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Fabrication of nanocrystalline Cd(Zn, S)Se thin films for PV-application: An
electrochemical approach
Conference Paper in AIP Conference Proceedings · July 2018
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Fabrication of nanocrystalline Cd(Zn, S)Se thin films for PV-application: An
electrochemical approach
G. T. Chavan, S. T. Pawar, V. M. Prakshale, M. S. Mane, S. Ezugwu, S. S. Kamble, N. B. Chaure, N. N. Maldar,
and L. P. Deshmukh
Citation: AIP Conference Proceedings 1989, 020005 (2018); doi: 10.1063/1.5047681
View online: https://doi.org/10.1063/1.5047681
View Table of Contents: http://aip.scitation.org/toc/apc/1989/1
Published by the American Institute of Physics
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Fabrication of Nanocrystalline Cd(Zn, S)Se Thin Films for
PV-Application: An Electrochemical Approach
G.T. Chavan a, S.T. Pawar a, V.M. Prakshale a, M.S. Mane a, S. Ezugwu b, S.S.
Kamble c, N.B. Chaure d, N.N. Maldar e and L.P. Deshmukh a,*
a
Thin Film & Solar Studies Research Laboratory, Solapur University, Solapur 413 255, M.S., India.
b
Department of Physics and Astronomy, University of Western Ontario, London, ON N6A 3K7, Canada.
c
Government Polytechnique, Vikramgadh, Palghar, M.S., India.
d
Department of Physics, Savitribai Phule Pune University, Pune - 411007, M.S., India.
e
Polymer Chemistry Department, Solapur University, Solapur 413 255, M.S., India.
*
[email protected]
Abstract
The design considerations of light-harvesting and energy-converting systems belong to one of the most highlighted fields in
modern research. Recently, it has been pointed out that binary semiconducting materials with addition of one/or two or even
more suitable elements provide a better prospect through their property engineering resulting in alloyed/multiphase
compositions. We are presenting the synthesis and growth of CdSe and Cd1-xZnxSySe1-y (0 ≤ x = y ≤ 0.35) thin film using
solution growth technique developed and made optimistic by us. The nature of the growth surface was determined by the
contact angle measurements. The EDS analysis confirmed substitution of Cd by Zn and Se by S at high x and y concentrations.
The structural determination using X-ray diffraction (XRD) analysis suggested formation of the polycrystalline films of
hexagonal-wurtzite structure. The SEM observations showed a network of rhomboidal flower like crystallites transformed from
an aggregated bunch of nano-sized globular grains as a result of addition of Zn and S in to CdSe.
The electrode/electrolyte PV-cells were then formed with these films as photoelectrodes and a sulphide/polysulphide as an
electrolyte (0.25 M) and investigated through the different electrical and optical characteristics in dark and under illumination.
The maximum open-circuit photo voltage of 400 mV and a short circuit photocurrent of 0.166 mA/cm2 were obtained from a
cell fabricated with an electrode composition of x = y = 0.075 (I/P illumination intensity is 13.4 mW/cm2). This resulted in the
energy conversion efficiency of 3.18% and a fill factor of 64.1% respectively. The enhancement in PV-performance is
explained adequately and supported by the changes in the electrode properties.
Keywords: Cd(Zn, S)Se thin film electrode; microstructure; EDS; Open circuit voltage; short circuit current; efficiency
INTRODUCTION
The environmental benign, cost effectiveness and alternative energy sources are todays global needs. An
extreme reliance on various nonrenewable energy sources brings not only an economical problem but also affects
the global economy and civilization. Thus development of cost effective and efficient solar cell devices is gaining
much popularity. Alterations and property engineering of the materials properties are of importance in this sense.
Thus quest for new semiconductor materials and up-gradation of the existing ones have key role in the Materials
Science [1]. Therefore, to develop a new multifunctional combination in this frame rule, it is essential to
incorporate various independent nanosized materials in a sequential manner. For their greater flexibility in
composition control and band gap modulation, quaternary alloy semiconductors have a wider range of potential
applications in tunable optoelectronic devices than the ternary ones [2]. The materials properties can be engineered
as expected by alloying semiconductor compounds resulting into a ternary / quaternary / multi-phase compositions.
This is a key for bandgap modulation and a facile way of tuning the optical, electronic/transport properties, surface
topographic evolution and many allied materials characteristics offering the enhanced potoactivity over a broad
range of the visible-NIR spectra [1, 3].
The quaternary materials are therefore attracting a great attention of the scientific and industrial
communities as they are the strong potential contenders referred to the various optoelectronic applications. On the
other hand, their synthesis techniques and methods are too crucial, tedious and cost intensive. Cd(Zn, S)Se is an
important but less studied material that combines the multiple features of the binary and even ternary components
Emerging Technologies: Micro to Nano (ETMN-2017)
AIP Conf. Proc. 1989, 020005-1–020005-5; https://doi.org/10.1063/1.5047681
Published by AIP Publishing. 978-0-7354-1705-2/$30.00
020005-1
composing it; the stability of the resulting material and its optimum band gap are of extremely importance in the
optoelectronic applications. In our case relatively high stability of ZnSe and CdS over CdSe can help to enhance
the resulting materials stability and that the end material can be grown suitably to obtain a homogenous alloy phase
with our indigenously developed and automated solution growth technique [4]. Therefore, in our studies it was
planned to obtain quaternary Cd1-xZnxSySe1-y (0 ≤ x = y ≤ 0.35) thin films of various composition under different
growth conditions. These films were then characterized to check their suitability for use in electrochemical
photovoltaic (PV) applications. We hope this polycrystalline quaternary material will open a wide range of
applications in the field of optoelectronics.
MATERIALS SYNTHESIS AND METHODS OF MEASUREMENTS
Cadmium selenide and cadmium zinc sulpho selenide [Cd1-xZnxSySe1-y (0 ≤ x = y ≤ 0.35)] thin film layers were
obtained on the spectroscopic grade glasses and mirror grade polished stainless-steel substrates using our solution
growth process [5]. The substrates were attached vertically to a substrate holder and immersed in the reaction bath.
The reaction bath was composed with 10 ml, 1 M CdSO 4, 33 ml (0.33 M) sodium selnosulphate and appropriate
quantities of 1 M ZnSO4 and 1 M Sulphur so as to maintain 1-x , x, 1-y and y respectively. The optimized working
conditions were: pH = 10 ± 0.1, deposition temperature = 70 ± 0.1 °C, deposition time = 100 mins and speed of the
substrate spinning was 65 rpm. The films were then taken of the reaction container, washed several times with
double distilled water and then with ammonium chloride to dissolve the precipitate if any.
The contact angle measurements were carried out to check the nature of glass- thin film surface. The film
composition was determined using a JEOL 6360-JED2300 energy dispersive spectroscope. A Rigaku X-ray
diffractometer was used for the determination of crystallographic properties. A Cu Kα (λ = 1.5406 Å) radiation
was used as target material. The range of scanning angels was from 20° to 80°. The microstructure of the film
samples was observed through an electron microscope LEO (Zeiss) 1540XB SEM. The PV-cells were then formed
and the electrical properties namely I-V and C-V characteristics in dark and power output characteristics under
illumination were recorded under a white light illumination of 13.4 mW/cm 2. The current flowing through the
junction and voltage applied across the junction were measured by the 6½, digit HP and 4½ digit HIL multimeters,
respectively. A potentiometric arrangement with two-electrode cell geometry was used for this purpose. For the
Capacitance-Voltage measurements, three-electrode geometry was used and the junction capacitance was
measured a 4 ½ digit capacitance meter (Philips).
RESULTS AND DISCUSSION
1. Wettability measurements
To understand the growth mechanism, wettability studies were carried out. The results showed that the glass-film
surface for CdSe is hydrophilic in nature with θ = 76.8°. The contact angle (θ) values showed unsystematic
behaviour with increasing concentration of Zn and S in CdSe. This is shown in fig. 1 and these changes can be
related to the possible topographical changes due to the addition of Zn and S in CdSe [5]. Consequently, the films
are useful for making good intimate contact with an aqueous electrolyte and in turn in the electrochemical PV-
cells.
2. EDS analysis
The elemental chemical analysis of the as-deposited CdSe and Cd1-xZnxSySe1-y thin films (0 ≤ x = y ≤ 0.35) was
carried out by an EDS technique. Fig. 1 shows the EDS micrographs of the five samples. The analysis revealed
that pure CdSe films are perfectly stoichiometric (Cd/Se = 0.99). With the simultaneous addition of Zn and S (0 ≤
x = y ≤ 0.075) in CdSe, Cd2+ went on increasing whereas, Se2- decreased drastically. We can interpret that both S2-
and Zn2+ replace Se2- from the CdSe lattice, the rate of Se2- replacement by S2- being significantly higher upto x =
y = 0.075. At higher values of Zn and S concentrations, films are non-stoichiometric and both Zn and S tends to
form separate phases of ZnSe and CdS observed form SEM micrographs.
020005-2
G X 1016, lines/m2
10
105
-4
Micro strain, (H x 10
8
90
6 75
Dislocation density,
60
4
45
2
G 30
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35
Composition parameter, x = y
FIGURE 1. Variation in the dislocation density and FIGURE 2. EDAX spectra for typical CdSe and Cd1-
micro strain with the sample composition. xZnxSySe1-y (0 ≤ x = y ≤ 0.35) thin films (corresponding
angle of contact is also shown).
3. XRD analysis
XRD technique was used to determine the phases and crystallinity of both CdSe and Cd(Zn, S)Se thin films. It was
expected that a stable single phase Cd(Zn, S)Se phase was to grow, however, a single or two minor phases of ZnS,
ZnSe and CdS were also detected in addition to Cd(Zn, S)Se phase when Zn2+ and S2− were added in CdSe (at
higher concentrations). The intensities of reflections of these phases are < 10 %. The d-values and I/Imax values are
in agreement with the standard JCPDS values [5]. This shows that the films are polycrystalline quaternary phase of
hexagonal wurtzite structure [5]. As a part of the structural studies, microstructural parameters like number of
crystallites (N), dislocation density (δ) and micro strain (ε) were evaluated using these studies and the standard
formulae. The micro strain and dislocation density decreased with increasing concentration of x = y up to 0.075, and
again increased at higher compositions as shown in fig. 2. The micro strain and dislocation density are the indication
of occurrence of dislocation network in the as-grown films. The decrease in the dislocation density up to 0.075
indicates the formation of good quality thin films [6]. Overall, composition parameter (x = y) plays a crucial role in
determining the quality of the material. Some of the materials characteristics are shown in table 1.
TABLE 1. Some crystallographic parameters calculated from the XRD analysis.
Composition No. of δ x 1016 Micro
parameter, Crystallites lines/m2 strain
(x = y) x 1018 m-3 x 10-4
0 3.60 9.77 113
0.01 3.30 8.82 107
0.025 3.03 7.39 98
0.05 1.91 4.37 75
0.075 1.01 2.23 54
0.1 1.67 3.92 71
0.15 1.45 4.69 78
0.2 1.14 4.81 79
0.25 1.11 4.88 80
0.3 1.41 5.97 88
0.35 1.40 7.04 96
4. Morphological Observations
The micrograph of the pure CdSe sample shows rounded spherical crystallites having size in terms of nanometers
that cover the substrate. A globule like structure over the already grown crystals is observed as a result of fusing two
020005-3
or more crystallites together. However, it is seen that, with the increase in composition parameter (x = y) the surface
topography changes from nano sized globular crystallites to an irregular network of polygonic petals (fig. 3). This
erratically tuned microstructure consists of smaller crystallites (almost spherical in shape) interlinked and grown
onto the larger petal like background. At, x = y = 0.075, the microstructure shows almost petal/flakes like structures;
nearly a homogeneous morphology with enhanced surface area. This enhanced surface morphology may enhance the
absorption of the incident solar radiation and therefore, contributes to the enhanced spectral sensitivity over a wide
range of solar spectrum that favours high conversion efficiency [5].
FIGURE 3. The SEM micrographs of CdSe and Cd1-xZnxSySe1-y thin films.
FIGURE 4. Power output curves for various Cd(Zn, S)Se based PV cells. (Inset-Mott –Schottky plots for different
photovoltaic cells of different photoelectrode compositions).
020005-4
5. Electrochemical photovoltaic studies
The variation of 1/C2 vs voltage (vs SCE) for six typical PV-cells is shown in fig. 4 (inset). The plots were
extrapolated to the voltage axis to give Vfb’, the flat band potential. The negative sign of the flat band potential
indicated the type of the materials as n-type. Vfb varied from -813 mV to -970 mV for the cell configuration whose
electrode composition is x = y = 0.075. For further increased electrode compositions, Vfb decreased. The power
output measurements were carried out on these cells at room temperature under illumination intensity of 13.4
mW/cm2. The Cd(Zn, S)Se based electrochemical photovoltaic (PV) cell with x = y = 0.075 showed a short circuit
current density (Isc) of 166 μA/cm2, open circuit voltage (Voc) of 400 mV, fill factor (FF) of 64% and the power
conversion efficiency (η) of 3.18%. We attribute this improved device performance mainly to the incremental
increase in short circuit photocurrent (Isc), open circuit photo voltage (Voc) and the enhanced flat band potential,
decrease in the dislocation density, enhancement in the film thickness and microstructural evolution.
CONCLUSIONS
In Summary, polycrystalline Cd(Zn, S)Se thin films with a wurtzite type structure were successfully synthesized by
a solution growth technique. The surface topography shows changes from nano sized rounded crystallites to an
irregular network of polygonic petals. The solar cell performance showed Voc, Isc, FF and efficiency to be 400 mV,
166 μA/cm2 and FF 64 % and η = 3.18 % respectively for the a PV cell with electrode composition of x = y = 0.075.
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