ABSTRACTS

Cadmium sulfide (CdS) thin films have been deposited on glass substrates at
30 °C for 36 h using chemical bath deposition technique. The deposition
was carried out in the pH range of 10–12 using aqueous solution of
cadmium nitrate and thioacetamide salts. Structure of these films was
characterized by X-ray diffraction (XRD) and scanning electron microscopy
(SEM). Elemental analyses of the films were studied by energy dispersive
X-ray analysis (EDX). The optical and electrical properties of the prepared
films were analyzed by absorbance spectra and Hall effects measurements,
respectively. Influence of the pH on the structural, optical and electrical
properties of CdS films was investigated. After all investigations, it was
concluded that the pH value of 10 is suitable for producing CdS films by
chemical bath deposition technique and the examined properties (good
crystallinity and low resistivity) of this film show its feasibility for
technological purposes, especially for solar cells.

CONTENTS:-
1. Introduction

2. Experimental details

3. Results and discussion

3.1. Structural properties
3.2. Surface properties
3.3. Electrical properties
3.4. Optical properties

4. Conclusions

5. References

1. Introduction
CdS, belonging to the II - VI group is an n-type semiconductor ,has direct band gap
(Eg = 2.42 eV) and its optical absorption issuitable for solar cells. The production
of CdS films has become increasingly important in recent years, since CdS and its
traditional p-type partner CdTe are leading and very promising materials for the
development of cost effective and reliable photovoltaics. The CdTe/CdS
polycrystalline solar cells are the most suitable photovoltaics because they provide
a potentially cheap, large area, stable photovoltaic technology. Although the
theoretical maximum efficiency for these cells is close to 30%, practically
achieved efficiencies are around 16.5% on laboratory scale. Hence, there is still
room to improve the efficiency of these structures.
CdS films have been prepared by various techniques such as spray pyrolysis,
chemical bath deposition (CBD), pulsed-laser deposition, deep technique, etc.
Among all those methods, CBD is most widely used deposition technique for CdS
thin films since 1960 s due to many advantages compared to others. First of all, the
chemicals used are commonly available and cheap. Beside there is no sophisticated
instrumentation needed and the synthesis of the films is very simple. For example,
the reactor can be a glass beaker and the substrates can be any material in various
shapes and sizes. Secondly, the film thickness and deposition rate is controlled by
pH, temperature and the relative concentrations of the reactants in the bath
solution. Third, the reaction takes place at low temperatures (27–80 ◦C). Hence,
considering those advantages, we have selected CBD method for depositing CdS
thin films.
Generally, for obtaining CdS thin films by CBD in aqueous solution, cadmium salt
is used as the Cd ion source, thiourea as the sulfur source, a base to adjust the pH
of solution, and a ligand to control the precipitation of chalcogenides and
hydroxides. As far as we know, several ligands have been utilized in the deposition
of CdS, such as NH3, triethanolamine, ethylenediamine, ethylenediaminetetra
acetic acid, nitrilotriacetic acid (NTA), cyano-complex, citrato-complex, and more
recently tartaric acid. Despite the advances in the processes of achieving CdS thin
film production, many issues are still opened, and new routes are welcome.
The present investigation has two different purposes: (i) growth of a thin film and
(ii) the effect of aqueous solution pH. The first purpose is related with a new
ligand. Up to now, according to our knowledge, the new ligand, isopropylxanthate,
used for obtaining CdS thin films by CBD have not been studied yet. The second
purpose is to interpret the effect of pH on the macro and microparameters of thin
CdS films
 .

2.Experimental details

CdS thin films were deposited by CBD method on

commercial glass substrates (76 × 25 mm2). In order to obtain the CdS thin film,
10 ml of 0.1 M cadmium nitrate [Cd(NO3)2.4H2O], 10 ml of 0.1 M thioacetamide
(CH3CSNH2), 200 l of 0.1 M isopropylxanthate [(CH3)2CHOCF2Na], which is
employed for the first time in our work, were used. All samples reported here
correspond to 36 h deposition time at a bath temperature of 30 ◦C. The film
deposition was carried out with the same basic bath composition. The pH of
solution was monitored by using a pH meter in order to prevent Cd(OH)2
precipitation (the formation of a Cd(OH)2 thin layer is a well known effect during
the CdS film growth [16,17]) during the addition of ammonia, NH3 (1%) into the
chemical bath.

CdS thin films can be prepared from decomposition of thioacetamide in an

alkaline solution containing a cadmium salt and a suitable complexing agent
which allows obtaining species of Cd2+ in this medium. The reaction process for
forming CdS thin films is considered as follows:

Cd(NO3)24H2O ↔ Cd2+ + 2NO3 − + 4H2O (1)

CH3CSNH2+H2O↔CH3COOH+H2S+NH3 (2)
H2S + H2O ↔ HS− + H3O+ (3)

HS− + H2O ↔ S2− + H3O+ (4)

NH3 + H2O ↔ NH4 + + OH− (5)

OH− + H3O+ ↔ 2H2O (6)

Cd2+ + S2− ↔ CdS (7)

Deposited films were yellow in colour and layer thicknesses were estimated by
the gravimetric weight difference method. For this, a sensitive microbalance was
utilized and film density was assumed as the bulk density of CdS (4.82 g cm−3).
Fig. 1 shows the variation of CdS film thickness as a function of the pH value. The
thickness increases from 393 to 710 nm when the pH decrases from 12 to 10.

The crystalline structure of the CdS thin films was confirmed by X-ray diffraction
(XRD) with a CuK1 radiation source (Rigaku RadB model, = 1.5406A)˚ over the
range 20◦ < 2 < 70◦ at a speed of 3◦ min−1 with a step size of 0.02◦. The surface
properties of all films were investigated using an EVO40-LEO computer controlled
digital scanning electron microscope (SEM). Chemical analysis by EDX was
performed with an EDXspectrometer attached to the SEM. The electrical
parameters like resistivity sheet resistance (Rs), carrier concentration (n) and
mobility (ρ) were determined using Van der Pauw method by a Hall Effect
measurement system (HS3000 Manual Ver 3.5) at room temperature. Specially
designed Hall probe on printed circuit board (PCB) was used to fix the sample of
the size 10 × 10 mm2. Silver paste was employed to ensure good electrical
contacts. The optical measurements of thin films were recorded by a Perkin Elmer
UV/VIS Lambda 2S spectrophotometer (double-beam) at room temperature by
placing an uncoated identical glass substrate in the reference beam. The optical
spectrum of the films recorded in the wavelength range of 350–1100 nm.
3. Results and discussion
3.1. Structural properties
XRD were performed to follow the change of layer crystallinity induced by the pH
of the chemical bath. Fig. 2 shows the diffraction patterns of single-crystalline CdS
films deposited at different pH ranging from 10 to 12. Only one peak can be
observed at the diffraction angle of ∼ 26.63◦ on the XRD spectrum for the CdS
films prepared at pH = 10–12. These diffraction patterns show that the films
deposited in this work are of a single-crystalline nature, with cubic structure and
preferential orientation in the (1 1 1) plane. The observed (d) values of the Bragg’s
interplanar spacing are compared with standard (d) values and they match well
as depicted in Table 1, indicating the formation of single-crystalline CdS film. The
diffraction patterns are also consistent with other cubic CdS thin films . The
intensity of the XRD peak corresponding to the (1 1 1) plane enhanced with the
decrease

Table 1
 The pH value, grain size (D) corresponding to the plane (111), and comparison of
the interplanar spacing (d) and lattice constant (a) between observed and
standard values of CdS film.

ph D(nm) Observed d Standard d Observed a Standard a

(A) (A) (A) (A)

10 76.58 3.337 3.355 5.779 5.811
11 59.16 3.347 3.355 5.797 5.811
12 28.54 3.345 3.355 5.794 5.811
of pH of the bath. Therefore, it can be concluded that the pH of the bath strongly
affects the formation of CdS films. An increase in the diffraction peak intensity,
depending on the pH value was also observed by Ben Nasr et al. in which ZnS thin
films were prepared by chemical bath deposition method.

To obtain information about the structural properties in detail, the grain size (D)
using the Scherrer formula (neglecting peak broadening due to residual stresses in
thefilms), dislocation density (ı), macrostrain e and lattice parameters (a = b = c
for cubic structure) along the (1 1 1) plane were calculated using the formulas
given below :

D = 0.9/ B cosθ (8)

δ= 1/D2 (9)

(e) = d − d0/ d0 (10)

dhkl= 1 /a2{( h2 + k2 + l 2)}−1/2 (11)

where B is the half width ofthe peak with maximum intensity as radian, D is the
grain size, is the Bragg angle, is the wavelength of the light used, d is the
interplanar spacing and d0 is the interplanar spacing without deformation.
Surface tensions, strains between the amorphous glass substrate and
depositedmaterial and inner strains as residual stresses in the films were
neglected. Dislocation density (ı) is defined as the length of dislocation lines per
unit volume of the crystal, and higher ı values indicate lower crystallinity levels for
the films. That is, ı values indicate the amount of defects in the structure.
Moreover, the number of crystallites per unit area (N) is calculated by using the
formula:

N=t/D3 (12)

where t is the film thickness. Grain size of the CdS films with different pH values
are listed in Table 1. It was clearly seen that the average grain size increased from
28.54 to 78.58 nm when the pH of chemical bath decreased from 12 to 10.
Furthermore, dislocation density, the number of crystallites and macrostrain of
CdS films are given in Fig. 3. The decrease of grain size results in an increase in the
grain boundaries and so the amount of defects in the structure. It was seen from
Fig. 3 that the ı values increase depending on the pH values. The increase of ı
values indicates that the dislocation defects in the structure increase. Besides, the
macrostrain e and number of crystallites of the CdS films increased with
increasing pH of the chemical bath.

As a result, XRD analyses showed that pH plays a significant role in the micro-
structure and structural properties of the cadmium sulfide films. The grain size of
the CdS film decreased when the pH increased from 10 to 12. As a result, the thin
film diverged from crystal structure. Moreover, the increase of the hydroxide
reaction caused formation of small grains, which was back to Fig. 2. It is clearly
seen that the optimum pH value of the deposited film was determined as 10.”
 Fig.4 SEM images of cds deposited at different solution ph , (a):10,(b):11 and
(c):12

3.2. Surface properties

Scanning electron microscopy (SEM) was used to investigate the effect of the pH
on film surface properties because the surface properties directly affect the
electrical and optical properties of the films. The SEM images of the CdS thin films
with different pH are presented in Fig. 4. The SEM analysis, as well as being in 186
agreement with the XRD results, supplied additional experimental confirmation.
As can be seen from Fig. 4a–c, the size of the crystallites decreased with
increasing solution pH. All films are dense and have strong adherence to the
substrates. It is observed from Fig. 4b and c that some aggregates of CdS
nanoparticles have revealed. These surface properties have strong effect on the
optical properties of films such as transmittance, absorbance and reflection. So, it
was concluded that the surface properties of the CdS films were improved for the
film grown at pH = 10. Similar behavior was reported previously by Mazón-
Montijo et al. and Suryajaya et al.

The EDX technique was used to estimate the composition of the CdS thin films.
Fig. 5 shows the average atomic ratio of Cd/S as a function of pH. It was seen that
Cd/S ratio decreases from 1.06 to 0.98 with increasing pH. EDX results indicate
that the average atomic ratio of Cd/S is nearly stoichiometric ratio (Cd/S = 1).

3.3. Electrical
properties
Electrical resistivity
carrier mobility and
carrier
concentration (n) of the CdS
films deposited at different
pH values of chemical
bath were measured
using Van der Pauw geometry and Hall effect measurements at room
temperature using Ag ohmic contacts and a magnetic field (0.540 T). It is seen
that all films have n-type conductivity. The dependence of electrical resistivity,
carrier mobility and carrier concentration ofthe CdS films on pH values are given
in Fig. 6. It was clearly seen that the electrical resistivity increased from 4.375 ×
105 to 8.931 × 105 cm with increase in pH from the relation:

ρ =1/Neч (13)
The increase in electrical resistivity may indicate a deviation in film stoichiometry
or a decrease in mobility and carrier concentration. The electrical resistivity values
are in consistent with previously reported values by Liu et al. and by Santos Cruz
et al. Moreover, measured resistivity values are higher than the Ref. , and lower
than the Ref. for cubic CdS thin films, it can be concluded that our films have
higher number of defects than the Ref., but lower than the latter. Additionally, it
was seen that mobility decreased from 1.636 × 102 to 7.510 × 10−1 cm2 V−1 s−1
with increasing pH. The mobility of CdS films deposited at pH = 10 are higher than
the other two films. This can be understood by considering the grain size of the
films at pH = 10 (78.58 nm) being larger than that of other two films at pH = 11
(59.15 nm) and pH = 12 (28.54 nm) . The carrier concentration is in the order of
1013 cm−3 for all films and these values are in agreement with that of chemical
bath deposited CdS films.
3.4. Optical properties
Transmission measurements are performed at room temperature in the range of
300 - 1100 nm to obtain information on the optical properties of the CdS thin
films obtained at different pH values. The transmission and reflectance spectra of
the films are shown in Fig. 7. Due to interference ofthefilms,transmission curves
showed fluctuations and wave-like patterns. In the wavelength range of 400–700
nm, the optical transmission is the largest ∼ 79% at pH = 10 and it decreases to
the value of ∼ 76% at pH = 12. Among all ofthe films grown, films grown at pH =
10 appear to have the best crystallinity and the highest transmission in the visible
region and it was found that transmission values of those films are higher than
that available inliterature [20].It canbe concludedthatfor the same deposition
time, films grown at low growth rate (pH = 12) are thinner and have lower
absorption with worse crystallinity whereas, films grown at higher growth rate
(pH = 10) are thicker have and higher absorption with better crystallinity. Hence, a
decrease in the pH values of chemical bath improves the film optical transmission
and crystallinity.

It is found that optical absorption coefficient, derived from transmittance, is a

function of photon energy and the presence of an absorption edge. In the
wavelength internal of 400–1100 nm, the optical absorption coefficient was
calculated to be of the of 105 cm−1. After determining absorption coefficient, the
value of optic band gap can be found. By using absorption coefficient, the value of
band gap can be determined by using the formula below :

(˛h) = A(h− Eg ) n (14)

 where˛is the absorptioncoefficient,(h)is thephotonenergy,A is a coefficient and
‘n’ gets the values of 1/2, 2, 3/2 and 3 for allowed direct, allowed indirect,
forbidden direct and forbidden indirect transitions, respectively. Additionally, in a
crystalline or polycrystalline material, both direct and indirect transitions can
occur depending on the band structure of the material. To determine whether the
films have allowed direct, allowed indirect, forbidden director forbidden indirect
gap, plots of (˛h)2 versus (h), (˛h)1/2 versus (h),(˛h)2/3 versus (h) or (˛h)1/3 versus
(h) were drawn, respectively. The plots for all transitions are depicted in Fig. 8a–d.
The straight-line portions were extrapolated to the energy axis at ˛= 0, to obtain
band gaps of the CdS thin films. It was seen that better linearity was observed in
the former case and determined that all films have a direct band transition.
Determined band gap energies are shown in Fig. 9 as a function pH. As can be
seen from this figure, band gap value for the allowed direct transition decreased
from 2.45 eV to 2.28 eV with increasing pH. However, band gap values of allowed
indirect, forbidden direct and forbidden indirect transitions increased from 1.50
eV to 1.78 eV, 1.56 eV to 1.75 eV and 1.40 eV to 1.84 eV, respectively. The
calculated direct band gap values are in good agreement with previously reported
values for cubic CdS thin films produced by chemical bath deposition .

The reflectivity (R) (Fig. 7) for CdS films can be calculated using the transmittance
(T) and absorbance (A) spectra from the expression :

T = (1 − R) 2 exp(−A) (15)

Refraction index (nr) and extinction coefficient (k) for CdS films are given by the
formulas [35]:

k = αƛ/4π (16)

nr =( 1 + R/ 1 – R) + ( 4R /(1 − R) 2 − k2)1/2 (17)

The refractive index and the extinction coefficient spectra of CdS films with
different pH values are shown in Figs. 10 and 11, respectively. In the visible
region, the values of nr and k changed in the range 4.145–1.839 and 0.059–0.017,
respectively. The refractive index of the thin films obtained at pH = 10 is n = 2.475
at the wavelength of 500 nm, which is in good agreement with that of bulk CdS.
However, the extinction coefficient of mentioned films at the same wavelength, k
= 0.0171, is smaller than 0.0186 for bulk CdS.
4.Conclusions
Cadmium sulfide thin films with a new ligand are prepared on glass substrates by
the CBD technique. The effects of pH value on the structural, optical and electrical
properties of the CdS films have been investigated. These studies show that the
structural, optical and electrical properties of deposited films are very sensitive to
the pH value of the chemical bath. SEM images show that deposited films were
dense, have well substrate adherence and crystalline nature with a cubic
structure. CdS films with a Cd/S ratio nearly equals to 1 have the best optical,
structural and electrical properties. It is particularly observed that the best
crystallinity, high transmission (79%), low electrical resistivity (4.375 × 105 cm) are
obtained at pH = 10. The decreasing of the pH value from 12 to 10 results in
increasing of the (1 1 1) diffraction peak intensity. The optical transmission is
found to increase while pH decreases from 12 to10. Considering all transitions, it
was determined that all films have a direct band gap value for the allowed direct
transition which decreased from 2.45 eV to 2.28 eV with increasing pH. From
these studies, we are able to optimize the process in order to produce the better
quality layer suitable for optical window in solar cells.