Semiconductor Science and Technology

Semicond. Sci. Technol. 36 (2021) 105008 (15pp) https://doi.org/10.1088/1361-6641/ac1962

Cu2ZnSnS4 thin film as a counter

electrode in zinc stannate-based
dye-sensitized solar cells
Mina Soltanmohammadi1,2, Vahid Karimi1,2, Soheil Alee1,2, Masoud Abrari1,2,
Morteza Ahmadi1,2 and Majid Ghanaatshoar1,2,∗
1
Laser and Plasma Research Institute, Shahid Beheshti University, Tehran, Iran
2
Solar Cells Research Group, Shahid Beheshti University, Tehran, Iran

E-mail: m-ghanaat@sbu.ac.ir

Received 15 April 2021, revised 13 July 2021

Accepted for publication 30 July 2021
Published 6 September 2021

Abstract
In this study, we deposited Cu2 ZnSnS4 (CZTS) thin films with various thicknesses using
electrodeposition and sputtering methods to exploit them as counter electrodes (CEs) in
Zn2 SnO4 -based dye-sensitized solar cells (DSSCs). The ternary Zn2 SnO4 compound with wide
bandgap energy, large corrosive resistivity, high electron mobility, and an appropriate
conduction band edge position concerning the dye molecules (N719) can be an outstanding
alternative for photoanode besides CZTS CE in DSSCs. On the other hand, CZTS is an
impressive candidate as a CE material, but its electrocatalytic activity for the recovery of I− /I−
3
ionic species can be different depending on the synthesis process. Our results indicated the
creation of porous morphology in the solution-based deposited films, which yields higher
electrocatalytic activity in the CE performance in comparison with the physical deposition
method, resulting in short circuit current densities of 9.77 and 8.40 mA cm−2 and open-circuit
voltages of 633 and 583 mV for the DSSCs prepared by the respective techniques. The large
active area and highly crystallized CZTS films, prepared by the electrodeposition method, led to
an around 50% efficiency improvement compared to the widely used, more expensive platinum.
Keywords: dye-sensitized solar cell, counter electrode, CZTS, ZTO

(Some figures may appear in colour only in the online journal)

1. Introduction CE are required [4]. Ideal CEs possess excellent electrocata-

Dye-sensitized solar cell (DSSC) is one of the most promising
types of third-generation photovoltaic devices [1], which con-
sists of three key components: a dye-sensitized semiconductor
photoanode, an electrolyte with a redox couple (triiodide/iod-
ide), and a counter electrode (CE) to convert light to electric
energy. In order to produce high-efficiency DSSCs [2], some
prominent features such as good stability [3] and low-cost
∗
Author to whom any correspondence should be addressed.
lytic activity for the efficient recovery of charge carrier reduc-
tion after electron injection and suitable electrical conductiv-
ity [5–7]. The ordinary CE for regeneration of iodide/triiodide
electrolyte is platinum (Pt) due to its extreme conductivity and
electrochemical response [8]. Moreover, Pt as a CE contributes
more than 40% of the DSSCs’ total cost [9]. Numerous can-
didates have been exploited to replace the low-abundance and
expensive Pt [10], such as carbon-based materials [11], con-
jugated polymers [12], binary metal oxides [13], metal sulf-
ides [14], and metal nitrides [15]. Various binary metal oxides
and sulfides entice much concentration due to having nearly
the same electrocatalytic activity as Pt [16–19].

1361-6641/21/105008+15$33.00 1 © 2021 IOP Publishing Ltd Printed in the UK

Semicond. Sci. Technol. 36 (2021) 105008
Quaternary semiconducting compound Cu2 ZnSnS4
(CZTS) is an emerging solar cell material whose constitu-
ents, Zn and Sn, are in Earth’s crust and environmentally
friendly [20, 21] with an admissible electrocatalytic ability.
This p-type kesterite material has been broadly considered as a
promising photo- and electrocatalyst candidate with due atten-
tion to owing high abundant, nontoxicity, and tunable energy
bandgap (1.0–1.5 eV) [22, 23]. The effect of the CZTS film
thickness on its electrocatalytic activity with the I− /I−
3 redox
species and the DSSC power conversion efficiency (PCE) still
is a great challenge. Recent studies focused on the fabrica-
tion and development of solar cells based on CZTS CE have
rarely been reported in the literature. So far, several depos-
ition methods for CZTS thin films have been investigated,
which include RF and direct-current (DC) magnetron sputter-
ing deposition [24, 25], co-evaporation [26], electron beam
evaporation [27], pulsed laser deposition [28], spray pyrolysis
deposition [29], spin coating [30], screen-printing [31], and
electrodeposition [32]. The electrodeposition technique as a
solution-based process is a suitable and affordable synthesis
method with low-cost precursors, high-rate deposition, and
low-temperature deposition conditions [33]. However, this
deposition method would face some limitations in large-scale
production in the industry. In contrast, the sputtering depos-
ition as a vacuum-based technique provides precise control
over film thickness in large area and industrial scales [25].
Although it increases the manufacturing costs it results in
higher-quality thin films [34]. The maximum PCE of DSSCs
based on CZTS CE, approached by DC magnetron sputtering,
was reported as 7.94%, in comparison to the Pt-based DSSCs
(8.55%) [2]. The DSSC efficiency with the electrodeposited
CZTS CE was achieved to be around 7.09%, which increased
to 8.67% by using mirror reflection [35]. In a recent study, a
PCE of 6.19% was also reported [36]. The DSSC comprised
the optimized CZTS CE, deposited by a low-cost solvothermal
method, besides TiO2 photoanode. Moreover, the lower effi-
ciency of the DSSC with co-electrodeposited CZTS CE and
the same used photoanode material was evaluated as 1% [37].
These results demonstrate the CZTS CEs influence, deposited
by chemical and physical methods with TiO2 photoanode, on
the operation of DSSCs.
As is known, the most commonly used wide-band-gap
material for photoanode is TiO2 by which the highest con-
version efficiency of 9.33% in TiO2 /N719/Pt structure in the
presence of I− /I−3 electrolyte was obtained, whereas the PCE
was enhanced to 12.8% upon the use of organic silyl-anchor
dyes [38]. However, specific physical properties of TiO2 pho-
toanode like low electron mobility, high dye-loading time, and
noticeable charge recombination on metal oxide/electrolyte
interface limit further enhancement in the solar cell perform-
ance [39]. Thus, zinc oxide with higher electron mobility com-
pared to TiO2 has been introduced as a photoanode. Still, the
unstable chemical behavior of this material became a challen-
ging issue for implementing it in large-scale production [40].
Other binary n-type metal oxide semiconductors such as SnO2
[41] and Nb2 O5 [42] have also been exploited as photoanode.
This study was continued by examining ternary semiconductor
2
M Soltanmohammadi et al
materials. For instance, BaSnO3 as photoanode represented
promising results along with the CZTS CE in DSSCs [43].
Zinc stannate (Zn2 SnO4 ) with a cubic inverse spinel struc-
ture and the space group symmetry Fd-3 m (No. 227) is also
a great candidate to be used as a photoanode. This compound
with a lattice constant of ∼8.65 Å has been used in DSSCs to
provide a low absorption coefficient and stability [44]. This n-
type semiconductor, as a non-toxic and economical material
with wide bandgap energy between 3.4 and 3.9 eV, is con-
sidered a convenient alternative for traditional TiO2 photoan-
ode in DSSCs. Zn2 SnO4 (ZTO) exhibits large corrosive res-
istivity and high electron mobility (10–12 cm2 V−1 s−1 ) [45],
which is ten times greater than that of TiO2 DSSCs. A con-
siderable attempt has been made to employ the ZTO layer
as a photoanode because this material would transfer elec-
trons with ease, mainly due to its high electron mobility prop-
erty. Moreover, the appropriate conduction band edge posi-
tion concerning the dye molecules (N719) introduces it as an
impressive alternative for photoanode in DSSCs [45]. It should
be noticed that the behavior of the semiconductor material in
electron injection from the lowest unoccupied molecular level
of the dye to the conduction band of the semiconductor is also
effective in device performance [46]. The highest reported per-
formance for ZTO-based DSSCs with Pt CE is 6.3% [47]. This
value varies upon the techniques for fabricating the materials
and the cell device.
CZTS had been employed as a CE in TiO2 -based DSSCs. In
this survey, in addition to discovering a potential economical
substitute to replace the Pt CE, a non-toxic Zn2 SnO4 semicon-
ductor with wide bandgap energy and high mobility prepared
by the co-precipitation method was introduced to be used as
a photoanode in DSSCs. The conduction band energy of ZTO
is similar to that of the traditional TiO2 photoanode energy
band diagram, where electrons generated from photoexcited
dyes can be injected easily. Herein, we survey the effect of
N719 dye-loaded ZTO films prepared by co-precipitation and
doctor-blade techniques as a photoanode besides the CZTS
CE on the DSSC performance. This is followed by study-
ing the influence of CZTS crystalline phase, morphology, and
its optical properties on DSSCs performance through both
vacuum and non-vacuum deposition processes. Furthermore,
sputtered Pt on FTO substrate is exploited as a reference CE
compared to CZTS CEs in assembling DSSC devices. In the
case of the CZTS CE, the survey’s focus is on the two meth-
ods of synthesis and thickness optimization of CZTS CE to
improve the efficiency of DSSCs. This work is beneficial to
understand the electrocatalytic reaction mechanism of CZTS
as CE of DSSCs.
2. Experimental details
In order to prepare a fine kesterite CZTS structure, the effect
of various deposition parameters in both deposition meth-
ods is studied, and numerous samples under different condi-
tions are deposited and characterized. But, eventually, only the
optimum deposition condition for each technique is reported.
Semicond. Sci. Technol. 36 (2021) 105008 M Soltanmohammadi et al

Figure 1. (a) A representation of the experimental set up for electrodeposition system including simple DC power supply and an
electrodeposition cell. (b) Schematic demonstration of a single-step electrodeposition process consisting a working electrode (FTO
substrate), a counter electrode (graphite), and an Ag/AgCl reference electrode in a Cu, Sn and Zn ions electrolyte solution. (c) An
electrodeposited CZTS film. (d) A representation of the experimental set up for sputtering system includes a vacuum chamber and three
metallic targets, (e) Schematic illustration of a sputtering process in a vacuum chamber with Zn, Cu, and Sn targets and a FTO substrate in a
substation rotation that rotates with 10 RPM speed. (f) A sputtered CZTS film.

Electrodeposition of CZTS thin films onto fluorine-doped
tin oxide (F:SnO2 , FTO, sheet resistance 15 Ω cm−2 ) coated
glass substrates were achieved by using a three-electrode sys-
tem composed of FTO working electrode (WE), Ag/AgCl
as a reference electrode, and cylindrical shape graphite that
acts the CE role (figures 1(a) and (b)). The precursor solution
used in this study included Cu2 SO4 , Zn2 SO4 , SnSO4 , sodium
thiosulfate, and trisodium citrate. The pH of the electrolyte
solution was kept around five by dissolving tartaric acid. The
deposition without stirring took place at room temperature by
fixing potential at −1.15 V vs. Ag/AgCl, which supplies accur-
ate applied current to redox Cu–Sn–Zn ions species. Mass and
charge transports have been considered two crucial parameters
for tuning the composition of electrodeposits, which can res-
ult in a significant variation of the layer thickness in different
electroplating durations. CZT stack from the electrolyte con-
taining salts of Cu, Zn, and Sn was electrodeposited on FTO
substrates in three deposition durations (63, 115, and 190 s).
After the deposition process, the sulfurization step was carried
out at a temperature of 550 ◦ C for 40 min in a furnace with 0.2
gr sulfur powder under high vacuum conditions. Figure 1(c)
shows the CZTS sample deposited by the electrodeposition
method.
A vacuum-based synthesis method was also employed to
approach CZTS thin films as CE under the same device config-
uration in order to investigate the effect of phase, morphology,
and electrocatalytic activity of sputtered CZTS on DSSCs per-
formance in comparison to the electrodeposited layers. The
setup image and schematic of the three-cathode sputtering sys-
tem are illustrated in figures 1(d) and (e). Kesterite CZTS thin
films were deposited on the fluorine-doped tin oxide substrate
using a two-step process. In the first step, Cu, Zn, and Sn
metallic targets were placed in the sputtering system and were
deposited using sequential DC sputtering to form the CZT
stack. At first, the Zn layer was deposited on FTO, and then it
was coated by the Sn layer. Finally, the Cu layer was deposited
on top of this stack. Three various sputtering deposition times
and sputtering parameters were considered to reach different
anticipated thicknesses illustrated in table 1. All these steps
were done in the same sputtering chamber to reduce any con-
tamination and stress, and all the samples were rotated with
10 rpm speed to achieve homogenous layers. In the second
stage, samples were put in the annealing furnace that contained
0.2 gr sulfur powder under 10−4 mbar pressure. The samples
were heated from room temperature to 350 ◦ C in 35 min (with
1 ◦ C per minute rate). Subsequently, samples were heated
from 350 ◦ C to 500 ◦ C for 18 min (with 8.3 ◦ C per minute
rate) and then maintained at 500 ◦ C for 30 min. This heat treat-
ment process in the presence of S causes the Sn, Zn, and Cu
layers to diffuse into each other along with the sulfur, which
forms a final CZTS product (figure 1(f)). The electrodeposited
and sputtered CZT samples were sulfurized at different heat

3
Semicond. Sci. Technol. 36 (2021) 105008
Table 1. Detail data of sputtering Zn/Sn/Cu stack layers in different
deposition durations.
Deposition Applied Applied
Target time (min) current (A) voltage (V)
Zn 2, 5 and 11 0.08 410
Sn 14, 32 and 70 0.01 338
Cu 3, 7 and 14 0.08 550
treatment temperatures and time durations because, obviously,
a solution-based deposited thin film would be crystallized at
different conditions with respect to a vacuum-based one.
To synthesize ZTO nanoparticles via the co-precipitation
method, as described in the previous work [48], we prepared
two individual solutions, including 1 M Zn (NO3 )2 .H2 O, and
0.5 M SnCl4 .5H2 O in distilled water, and then we mixed them.
The pH value of the resultant solution was adjusted at 10 using
0.5 M NaOH. The zinc stannate nanoparticles were obtained
by washing, centrifuging, and drying the final solution and,
subsequently, annealing of resultant powder at 1000 ◦ C for
3 h. We deposited the ZTO nanoparticles on FTO glass using
the doctor-blade technique to obtain desired mesoporous lay-
ers. In order to sinter the layers, the ZTO films were placed
in a furnace and heated to the temperature of 500 ◦ C. After
removing them from the furnace, they were immersed in an
ethanolic solution of N719 dye for 22 h at room temperature.
Afterward, the excess adsorbed dye molecules were removed
using absolute ethanol, and then the ZTO photoanodes dried in
the air atmosphere immediately. The sandwich-type solar cell
was assembled by clipping the prepared CZTS/FTO or Pt/FTO
with ZTO photoanode in a redox mediator solution containing
0.05 M iodine and 0.5 M lithium iodide in acetonitrile as an
open-cell (figure 2(a)). A completely fabricated DSSC device
can be seen in figure 2(b).
X-ray diffraction (XRD) pattern was obtained by STOE
STADI-P Co., Germany x-ray diffractometer with high-
intensity Cu-Kα radiation (λ = 1.5418 Å) in an angle range of
10◦ –80◦ , to indicate the phase and the crystallographic struc-
ture of the synthesized CZTS thin films. The crystallite size
and strain were respectively calculated using Debye–Scherrer
and Williamson–Hall (W–H) formula. The dislocation density
of the CZTS material was calculated through Williamson and
Smallman’s formula. Moreover, to discern the kesterite CZTS
structure of Cu2 SnS3 and ZnS phases, Raman spectroscopy
(Takram P50C0R10) was employed using an InGaAs detector
and a solid-state Nd-YAG (532 nm) laser with 15.0 kV oper-
ating voltage. The morphologies of the CEs and film thick-
ness were characterized by Mira III, Tescan, Czech Repub-
lic field-emission scanning electron microscope (FESEM).
The elemental composition of the specimen was determined
using energy-dispersive x-ray spectroscopy (EDX, Oxford 80-
XMAX, England). Atomic force microscopy (AFM) (Brisk,
Ara research, Iran) was used to evaluate the surface rough-
ness. To investigate the optical properties of the synthes-
ized thin films, a reflective UV–Vis spectrometer (3648
Avantes spectrophotometer, Netherland) was employed. Then
the optical bandgap of the fabricated CEs was calculated via
4
M Soltanmohammadi et al
the Tauc formula using acquired absorption spectrum data.
The sheet resistance of layers was calculated using a four-
point probe resistance tester (Zhuhai Kaivo Optoelectronic
Technology Co., Ltd, China). All characterizations and optical
properties of the ZTO photoanode were reported in detail in
our previous work [48]. The assembled DSSCs were illu-
minated under a solar simulator (Sharif Solar, SIM-1000) at
an air mass (AM) of 1.5 with the incident light intensity of
(100 mW cm−2 ) to measure the current density–voltage (J–V)
of the solar cell devices. Cyclic voltammetry (CV), Tafel plots,
and electrochemical impedance spectroscopy (EIS) curves
were conducted by using a three-electrode electrochemical
system in a solution, containing 0.05 M iodine and 0.5 M lith-
ium iodide, at a scan rate of 5 mV s−1 using potentiostat/gal-
vanostat (Origaflex- OGF500, Methrohm, France) equipped
under the dark condition. The electrochemical impedance
spectroscopy based on identical CEs was set at the poten-
tial bias of V oc with the testing frequency range of 0.1 Hz to
10 kHz, and the applying perturbation amplitude of 10 mV.
3. Results and discussion
The cross-sectional FESEM images of electrodeposited and
sputtered CZTS films on the FTO substrate are shown in
figure 3. The thicknesses of CZTS films, electrodeposited with
durations of 63, 115, and 190 s, are 270, 410, and 940 nm,
respectively. These samples are labeled as CZTS-E1, CZTS-
E2, and CZTS-E3, correspondingly. On the other hand, the
sputtered samples have thicknesses of around 237, 427, and
920 nm, which are labeled as CZTS-S1, CZTS-S2, and CZTS-
S3, respectively. The thicknesses of these three layers are
nearly equal to those of the electrodeposited films, making it
possible to compare these two kinds of layers. Both sets of thin
layers have good adherence to polycrystalline tetragonal shape
structure substrates (FTO in our study) [49]. As displayed in
the FESEM images, the thickness of CZTS layers in both tech-
niques is boosted with deposition time due to the increase in
the Cu–Zn–Sn precursor on the FTO substrate. It should be
noted that the resistance of layers has a significant reliance on
the film thickness. This physical parameter has an impressive
influence on solar cell efficiency. The FESEM images reveal
that the sputtered CZTS CEs demonstrate a very dense and
compact structure without cracks. However, the CZTS CEs
prepared by the electrodeposition method shows a rough struc-
ture. Moreover, the grains within the layers are considered
bulkier when the films become thicker through longer depos-
ition times. This is followed by higher surface roughness in
the thicker CZTS films. Furthermore, electrodeposition as a
chemical solution process generally leads to approximately
porous structure layers compared to the sputtering method in
a vacuum chamber, which results in higher electrocatalytic
activity due to the large surface area [50].
Figures 4(a) and (b) exhibit the top-view FESEM images of
the CZTS-E2 and CZTS-S2 layers. The surface morphology
of the CZTS-E2 and CZTS-S2 films is composed of clusters
of nanoparticles, with an average grain size of 141 nm and
111 nm, respectively. Larger grain sizes were found on the
Semicond. Sci. Technol. 36 (2021) 105008 M Soltanmohammadi et al

Figure 2. (a) The schematic diagram demonstrates the complete solar cell structure consisting CZTS deposited layer onto the FTO
substrates, ZTO layer prepared on the FTO glass substrate immersed in N719 dye molecules, and the iodide/triiodide electrolyte, between
the electrodes. (b) A fabricated complete solar cell with CZTS counter electrode.

Figure 3. FESEM of CZTS layers (deposited on FTO substrates) synthesized by different deposition methods and time durations.
(a) Electrodepositing—63 s (CZTS-E1, SEM MAG = 75.0 kx, WD = 10.85 mm), (b) electrodepositing—115 s (CZTS-E2, SEM
MAG = 50.0 kx, WD = 11.40 mm), (c) electrodepositing—190 s (CZTS-E3, SEM MAG = 50.0 kx, WD = 12.91 mm),
(d) sputtering—17 min (CZTS-S1, SEM MAG = 75.0 kx, WD = 10.89 mm), (e) sputtering—45 min (CZTS-S2, SEM MAG = 50.0 kx,
WD = 12.88 mm), and (f) sputtering—95 min (CZTS-S3, SEM MAG = 25.0 kx, WD = 11.85 mm).

5
Semicond. Sci. Technol. 36 (2021) 105008
Figure 4. Top view FESEM images of the (a) CZTS-E2 (SEM MAG = 75.0 kx, WD = 9.96 mm) and (b) CZTS-S2 (SEM MAG = 100.0
kx, WD = 11.80 mm) layers, and AFM images of (c) the CZTS-E2 and (d) CZTS-S2 layers.
electrodeposited layer. As was expected, the CZTS-E2 thin
film shows a porous structure. It could improve the CZTS/elec-
trolyte interfacial contact area and therefore increase the pos-
sibility for interfacial electron transfer.
The AFM images of CZTS-E2 and CZTS-S2 samples on
the FTO substrates have been demonstrated in figures 4(c) and
(d). The value of the root mean square (RMS) roughness is
238.79 nm and 98.64 nm, correspondingly. The larger rough-
ness of the electrodeposited layer helps to enhance the elec-
trocatalytic activity for ions reduction. Comparing to previ-
ously published paper with RMS roughness between 45 and
71 nm in different layers [23], our samples demonstrate super-
ior RMS roughness that may result in better DSSCs perform-
ance. This result is in agreement with the FESEM images.
Moreover, all samples possess a desirable structural qual-
ity with excellent uniformity and adhesivity, making them a
proper candidate for replacing commonly used Pt CEs. The
film’s surface cannot be easily scratched off, indicating that
the film surface is mechanically robust (good adherence to the
substrate) [51]. However, it is clear that the sputtered CZTS
layers have slightly better uniformity and adhesivity in com-
parison with the layers prepared by the solution-based process.
CZTS structure consists of two tetragonal structures termed
stannite and kesterite, as reported by Ito [37]. Kesterite
structure is attributed to the space group I4̄2 m with a statistical
distribution of copper and zinc on the Wyckoff position 4d
[52]. Figures 5(a) and (b) demonstrate the XRD pattern of the
6
M Soltanmohammadi et al
acquired CZTS layers through various deposition durations in
electrodeposition and sputtering techniques. The peaks loc-
ated at 2θ = 28.53◦ , 33.10◦ , 47.28◦ , and 56.12◦ are indexed as
(112), (200), (220), and (312) crystallographic planes of kes-
terite CZTS (JCPDS 26-0575), respectively. The CZTS films
grow with a preferred grain orientation along (112) direction.
These CZTS film structure patterns are in good agreement with
the reported profile of kesterite Cu2 ZnSnS4 [53]. This meas-
urement indicates that the crystal structure of CZTS did not
change in the two mentioned deposition processes. Besides the
FTO peaks, which are from the substrate, there is no additional
peak related to secondary phases. The larger crystallite size of
the CZTS film upon an increase in thickness can also be seen
in the XRD pattern. The peaks with relatively higher intensity
and sharpness are detected in the thickest CZTS-E3 CZTS-S3
samples. This result is in agreement with the survey conducted
by Jarernboon et al [1].
The crystallite size value for electrodeposited and sputtered
CZTS thin films were determined using the Debye-Scherrer
λ
formula [54], Dhkl = βKcos θ , where Dhkl is the crystallite size
perpendicular to crystal face <hkl>, K = 0.9 is the shape
constant, λ = 0.15405 nm (Cu Kα radiation), β stands for
the full width at half maximum (FWHM) of peaks and θ is
the angle of diffraction. The crystallite sizes of CZTS-E1,
CZTS-E2, and CZTS-E3 samples were found to be ∼23.9,
∼35.7, and ∼40.5 nm, which show an upward trend by an
increase in the film thickness. Additionally, the crystal quality
Semicond. Sci. Technol. 36 (2021) 105008 M Soltanmohammadi et al

Figure 5. X-ray diffraction patterns of CZTS layers on FTO substrates produced by (a) electrodeposition and (b) sputtering methods.
Williamson–Hall plots of layers deposited by (c) electrodeposition and (d) sputtering methods. The Raman spectroscopy measurement of
different CZTS layers, prepared on FTO by (e) electrodeposition and (f) sputtering methods.

of CZTS-S1 and CZTS-S2 samples was relatively low because
of the smaller crystallite size of ∼21.9 and ∼24.5 nm, respect-
ively. The Debye–Scherrer calculation for CZTS-S3 with nar-
rower FWHM revealed a crystallite size of about 28.2 nm.
As it is seen, the crystallite size of the films increases with
film thickness. However, the electrodeposited CZTS films
demonstrate a better crystalline structure with a slightly lar-
ger crystallite size rather than the sputtered layers. Thus,
it is possible to predict a better charge transport and less
charge recombination in the sample with larger crystallites.
To be specific, the sheet resistance of the CZTS-E2 and
CZTS-S2 layers, measured by a four-point probe resistance
tester, is 217 mΩ sq−1 and 11.65 Ω sq−1 , respectively, which
proves the better electrical property of the electrodeposited
sample.
Based on the XRD data, The Williamson–Hall plots have
been acquired to estimate the strain in the crystal lattice. The
Williamson–Hall equation is written as [55]:
Kλ
β cos (θ) = + 4ε sin (θ) , (1)
D
where β is the FWHM of each peak, D is the crystallite
size, and ε is the strain. The slope of β cos (θ) versus 4 sin (θ)
gives the strain in the nanostructure. Figures 5(c) and (d) show
Williamson–Hall plots for all the deposited samples, and the
strain in each sample is summarized in table 2. As can be seen,

7
Semicond. Sci. Technol. 36 (2021) 105008
Table 2. Calculated strain and dislocation of different deposited
layers.
Thickness δ(dislocation
Sample (nm) ε (strain) density) × (10 9 )2
CZTS-E1 270 −0.607 0.0017
CZTS-E2 410 0.334 0.0007
CZTS-E3 940 0.166 0.0006
CZTS-S1 237 0.158 0.0020
CZTS-S2 427 0.223 0.0016
CZTS-S3 920 0.154 0.0012
the highest strain is attributed to the CZTS-E1, and the change
in the strain of the sputtered CZTS layers is not considerable.
The dislocation density is also defined as the length of the dis-
location lines per unit volume of the crystal and is also calcu-
lated through [56]:
1 The optical bandgap of all CZTS films has been calculated by
δ= . (2)
D2
A downward trend can be seen in dislocation density value
by increasing the thickness of the CE. As discussed above, a
rise in crystallite size results in crystallinity and conductiv-
ity enhancement and improves the electronic properties of the
materials [57]. According to equation (2), this is accompanied
by a decline in dislocation density value.
Since the XRD peaks of the kesterite CZTS phase are very
close to the profiles of ZnS (JCPDS no. 89-2426) and Cu2 SnS3
(JCPDS no. 89-4714) compounds, additional Raman meas-
urement is crucial [58]. Hence, Raman spectroscopy was util-
ized to identify the phase with more confidence. The results of
the Raman spectroscopy have been illustrated in figures 5(e)
and (f). Three vibration peaks at 286, 336, and 367 cm−1
were perceived in the Raman spectra of the sputtered CZTS
samples, which were indexed to kesterite CZTS film. Like-
wise, the Raman spectrum of the electrodeposited CZTS
samples authenticated the nature of the CZTS kesterite struc-
ture with peaks at around 286, 335, and 372 cm−1 , which
correspond to previously published values of the peak char-
acterization [2]. In addition to a substantial Raman shift of the
peak of 372 cm−1 from 367 cm−1 , an observable deviation of
335 cm−1 peak from 336 cm−1 in the sputtered samples can be
seen. These shifts may be caused by residual micro-stress. The
wrinkle patterns and broad peaks at CZTS-S1 and CZTS-S2
Raman spectra are evidence of the disorder in cations place-
ment and residual compression tension of CZTS elements. No
binary or ternary sulfides peaks are discerned in samples pre-
pared by both the chemical and physical deposition processes,
confirming the high purity of the CZTS layers. By comparing
the electrodeposited and sputtered thin films, the clear pres-
ence of thinner Raman scattering peaks in the electrodepos-
ited samples demonstrates a better quality, which is in good
agreement with the XRD data. The Raman peaks (especially
at 336 cm−1 ) of the CZTS-E3 and CZTS-S3 films also have
the highest intensity, as seen in figure 5.
We determined the detailed atomic ratio of the samples by
energy dispersive x-ray analysis (EDX). The corresponding
8
M Soltanmohammadi et al
average atomic percentage of Cu, Zn, Sn, and S in the elec-
trodeposited layer is 24.12%, 11.95%, 12.66%, and 51.27%,
respectively, and this value is 24.67%, 12.87%, 13.08%, and
49.38% for the sputtered layer. They are so close to the most
acceptable values of the best CZTS stoichiometry relation with
25% Cu, 12.5% Zn, 12.5% Sn, and 50% S. In a previous study
conducted by Khattak et al [59], the composition ratio attrib-
uted to Cu, Zn, Sn and S elements in the electrodeposited
CZTS thin films had the values of 25.22%, 11.33%, 13.33%,
and 50.11% respectively, which are so close to what we
reported.
Figures 6(a) and (b) depict the variation of (hυα)2 as
a function of bandgap energy (Eg ) for electrodeposited and
sputtered CZTS thin films. Near the absorption edge or in
the strong absorption zone of the transmittance spectra, the
absorption coefficient, α, is related to the incident photon
n
energy (hυ) as hυ α = A(hυ − Eg ) where A is a constant and
n is equal to 1/2 for direct semiconductors such as CZTS [60].
using the Tauc formula. The obtained values of the bandgap
energy of layers started from 1.33 to 1.52 eV, which is a
suitable period for visible-driven photocatalysts. It is acknow-
ledged that the optimum bandgap value of the kesterite struc-
ture CZTS thin film, as a p-type semiconductor, is close to
1.5 eV [1]. Moreover, the bandgap energies of the layers from
both depositing methods have the same trend. As the thickness
of the CZTS films increases, the value of the bandgap becomes
greater. Thus, the samples with outstanding crystalline qual-
ity also demonstrate a suitable optical bandgap. Bandgap vari-
ation is accompanied by the change in optical parameters of
the thin films, such as the refractive index, which can be cal-
culated from both Moss relation and Herve and Vandamme
relation [61], which respectively are written as:
Eg n4 = k, (3)
√
A
n= 1+
Eg + B
, (4)
where k is a constant value (108 eV), and A and B in equation
(4) have the constant values of 13.6 and 3.4 eV, respectively.
The ultimate values can be seen in table 3. It is clear that both
calculated values from the two equations are approximately
the same and so close to the values previously reported by
Fouad et al [20].
Through absorbance values calculated from UV-visible
spectroscopy, we can evaluate the absorption coefficient and
extinction coefficient (K0 ) of the thin films. The extinction
coefficient is assessed by K0 = αλ 4π where λ stands for the
wavelength of the incident light [62]. Figure 7(a) represents
the dependence of the extinction coefficient on the wavelength
of CZTS-E2 and CZTS-S2 thin films. As can be seen, around
λ = 500 nm, which is in the absorption region of N719 dye
molecules, the extinction coefficients of the two samples are
nearly equal and with a low value that does not perturb light
absorbing by dye molecules and so, the DSSC performance.
Semicond. Sci. Technol. 36 (2021) 105008 M Soltanmohammadi et al

Figure 6. The Tauc plots acquired from UV-visible spectra of CZTS thin films. The interception of the dashed slopes with x-axis, represents
the bandgap energy of the prepared layers by (a) electrodeposition and (b) sputtering methods.

Table 3. Calculated reflective index of different deposited layers. figures 8(b)–(d). This analysis implies (25.06% Zn), (12.53%
n, Herver and Sn), and (62.41% O) ensuring ZTO alloy formation. The map-
Bandgap n, Moss Vandamme ping images also display homogeneous and uniform compos-
Sample energy (eV) relation [61] relation [61] ition distribution.
To analyze the CZTS electrocatalytic properties, we carried
CZTS-E1 1.33 3.00 3.04 out the CV experiment. Figures 9(a) and (b) illustrate the CV
CZTS-E2 1.47 2.92 2.96 curves of the CEs with a scan rate of 5 mVs−1 . All the CEs
CZTS-E3 1.48 2.92 2.96
with different thicknesses exhibited two reduction peaks. One
CZTS-S1 1.47 2.92 2.96
CZTS-S2 1.45 2.93 2.97
peak is assigned to the redox reaction of I− −
3 /I electrolyte,
CZTS-S3 1.52 2.90 2.93 while the other one is related to the reduction of I2 /I−
3 at the
CE/electrolyte interface, according to the following reactions,
respectively [63]:

We also calculated the Urbach energy related to the dens- I− −

ity of localized states in the bandgap induced by structural
disorder (stress and dislocation). The absorption coefficient
has an exponential dependence on photon energy(and) Urbach
energy, which is estimated by [62] α = α0 exp hEuυ , where
α0 is a constant and Eu is the Urbach energy. Figure 7(b)
shows a linear plot of lnα vs. hν and the Urbach energy can
be obtained from the slope, as displayed in the figure. The
Urbach energy values is 0.70 meV for CZTS-E2 and 0.85 meV
for CZTS-S2 sample. It can be concluded that the electrode-
posited CZTS film presents an improved crystallinity, as com-
pared with those grown by sputtering method. This is in con-
sistent with the results deduced from XRD patterns.
Having provided the proper CZTS CEs, we fabricate the
DSSCs based on the ZTO photoanode to get a better under-
standing of the structure of a complete cell and investigate its
morphological features, FESEM and elemental distribution of
the ZTO-photoanode are evaluated. Figure 8(a) demonstrates
the FESEM cross-sectional image of the ZTO-photoanode
deposited by doctor blade technique on FTO substrate. The
ZTO layer tends to aggregate and is formed by the packing of
nano-sized particles. To examine the compositional elements
and purity of the ZTO layer, the EDX analysis is provided,
and elemental mapping images of the ZTO layer are shown in
3 + 2e → 3I , (5)
3I2 + 2e → 2I−
3 . (6)
As it has been reported in the literature [44] when a negat-
ive pulsed electrical bias (reverse bias) is applied to a DSSC
under illumination conditions, plenty of I− ions are produced
in the vicinity of the CE via the reduction equation (5). There-
fore, the peak current density (J pc ) of a CV curve implies
the electrocatalytic ability of CEs for the reduction of I− 3 in
DSSCs. It clearly means that the electrode with a high peak
current density of I− − −
3 to I reduction through the I3 + 2e →
−
3I equation shows superior electrocatalytic capacity at the
CZTS CE [45]. Thus, as shown in figure 9, the larger peak cur-
rent responses led to the enhancement of the electrocatalytic
activity of CZTS-E2 CE compared to CZTS-E1 and CZTS-E3
CEs with moderately lower J pc . This electrocatalytic activity
trend is also observed in CZTS films prepared by the sput-
tering method. It is also detected that the value of J pc for the
electrodeposited CZTS films is larger than that of the sputtered
CZTS CEs. Furthermore, the J pc values suggest that the elec-
trodeposited kesterite CZTS CEs possess higher electrocata-
lytic activity to reduce triiodides rather than the sputtered CEs.

9
Semicond. Sci. Technol. 36 (2021) 105008 M Soltanmohammadi et al

Figure 7. (a) Extinction coefficient of the CZTS-E2 and CZTS-S2 layers. (b) The slope of the carvers demonstrates the Urbach energy of
the CZTS-S2 and CZTS-E2 layers.

Figure 8. (a) Cross section FESEM image of ZTO-photoanode. Elemental mapping images of (b) Sn, (c) Zn, and (d) O in the ZTO
photoanode.

10
Semicond. Sci. Technol. 36 (2021) 105008 M Soltanmohammadi et al

Figure 9. Cyclic voltammograms of Pt and various CZTS CEs obtained by (a) electrodepositing and (b) sputtering processes at a scan rate
of 5 mV s−1 in acetonitrile solution containing 0.05 M iodine and 0.5 M lithium iodide as supporting electrolyte. Tafel polarization curves
of Pt and various CZTS films fabricated by using (c) electrodepositing and (d) sputtering processes. Nyquist plots of the DSSCs with
different counter electrodes deposited by (e) electrodepositing and (f) sputtering processes.

A greater electrocatalytic activity effectively results in the
charge transport improvement of the films. The cyclic voltam-
mogram curves of the sputtered CEs display a much more
similar shape of the Pt curve relative to those of solution-
based films. Remarkably, these results demonstrate that the
cost-effective CZTS thin film deposited by the electrodepos-
ition method is an outstanding choice to be used instead of the
expensive Pt layer in DSSCs.
To further confirm the electrocatalytic activities of the fab-
ricated CEs in an ionic electrolyte, Tafel polarization was plot-
ted for all the CEs from CV measurement. The Tafel curves
for the electrodeposited and sputtered samples are shown in
figures 9(c) and (d). The exchange current density (J 0 ), which
can be acquired from the slope at middle potential and extra-
polated interception of the cathodic branch with equilibrium
potential, defines the electrochemical activity of different CEs

11
Semicond. Sci. Technol. 36 (2021) 105008
[64]. In general, J 0 is reversely proportional to series resist-
ance (Rct ), as below [65]:
RT
J0 = , (7)
nFRct
where R is the gas constant, T stands for the absolute temper-
ature in Kelvin, n shows the number of electrons involved in
the electrochemical reduction of triiodide in the electrode, F is
the Faraday constant, and Rct is the charge transfer resistance
at electrolyte/CE interface. The amount of J 0 for the electrode-
posited samples increases in the order of CZTS-E1, CZTS-E3,
and CZTS-E2. So, the amount of Rct decreases with increasing
J 0 , which can be useful in improving the performance of cells.
This result represents the comprehensive agreement of the
electrocatalytic activity of the electrodeposited CEs with the
electrochemical data acquired from the CV curves for reduc-
tion of the redox electrolyte (I− /I−3 ). On the other hand, for
the CEs prepared by the sputtering method, the higher elec-
trocatalytic activity of CZTS-S2 and CZTS-S3 relative to that
of CZTS-S1 and Pt CEs with much more exchange current
density is presented in figure 9. The larger peak current dens-
ity and the exchange current density of CZTS-S2 and CZTS-
E2 CEs demonstrated in the CV analysis and Tafel polariza-
tion curves measurement, respectively, could be fundament-
ally attributed to their more efficient electrocatalytic activity
and the interfacial charge-transfer property of thin films [66].
In addition to the electrocatalytic ability of CEs for converting
the redox species to each other, the charge transport through
the CE has a significant influence on the DSSCs performance.
As evaluated in the XRD analysis, the crystallite size of lay-
ers perceptibly surges in thicker thin films, resulting in the
point that the electron transport occurs with more ease in these
samples [67]. Therefore, the impressive electrocatalytic activ-
ity of a catalyst depends strongly on evaluating the extreme
charge transport (passing electrons through the CE) and charge
transfer (passing electrons through the CE/electrolyte inter-
face) factors due to the remarkable crystalline quality of CE
materials in DSSC devices. Although rising the thickness of
the CE within a longer deposition time yields crystallite size
enlargement, it also leads to an increase in series resistance
(Rs ), which reduces the current of a dummy cell.
To elucidate how various sputtered and electrodeposited
CZTS CEs can affect the charge transfer and the electrocata-
lytic activity of a DSSC device, EIS measurement was carried
out. In this measurement, the CZTS CE as the WE, a wire of
platinum as the CE, and a standard Ag/AgCl reference elec-
trode were used, which all had been immersed in the electro-
lyte solution. The Nyquist plots of all the samples are high-
lighted in figures 9(e) and (f). In general, the Nyquist plots of
the CE consist of three semicircles, which are located in three
dynamic frequency ranges of low-frequency, mid-frequency,
and high-frequency regions [68]. Since the main focus of our
study is on the performance of various CZTS CEs, the EIS
analysis is only performed on the symmetric cell structure of
the CZTS CEs to represent corresponding impedance. As it
can be seen in figure 9, Nyquist diagrams mainly consist of
one large semicircle. In some samples, there are two semi-
circles (a large semicircle at lower frequencies and a small
12
M Soltanmohammadi et al
semicircle at higher frequencies). The large semicircle arises
from the interactions of the electrolyte and CZTS CE (electro-
lyte/CE), and the small semicircle appears because of the plat-
inum wire electrode and electrolyte interaction, which corres-
ponds to low impedance. By analyzing figure 9(e), we can see
that only the Pt CE sample has a very small semicircle in the
low-frequency region, indicating the electrolyte species diffu-
sion and Warburg impedance [69]. As is known, the diameter
of the large semicircle represents the amount of Rct between
the CE and the electrolyte. Under the dark condition, the lower
value of Rct is favorable because it facilitates the electron trans-
fer from CE to the electrolyte and speeds up the reduction of
I−
3 [70]. Consequently, more current would be produced in
the dummy cell. The smallest value of Rct for the electrode-
posited CZTS CEs is related to the CZTS-E2 sample, which
implies that it has a high electrocatalytic ability to reduce trii-
odide ions and can be superseded the expensive Pt in DSSCs.
The conclusions for the electrocatalytic activity derived from
the EIS and CV data are consistent. This is followed by the
result that CZTS-E1 has a higher Rct value than CZTS-E3
and Pt samples. This also establishes a possible explanation
for the great electrocatalytic activity of the CZTS CEs com-
pared to Pt. As the same token, the smallest value of Rct in the
case of CZTS-S2 reflects the highest electrocatalytic activity
of this layer among the other sputtered samples that are con-
firmed by CV measurement. Totally, CZTS-S2 and CZTS-E2
samples possess greater electronic transport properties rather
than the other films. The series resistant (Rs ) value of a CE,
which was obtained through fitting the EIS spectra in figure 9
and defined by the intercept on the real axis, is another main
factor in producing the outstanding solar cell performance. As
seen by increasing the thickness of the CZTS films and thereby
increasing Rs , a further reduction in the performance of solar
cells in the thickest layers may occur.
Figures 10(a) and (b) illustrate the current density–voltage
(J–V) curves of the DSSCs based on sputtered and electrode-
posited CZTS CEs and Pt with ZTO photoanode. In addition,
the solar cell photovoltaic parameters are listed in table 4. The
PCE was analyzed at an illumination of 100 mW cm−2 under
standard AM 1.5 conditions. The champion cells of electrode-
posited (CZTS-E2) and sputtered (CZTS-S2) DSSCs with
short-circuit current density (Jsc ) of 9.77 and 8.40 mA cm−2 ,
open-circuit voltage (V oc ) of 633 and 583 mV, and fill factor
(FF) of 43% and 38% show PCE of around 2.66% and
2.15%, respectively. However, the standard device with Pt
CE possesses lower efficiency (1.78%), ascribed to lower Jsc
(7.55 mA cm−2 ), V oc (620 mV), and FF (38%) than the super-
ior CZTS-based DSSCs. The electrochemical properties of the
CZTS CEs and photovoltaic performance of its dummy cells
confirm that it is an economical and noble material for devel-
oping ZTO-based DSSCs, rather than Pt CE. Furthermore, in
comparison to the device with sputtered CZTS CEs, it is noted
that the DSSCs based on the electrodeposited CZTS CEs have
much higher solar performance due to higher porosity and the
active area created by the non-vacuum deposition method.
The improvement in the efficiency of the DSSCs using the
CZTS CEs based on thickness optimization is caused by the
increase of J sc and V oc . This conclusion can be deducted from
Semicond. Sci. Technol. 36 (2021) 105008 M Soltanmohammadi et al

Figure 10. Current density–voltage characteristics of the DSSCs with different CEs prepared by (a) electrodepositing and (b) sputtering
methods under AM 1.5 sun-light illumination of 100 mW cm−2 .

Table 4. Photovoltaic characteristics of the DSSCs with different 4. Conclusions

counter electrodes prepared by electrodepositing and sputtering
methods. Well-crystalline kesterite CZTS thin films, synthesized on
Sample V oc (mV) J sc (mA cm−2 ) FF (%) Efficiency (%) FTO substrates by two different processes (sputtering and
electrodepositing), were used as the CE in the ZTO-based
Pt 620 7.55 38 1.78 DSSCs. The photovoltaic and electrocatalytic performance of
CZTS-E1 620 8.20 40 2.03
DSSCs was dependent on the crystal quality and morphology
CZTS-E2 633 9.77 43 2.66
of the CEs. It was realized that the crystallinity of the CZTS
CZTS-E3 602 7.79 43 2.02
CZTS-S1 583 7.92 36 1.66 layers produced by both deposition techniques was improved
CZTS-S2 583 8.40 44 2.15 by an optimization process that could achieve low disloca-
tion density and high conductivity. The chemical deposition
route prepared CEs with porous structure and high surface
Table 5. Physical parameters of the optimized layers. roughness, which can be considered a practical approach to
enhance the electrocatalytic performance of DSSCs. It was
Thickness Bandgap Crystalline found that the optimized CZTS-S2 and CZTS-E2 layers pos-
Sample (nm) (eV) size (nm) Rs (Ω) Rct (Ω)
sess the lowest Rct among other deposited layers and higher
CZTS-E2 410.95 1.47 35.7 26.10 13.95 electrocatalytic activity than that of Pt CE for I− −
3 /I redox
CZTS-S2 427.77 1.45 24.5 66.23 42.02 reaction. The devices with optimum CZTS CE thicknesses
showed the conversion efficiency of 2.15% (CZTS-S2) and
2.66% (CZTS-E2), which were superior to that of the tra-
ditional Pt-based cell (1.78%). According to these results,
the data in tables 4 and 5. Particularly, the V oc of samples with CZTS CE substitution is helpful to improve potential elec-
around 500 nm thickness (CZTS-S2) markedly owns the max- trocatalytic performance, especially by utilizing a feasible and
imum value due to the large crystallite size, which led to more economical non-vacuum technique. The use of cost-effective
conductivity. So, the superior values of V oc and FF further CZTS as an alternative to noble Pt, in combination with the
confirm the crystal quality of the CZTS-S2 sample with the physical- or chemical-based fabrication methods, can promote
bandgap energy of 1.47 eV. Compared to the sample in which the possibility of developing low-cost, scalable, and efficient
the CZTS CE was prepared by the sputtering method (CZTS- DSSCs. Adding Se to the structure of the CZTS layer to vary
S2), the electrodeposited sample with nearly the same thick- the material bandgap energy and improve its electrical and
ness demonstrated a larger J sc , thus higher efficiency which optical properties in ZTO-based DSSCs can be done in future
can be explained by the CV and Tafel analyses. The highest J sc investigations.
for DSSCs based on CZTS-S2 and CZTS-E2 CEs comes from
a better electrocatalytic activity and lower Rct resistivity. The
value of J sc is principally influenced by the electrons, excited
to the conduction band and transmitted through the ZTO pho- Data availability statement
toanode and the electrolyte. In the CZTS-S2 with higher series
resistance, the recombination of carriers will increase dramat- The data that support the findings of this study are available
ically, and so, J sc reduces. upon reasonable request from the authors.

13
Semicond. Sci. Technol. 36 (2021) 105008
ORCID iDs
Mina Soltanmohammadi  https://orcid.org/0000-0003-
3081-3646
Vahid Karimi  https://orcid.org/0000-0002-9011-0339
Soheil Alee  https://orcid.org/0000-0002-0444-734X
Masoud Abrari  https://orcid.org/0000-0003-0290-978
Morteza Ahmadi  https://orcid.org/0000-0003-0788-5641
Majid Ghanaatshoar  https://orcid.org/0000-0003-4614-
1549
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