in the solution
physical properties with several deposition techniques such at substrate temperature of 370 °C using the Spray pyroly-
as sputtering [5, 6], chemical vapor deposition [7], sol–gel sis technique (SPT). Camara et al. [19] synthesized copper
method [8], painting [9, 10], electrodeposition [11, 12], rich CZTS nanoparticles by a simple hydrothermal method
spray Pyrolysis [13–15]. Among all these techniques chemi- with different concentration ratios of sulfur and copper and
cal spray pyrolysis technique is one of the most useful and investigated the better results. No any literature gives the
simplest, reasonable, environmentally friendly, negligible detailed idea about the microstructural properties as well as
waste of chemicals with utilization best efficiencies closer optical properties with their dispersion parameters, dielec-
to 100% with large deposition area. tric constants, optical conductivity, etc. In this study, the
In CZTS thin film to achieve highly pure kesterite phase effect of copper concentration on the crystallographic micro-
and high efficient photovoltaics with large crystallite size structural and optical properties of the C ­ u2ZnSnS4 (CZTS)
throughout the experiment, the elemental concentration thin film is reported. The optical properties of materials,
such as dielectric functions ε = εr + iεi and refractive indies
* R. J. Deokate N = n + ik=[ε]1/2, dispersion parameters, optical conductivity
deokate2000@yahoo.co.in; rjdeokate@gamil.com (σopt), etc. are essential to improve and elevate PV device
structure [19–21].
1
Vidya Pratishthan’s, Arts, Science and Commerce College,
Baramati, MS 413 133, India

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 Journal of Materials Science: Materials in Electronics

2 Experimental details 0.145 M

0.150 M
0.155 M
2.1 Film deposition and characterization

(112)
0.160 M

(220)

(312)
0.165 M

Intensity (A.U.)
The ­C u 2ZnSnS 4 thin films were deposited by chemical
spray pyrolysis technique at optimized substrate tempera-
ture at 350 °C. The concentrations of zinc, Tin and sulfur
are kept at optimized value of 0.25 M, 0.25 M and 0.40 M
respectively and the concentration of copper is varied from
0.145 to 0.165 M by an interval of 0.05 [17]. To recom-
pense the loss of sulfur during spray deposition, excess
amount of sulfur is taken. The other experimental param-
eters such as nozzle to substrate distance, carrier gas, etc.
and spray deposition set-up were steady [17]. X-ray dif- 20 30 40 50 60 70 80
2θ (Deg.)
fractometer (XRD Bruker AXS D8 Advance Model) was
used to study the structural and crystallographic properties
of the films with the Cu-Kα (λ = 1.5406 Å) radiation source Fig. 1  X-ray diffraction analysis of CZTS thin films with different
copper concentrations
in 2θ range 20°–80°. At room temperature Raman scatter-
ing was performed using the micro-Raman spectrometer
The local distortion of the lattice planes due to the plastic
(Jobin–Yvon Lab RAM HR 800UV) with the excitation by
deformation, interplaner spacing variation is calculated by
514.5 nm photons of 20 mW Argon ion laser. Uv–visible
microstrain (ε) using following formula [23]:
spectroscopy (UV-1800 Shimadzu Uv–Vis-NIR Spectro-
photometer) in the wavelength range 200–1100 nm at room βcosθ
𝜀= (1)
temperature was used to study the optical parameters. 4
where, β is the full width at half maximum (FWHM) of the
prominent peak and θ is the half of the diffraction angle
(2θ). The lattice (d-spacing) parameters were calculated by
3 Result and discussion
Bragg’s diffraction equation. The microstrain indicated very
smaller the variation in the lattice spacing and analogous
3.1 X‑ray diffraction study
results were observed for the prepared CZTS thin films. Fig-
ure 2b shows that, microstrain varied in the range 9.4 × 10− 3
Figure 1 shows the X-ray diffraction patterns of CZTS thin
to 2 × 10− 3, change in the lattice spacing attributed to
film deposited for different Cu-concentrations. The major
enhancement in crystal growth [24, 25]. The crystallite size
diffraction peaks corresponding to the Milar (h k l) planes
(D) was calculated using Scherrer’s formula and the disloca-
(1 1 2), (2 2 0) and (3 1 2) are observed at 2θ° 28.47°,
tion density (δ) was obtained by calculating the reciprocal
47.42° and 56.24°, respectively. The observed results are
of the square of the crystallite size [26, 27]. Maximum crys-
matched with the standard results and confirmed the pre-
tallite size 16.67 nm was observed to the 0.155 M copper
pared thin films are polycrystalline CZTS with kesterite
concentration representing least crystal defects and plastic
phase [22]. Absence of the impurity peaks and secondary
deformations. As shown in Fig. 2c, dislocation density of the
phases gives the formation of the pure and good quality
CZTS thin films with Cu-variation showed minimum value
CZTS thin films and it is also confirmed by Raman analy-
for 0.155 M copper precursor concentration.
sis. Some authors have detected the other secondary phases
The preferential orientation or the random growth of the
(CdS, ZnS) in the CZTS thin film with variation of Cu
polycrystals collected from the relative intensities of the XRD
concentration. The XRD patterns showed increase in peak
pattern calculated by the texture coefficient ­(TChkl) using the
intensity upto 0.155M cu-concentration as shown in the
following [28]:
Fig. 2a. The maximum crystalline size value was observed
for 0.155 M copper concentration and further decreased Ihkl
at higher copper concentration (0.165 M). Exactly oppo- I0 hkl

site behaviour in full width at half maximum (FWHM)

TChkl = 1 ∑ Ihkl (2)
is observed due to the large grain formation at 0.155 M N
N
I0 hkl

copper concentration. The calculated lattice parameters

showed the values a = 5.42 Å and c = 10.84 Å and the value where, Ihkl is the intensity count of the observed peak, Iοhkl
of c/2a is close to 1, indicates tetragonal unit cell [22]. is the corresponding standard relative intensity count from

13
Journal of Materials Science: Materials in Electronics

(a) (b) 3.142 10

0.040 16
3.140
0.035 14
8

Microstrain (ε) × 10-3

Crystallite size (nm)
12 3.138
0.030

d-spacing (A°)
FWHM (Rad.)

10 3.136
0.025 6
8
3.134
0.020
6 4
3.132
0.015
4

0.010 3.130
2 2

0.005 0 3.128
0.145 0.150 0.155 0.160 0.165
0.145 0.150 0.155 0.160 0.165
Cu-Concentration (M)
Cu-Concentration (M)
(c) (d)

Dislocation Density δ × 10 (Lines/m )

2
20 8 36
1.45
18 7
35

Texture co-efficient (T.C.)

16 1.40
Crystallite Size D (nm)

Standard deviation σ
6
14 1.35
16

5 34
12 1.30
4
10 33
1.25
8 3
1.20 32
6 2
4 1.15
1
31
2 1.10
0
0
0.145 0.150 0.155 0.160 0.165 1.05 30
0.145 0.150 0.155 0.160 0.165
Cu-Concentration (M)
Cu-concentration (M)

Fig. 2  a Variation of full width at half maximum and crystalline size and dislocation density with various copper concentration, d effect of
of the CZTS thin films with different copper concentration, b inter- copper variation on the texture coefficient and standard deviation in
planer spacing (d) and microstrain (ε) variation in the CZTS with the the intensities of the peaks
variation of copper concentration, c interrelation of crystallite size

the JCPDS data and N is the number of peaks of the planes where, I is the relative intensity of the peak and N is the
observed in the pattern. The texture coefficient is greater number of peaks observed. Figure 2d shows that standard
than one when the hkl-planes are preferentially oriented. deviation for various copper concentration which is found
The lower values of the texture coefficient show poor crys- in the range between 34.48 and 30. The decrease in standard
tallinity in the thin film and the CZTS thin film deposited deviation was attributed to improved crystallinity and reori-
with 0.155 M copper concentration gives maximum texture entational effects [30].
coefficient shown in Fig. 2d, which confirmed the maximum
crystallite size for that particular copper concentration. The 3.2 Raman spectroscopy study
standard deviation (σ) in the intensities of various peaks was
calculated to elucidate the growth mechanism of the CZTS Many secondary phases may appear in the quaternary kester-
films [29]: ite compounds at the time of synthesis which may be affect
on the grain growth, percentage phase purity, optical and
electrical properties, solar cell property. Figure 3 gives the
�
� � �2
� ∑
Raman spectroscopy analysis of CZTS thin films prepared
�∑ I
� (I)2 − N
(3)
�
�N N for different copper concentrations. In Raman spectra peaks
𝛔= are observed, at 328 cm−1 with dominant peak and shoul-
N
der peak at 366 cm−1 which are basically of sulfur-kesterite

13
 Journal of Materials Science: Materials in Electronics

CZTS phase [31]. This observation is in agree with the XRD

328 cm-1
0.145 M results The peak observed at 366 cm−1 is very week as com-

CZTS
0.150 M
0.155 M
pared to the strong Raman peak at 328 cm−1 corresponds to
0.160 M the preferential growth of the CZTS.
0.165 M
Intensity (A.U.)

3.3 Optical spectroscopy study

366 cm-1
CZTS
The Fig. 4a shows the absorbance (A) spectra of the CZTS
thin film which provides the relation between absorb-
ance (A) and wavelength (λ). At shorter wavelength side
(λ = 300–500 nm), maximum absorbance is observed and
decreased continuously towards higher wavelength region
200 300 400 500 (λ > 900 nm).
Raman Shift (cm
-1
) Figure 4b gives the transmittance (T) spectra of the CZTS
thin films opposite to the absorbance, low transmittance at
Fig. 3  Raman spectroscopy analysis of synthesized CZTS thin film
photons of shorter wavelength side and about 18% transmit-
with different copper concentrations tance at longer wavelength side. The absorbance increased as

(a) 4.5 (b) 20

0.145 M
4.0 0.150 M
0.145 M
0.150 M 0.155 M
3.5 16
0.155 M 0.160 M
Absorbance (A.U.)

0.160 M 0.165 M
3.0
Transmitance (%)

0.165 M
12
2.5

2.0 8

1.5
4
1.0

0.5 0
200 400 600 800 1000 1200 200 400 600 800 1000 1200
Wavelength (λ) (nm) Wavelength λ (nm)

(c) (d)
3.5 0.5
5
× 10

3.0 0.145 M
)

0.4
-1

0.150 M
Absorption Coefficient α (cm

0.155 M
Reflectance (%)

2.5 0.160 M
0.3 0.165 M
0.145 M
2.0 0.150 M
0.155 M
0.160 M 0.2
0.165 M
1.5

0.1
1.0

0.5 0.0
1.5 2.0 2.5 3.0 3.5 4.0 400 600 800 1000
Photon Energy hν (eV) Wavelength λ (nm)

Fig. 4  a Absorbance (A) spectra of CZTS thin films, b transmittance (T) spectra of CZTS thin films, c the absorption coefficient (α) versus
wavelength (λ) for the CZTS thin films, d reflectance (R) spectra of CZTS thin films

13
Journal of Materials Science: Materials in Electronics

the concentration of the copper increased in the CZTS thin and therefore its impact on the band gaps is also common
films and showed maximum for 0.155 M copper concentra- [39].
tion further slightly decreased. From the transmittance and The refractive index (n) of the CZTS thin films was calcu-
reflectance data, the absorption coefficient (α) was calcu- lated using the relation (7), where, R is the reflectance and (­ k0)
lated by the relation [32, 33]: is the extinction coefficient which is measure of the fraction
of light scattering loss and absorption per unit distance of the
(1 − R)2 medium penetration of materials and calculated by using the
[ ]
1
𝛼= ln (4) relation (8) as given bellow [40]:
d T

where, (R) is the reflectance, (T) is the transmittance and (d) ]1∕
2
[
1+R 4R 2 (7)
is the thickness of the film. The change of absorption coef- n=
1−R
+ 2
− k0
(1 − R)
ficient (α) with respect to the photon energy (hν) is shown in
the Fig. 4c, which ascribes the synthesized CZTS thin films
have very high absorption coefficient in the visible and near- 𝛼𝜆
k0 = (8)
IR region of the order of 1­ 05 cm−1. This can be attributed to 4𝜋
the increase in the probability of the occurrence of the direct Figure 5b gives the relation between extinction coefficient
transition [34]. ­(k0) and the wavelength (λ). Figure depicts the continuous var-
Total reflectance of the CZTS thin film was calculated iation in (­ k0) over the wavelength range and shows maximum
using the relation between absorbance (A), transmittance value at 500–650 nm and further decreased to higher wave-
(T) and reflectance (R) as given bellow: lengths, resulting the direct relation is very easy to absorp-
)]1∕ tion of light. The lower values (0.004–0.013) indicated the
2 strong absorbance of the CZTS thin films. Refractive index
[ (
T (5)
R= 1−
exp(−A) is an essential property of the material because it is related to
the electronic polarizability of ion and local field inside the
The reflectance spectra for 0.145, 0.150, 0.155, 0.160 and material in the design of heterostructure lasers in optoelec-
0.165 M copper concentration of CZTS thin films are shown tronic devices as well as in solar cell applications [41]. The
in Fig. 4d and it reveals that the reflectance of all the thin plot of refractive index (n) versus photon energy (hν) is shown
films is < 0.5% in 300–1100 nm wavelength range. As the in Fig. 5c. Refractive index varies from 6 to 1.5 in the range of
concentration of copper increases from 0.145 to 0.160 M 1.1–2.5 eV photon energy (hν) and remains steady for higher
in the CZTS thin films, the reflectance goes on decreased photon energy. The higher values of refractive index attributed
between 0.48–0.38% and again increased to 0.40% for higher to the high crystallinity and densification of the thin films [42].
copper concentration (0.165 M). The single oscillator parameters as Wemple–DiDomenic dis-
The plot of (αhν)2 versus (hν) shown in the Fig. 5a is the persion parameter ­(E0), dispersion energy ­(Ed), static refractive
plot determining the optical band gap by the experimen- index ­(n0), etc. can be calculated by the single oscillator model
tal values of absorption coefficient as a function of photon using the Wemple–DiDomenico (WDD) relation [43–46]:
energy using Eq. (6) [35]:
E0 Ed
(𝛼h𝜈)n = A(h𝜈-Eg ) (6) n2 (h𝜈) = 1 + (9)
E02 − (h𝜈)2
where, α is the absorption coefficient, hν is the photon
energy, n is the exponent determines the type of electronic where, (n) is the refractive index, (­ E0) is the single oscillator
transitions causing the absorption and take the values 1/2 energy, ­(Ed) is the dispersion energy which is the strength of
for indirect transitions and 2 for the direct transitions, A is inter band optical transition and (hν) is the photon energy.
the probabilistic parameter for the transition and E ­ g is the The values of E ­ 0 and E
­ d can be found by plotting the graph
optical band gap energy. The optical band gap energy values of ­(n2 − 1)−1 versus (hν)2 as shown in Fig. 5d, the intercept
observed between 1.45 and 1.47 eV and is in the range of on Y-axis gives the value of ­E0/Ed and the slope of the line
required band gap value for the solar cell application [3, 4, gives the value of 1/(E0Ed). The calculated values of E ­ 0 and
22, 36, 37]. For the lower copper concentration, band gap ­Ed are tabulated in the Table 1. Using these values (­ E0 and
value has 1.45 eV and increases continuously with increase ­Ed), the static refractive index (­ n0) can be calculated by the
in copper concentration. Rendering to the equilibrium of formula:
the maximum of valence band and minimum of conduction
band states, the band gap tunneling may be implicit [38].
√( )
Ed
With different compositions, the disorder between Cu and n0 = 1+ (10)
E0
Zn cations is extremely likely in the CZTS semiconductors,

13
 Journal of Materials Science: Materials in Electronics

(a) 1.00 (b)

0.145 M
0.150 M
0.155 M 0.012 0.145 M

Extinction co-efficient (k0)

0.80 0.160 M 0.150 M
11

0.165 M
0.155 M
× 10

Band Gap 0.010 0.160 M

0.60 0.145 M= 1.45 eV 0.165 M
(αhν) (eV.cm )
-2

0.150 M= 1.45 eV
0.155 M= 1.46 eV
0.160 M= 1.46 eV 0.008
0.40 0.165 M= 1.47 eV
2

0.006
0.20

0.004
0.00
1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 300 450 600 750 900 1050 1200
Photon Energy hν (eV) Wavelength λ (nm)
(c) (d)
6
1.0
5 0.145 M
0.145 M
Refractive Index (n)

0.150 M
0.150 M 0.8 0.155 M
0.155 M
4 0.160 M
0.160 M
0.165 M
-1

0.165 M
(n -1)
0.6
2

3
0.4
2
0.2
1
0.0
1.0 1.5 2.0 2.5 3.0 3.5 4.0 30 × 10-7 25 × 10-7 20 × 10-7 15 × 10-7 10 × 10-7
Photon Energy hν (eV) Wavelength λ (nm)
-2 -2

Fig. 5  a Plot of (αhν)2 versus photon energy (hν) of CZTS samples for CZTS thin films, c refractive index (n) of CZTS thin films, d the
gives variation in optical band gap with different copper concentra- plot of refractive index factor ­(n2 − 1)−1 versus reciprocal of square of
tion, b the plot of extinction coefficient ­(k0) versus wavelength (λ) wavelength

Table 1  The band gaps and the estimated values of the oscilla- dielectric constants; real part of dielectric constant (is to
tor parameters ­E0 and ­Ed as well as other related optical parameters measure how much that material will slow down the speed of
extrapolated from WDD model
light) and imaginary part of dielectric constant (is to meas-
CZTS thin film Ed (eV) E0 (eV) n0 Eg (eV) E0/Eg ure how a dielectric material absorbs energy from an electric
field due to dipole motion). The real dielectric constant (εr)
0.145 M 2.41 1.34 1.67 1.45 0.92
and imaginary dielectric constant (εi) can be calculated by
0.150 M 1.94 1.33 1.56 1.45 0.91
using the values of refractive index (n) and extinction coef-
0.155 M 1.45 1.30 1.45 1.46 0.89
ficient ­(k0) by using the following relations [47–49]:
0.160 M 1.38 1.40 1.40 1.46 0.95
0.165 M 1.75 1.32 1.52 1.47 0.89 𝜀r = (n2 − k0 2 ) (11)

𝜀i = 2nk0 (12)
Figure 6a and b gives the variation of (εr) and (εi) with
The values of ­(n0) can be calculated by extrapolating the
respective of photon energy (hν), respectively. The values
Wemple–DiDomenico (WDD) equation (Eq. 9) to hν → 0
of the real dielectric constants are higher than the imagi-
and tabulated in Table 1.
nary dielectric constants and both are decreases expo-
The essential property of the optoelectronic semicon-
nentially with increase in the photon energy. The optical
ductor material is dielectric nature. There are two parts of

13
Journal of Materials Science: Materials in Electronics

(a) (b)
0.06
30

Imaginary Dielectric Constant (εi)

0.145 M
Real Dielectric Constant (εr)

0.150 M 0.145 M
25 0.155 M 0.05 0.150 M
0.160 M
0.155 M
0.165 M
20 0.160 M
0.165 M
0.04
15

10 0.03

5
0.02

0
1.25 1.50 1.75 2.00 1.5 2.0 2.5 3.0 3.5 4.0
Photon Energy hν (eV) Photon Energy hν (eV)

Fig. 6  a Variation of real dielectric constant (εr) with respect to photon energy (hν) of CZTS thin films, b variation of imaginary dielectric con-
stant (εi) with respect to photon energy (hν) of CZTS thin films

10.0 the electrons due to high optical absorbance and low extinction
coefficient [51].
12
× 10

0.145 M
9.50
0.150 M
4 Conclusions
)

0.155 M
-1
Optical Conductivity σ (s

9.00 0.160 M
0.165 M
In summary, the C ­ u2ZnSnS4 (CZTS) thin films were deposited
8.50 by spray pyrolysis technique and reported the influence of cop-
per concentration on the microstructural and optical proper-
8.00 ties. The X-ray diffraction and Raman spectroscopy analyses
confirmed the pure kesterite CZTS phase with the expected
7.50 results. The optical constants were confirmed by means of
absorbance, transmittance and reflectance measurements at
7.00 room temperature. The as synthesized CZTS thin films showed
300 450 600 750 900 1050 good optical absorption (> 105 cm−1) in the visible region and
Wavelength λ (nm) the optical band gap energy in the range 1.45–1.47 eV. Fitting
of the refractive indices rendering to the Wemple–DiDomen-
Fig. 7  Optical conductivity (σ) of CZTS thin films as a function of ico (WDD) model, results in the dispersion of parameters that
wavelength (λ) are directly related to the structural properties of the CZTS
thin films.
response of a material is possibly deliberates in terms of
optical conductivity. The optical conductivity of the mate- Acknowledgements  Authors are wishing thanks to the Science and
Engineering Research Board, Department of Science and Technology
rial can be calculated by the relation, where c is the veloc- (SERB/DST), New Delhi, India for their financial assistance through
ity of light [50]: the fast track project (SB/FTP/PS-079/2014) titled “Fabrication of
efficient ­Cu2ZnSnS4 (CZTS) thin film solar cells using economical
𝛼nc Spray Pyrolysis”.
𝜎=
4𝜋 (13)

Figure 7 gives the relation between optical conductivity (σ)

and wavelength (λ). Figure showed the very large values (of References
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 Journal of Materials Science: Materials in Electronics

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