Solar Energy Vol. 64, Nos 1–3, pp.

41–47, 1998
© 1998 Elsevier Science Ltd
PII: S0038-092X(98)00047-4 All rights reserved. Printed in Great Britain
0038-092X/98 $—see front matter

PROPERTIES OF CADMIUM SULFIDE THIN FILMS DEPOSITED BY

CHEMICAL BATH DEPOSITION WITH ULTRASONICATION
JUN YOUNG CHOI,* KANG-JIN KIM,** JI-BEOM YOO*** and DONGHWAN KIM*
* Division of Materials Science and Engineering, Korea University, Seoul, 136-701, South Korea
** Department of Chemistry, Korea University, Seoul, 136-701, South Korea
*** Department of Materials Science and Engineering, Sungkyunkwan University, Suwon 440-746,
South Korea

Received 24 September 1997; revised version accepted 31 March 1998

Communicated by MAKOTO KONAGAI

Abstract—Ultrasonic agitation was applied during the chemical bath deposition of CdS thin films.
Ultrasonication resulted in a dramatic difference in surface morphology, growth rate, and optical proper-
ties of CdS films. There were virtually no colloidal particles adsorbed on the surface. The surface roughness
measured by atomic force microscopy was reduced by a factor of two. Band gap energy increased to
2.39 eV from 2.37 eV. X-ray patterns showed that the preferred orientation changed from
hexagonal(002)/cubic(111) to hexagonal(101). Optical transmission improved in the wavelength range
longer than 520 nm. The chemical reaction for CdS formation started at a lower temperature under
ultrasonication, and dense films were obtained even when the chemical composition of the aqueous
solution deviated far from the optimum conditions. © 1998 Elsevier Science Ltd. All rights reserved.

1. INTRODUCTION growth of CBD CdS films has been reported

Thin film cadmium sulfide is a suitable n-type
semiconductor for a window layer in CdTe/CdS
heterojunction solar cells. Uniform and
transparent CdS films are needed to produce
high efficiency solar cells. Various techniques,
such as vacuum evaporation ( Kim et al., 1994),
spray deposition, electrodeposition (Morris
et al., 1991), screen printing (Park et al., 1992),
chemical vapor deposition (Berry et al., 1992),
RF sputtering (Tomita et al., 1994) and chemi-
cal bath deposition (CBD) (Lanning and
Armstrong, 1992; Kaur et al., 1980; Lincot and
Ortega, 1992; Rieke and Bentjen, 1993) have
been used to make CdS layers, but there are
some problems in each method. For example,
it is difficult to obtain stoichiometric CdS by
the evaporation technique and a high temper-
ature is required in spray deposition.
The CBD process, which produces CdS films
through reactions between Cd and S ions in an
alkaline solution, is used to make high quality
films which have few defects and a uniform
stoichiometry. CBD-grown CdS films also have
excellent electrical and optical properties.
Moreover, the process is readily scalable to
large-area processing with low fabrication cost.
The deposition process is controlled by the
chemical reaction kinetics in an ammonia solu-
tion of cadmium salt ( Kaur et al., 1980).
Although research work that observed the
41
constantly, the mechanism of CdS deposition
does not seem to have been established. This is
because most of the studies were concerned with
optimizing the reaction conditions (e.g. pH,
temperature, solute concentrations) to produce
CdS films that were adequate for solar cells.
The aim of this study is to investigate the
influence of ultrasonication on the CdS depos-
ition through observing the characteristic
change of CdS films and to shed light upon the
mechanism of the CdS deposition.
To produce CdS thin films, an alkaline solu-
tion of cadmium salt and a thiourea solution
are prepared. The film growth takes place
through ion-by-ion condensation of Cd2+ and
S2− ions on the substrate when Cd2+ and S2−
ions exist over the solubility limit (Lincot and
Ortega, 1992). Typical reaction steps involving
cadmium acetate are as follows:
(NH ) CS+2OH−S2−+CN H +2H O
22 2 2 2
(1)
Cd(NH )2+Cd2++4NH (2)
34 3
Cd2++S2−CdS (3)
Sulfide ions are released by the hydrolysis
of thiourea, but Cd2+ ions form tetra-
aminecadmium(II ) complex ions by combining
with NH in the range of pH 10–11 (Rieke and
3
Bentjen, 1993). These Cd(NH )2+ complexes
34
42 J. Y. Choi et al.
adsorb on the glass, then a heterogeneous nucle-
ation and growth takes place by ionic exchange
reaction with S2− ions (Pavaskar et al., 1977).
This process is called an ion-by-ion process. In
this manner, CdS is deposited in the form of
transparent, uniform and adherent film. In con-
trast, CdS colloidal particles which precipitate
homogeneously in the bulk solution adsorb
randomly on the growing film, and thus form
opaque, non-uniform and poorly adherent ‘‘B-
quality’’ films ( Kaur et al., 1980; Lincot and
Ortega, 1992). This is called a colloid-by-colloid
process and usually happens at a later stage of
the deposition.
High quality films, having less ‘‘B-quality’’
characteristics, can be obtained by controlling
pH, the concentration of precursors and the
reaction temperature. However, it is very diffi-
cult and time-consuming to control the condi-
tions precisely, because the two reactions (ion-
by-ion and colloid-by-colloid ) are usually
taking place at the same time, no matter how
well one controls the conditions (Ortega-Borges
and Lincot, 1993). Our study is focused on
using external forces, such as ultrasonic agita-
tion, that may eliminate the ‘‘B-quality’’
component.
Recently, ultrasonication was applied to vari-
ous fields of science (Suslick, 1995). The forma-
tion, growth, and implosive collapse of bubbles
occurs when ultrasounds having a frequency
from around 15 kHz to tens of megahertz pass
Fig. 1. Schematic diagram of the CBD system used in this study.
through a liquid. This is called acoustic cavita-
tion and it induces hot spots with a temperature
of 5000 K and a pressure of 1.7×105 kPa within
a very short time period.
In some cases, ultrasound shows catalytic
properties in some chemical reactions (Suslick,
1995). Thus, ultrasonication is expected to make
differences in the chemical reactions as well as
in the physical state of the films, such as the
surface morphology and microstructure. This
study shows that ultrasonication has a tremen-
dous influence on the growth rate, optical prop-
erties and microstructure of CdS films and the
chemical reaction of the CdS formation. We
believe that similar results would be obtained if
ultrasonication were applied to any other
electroless deposition system. To our best
knowledge, this is the first study of the effect of
ultrasonication on the deposition of thin films.
2. EXPERIMENT
This study was carried out using aqueous
solutions of Cd salt (cadmium acetate) concen-
trations in the range of 0.004 to 0.016 , thio-
urea concentrations of 0.005 to 0.015 ,
buffering agent NH Ac of 0.02 to 0.08  in
4
1.74  ammonia solutions. The reaction temper-
ature was fixed between 80 and 83°C and the
solution was stirred vigorously. The above con-
dition is known as an optimum condition for
 Properties of cadmium sulfide thin films
Fig. 2. XRD patterns of CdS films deposited (a) without ultrasonication, (b) with ultrasonication; deposition time: 40 min.
producing high quality CdS films (Dhere
et al., 1995).
The deposition system ( Fig. 1) was a rectan-
gular bath (15 cm×10 cm×13 cm) with trans-
ducers on two sides. The substrates were placed
at 2 cm away from the sides facing the trans-
ducer (nominal frequency of 20 kHz and power
of 132 W ). The solution was mixed at room
temperature, then heated to the reaction temper-
ature while being stirred by an impeller. The
substrates were indium–tin oxide (ITO) coated
Corning@ 7059 glasses. The structure of CdS
films was analyzed using an X-ray diffracto-
meter (Rigaku 20B) equipped with a Cu Ka
target. Film thickness was measured by a profi-
lometer (Alpha-step@ surface profiler 200).
Surface morphology was observed using scan-
ning electron microscopy (FE-SEM, Hitachi
S-4200) and atomic force microscopy (AFM ).
The optical absorption data were obtained from
an HP-UV 8042 spectrophotometer.
3. RESULTS AND DISCUSSION
3.1. Structure of CdS films
CdS films, which were deposited on ITO
glass, can have either a hexagonal or a cubic
structure or, a mixed structure of the two,
depending on the preparation conditions ( Kaur
et al., 1980; Lincot and Ortega, 1993). The
hexagonal structure is the stable phase of CdS
at room temperature.
43
Our CdS films had a mixed structure, as
shown in the X-ray diffraction ( XRD) pattern
(Fig. 2). It seemed that the film consisted of an
fcc structure with a hint of hexagonal phase
judging from the XRD intensities of the
fcc(111) and hexagonal(002) peaks. However,
under ultrasonication, a noticeable change in
the crystal structure occurred. A peak from the
hexagonal structure, wurtzite, was observed at
about 27° corresponding to the (101) reflection,
whereas the peak intensity of the cubic(111)
decreased to nil. The results indicate that, under
ultrasonication, only the stable phase of CdS
formed, probably due to the high temperature
( locally) induced by the ultrasonication.
We also examined the XRD pattern of colloi-
Fig. 3. Film thickness versus deposition time, with and with-
out ultrasonication. [CdAc ]: 0.004 ; [ Tu]: 0.005 ;
2
[NH Ac]: 0.02 ; [NH OH ]: 0.4 .
4 4
44 J. Y. Choi et al.

dal particles suspended in the solution.

Colloidal particles, produced under ultrasonica-
tion, had no sharp peaks, whereas well-defined
patterns were observed from the particles with
no ultrasonication.

3.2. Deposition rates

Figure 3 shows the thickness change of CdS
films with increasing deposition time. There are
two different regimes. In the short time regime
(regime A, before 20 min), two curves almost
coincide with each other, but with increasing
time the difference in growth rates widens
between the two conditions. The implication of
this result is that the ultrasonic agitation sup-
presses the growth of the ‘‘B-quality’’ compo-
nent in the film which consists of the adsorbed
colloidal particles. We believe that the ultrasonic
impact breaks the inherently loose connection
between the adsorbed particles and the surface
of the growing film. It should be noted that the
plateau, where the film no longer grows, begins
at a shorter time and a lower thickness
(~120 nm) under ultrasonication.
For solutions with higher Cd concentrations
this phenomenon became more apparent. With
increasing Cd concentration the thickness of the
CdS films became thicker up to 200–300 nm,
but no increase in thickness over 150 nm was Fig. 4. SEM images of CdS films (a) without ultrasonication,
(b) with ultrasonication. [CdAc ]: 0.008 ; [ Tu]: 0.005 ;
observed under ultrasonication. The growth rate 2
[NH Ac]: 0.08 ; [NH OH ]: 0.4 ; deposition time: 40 min.
can easily be controlled at any condition using 4 4
ultrasonication owing to the large plateau
region. Also, for a given thickness, such as CdS films deposited by the normal CBD system
100 nm, it takes much less time (~30 min) to was 12–15 nm, ultrasonication reduced it to
obtain high quality films without adsorbed CdS 3–5 nm. The results seem to indicate that ultra-
particles when ultrasonication is applied, sonication suppresses the growth of CdS grains
because with ultrasonication it is not necessary by the high pressures impacted on the growing
to slow down the growth rate for suppressing surface to make CdS films nanocrystalline
the homogeneous nucleation in the bulk solu- (Suslick, 1995). Also, it is possible that the
tion. Therefore, the throughput is enhanced. ultrasonication may have facilitated the nucle-
ation of CdS so that there was a uniform
3.3. Surface morphology nucleation throughout the substrate surface.
The most dramatic results of ultrasonic agita- To observe the influence of ultrasonication
tion appear in the microstructure of CdS. on the CdS microstructure more clearly, we
Figure 4 is the surface morphology of CdS films investigated CdS films deposited under higher
observed by SEM. Though the composition of Cd concentrations. There was little change in
the solution was optimized in terms of concen- the ultrasonicated films, whereas much higher
tration, pH, and temperature to obtain high densities of adsorbed particles and larger grains
quality films, it is noteworthy that CdS films were observed on films without ultrasonication.
formed under ultrasonic agitation showed an CdS films with uniform, compact and nano-
even more compact and smooth surface. Not sized grains could be obtained even under non-
only were there no adsorbed colloidal particles, optimal conditions.
shown as white boulders on the surface, but Figure 5 is the surface morphology of CdS
there was a remarkable difference in grain sizes colloidal particles precipitated homogeneously
and their uniformity. Whereas the grain size of in the bulk solution. CdS particles formed with-
 Properties of cadmium sulfide thin films
Fig. 5. The surface morphology of CdS colloidal particles
in the solution (a) without ultrasonication, (b) with ultra-
sonication. [CdAc ]: 0.008 ; [ Tu]: 0.005 ; [NH Ac]:
2 4
0.08 ; [NH OH ]: 0.4 ; deposition time: 40 min.
4
out ultrasonication revealed a larger structure
which consisted of plate-like shapes ( Fig. 5(a)).
As might be expected, ultrasonication changed
the rough and plate-like surface of the particles
to a smooth one. When observed at low magni-
fication, the size and shape of the particles
formed under ultrasonication were more uni-
form than the others. Judging from the results,
the effect of ultrasonication is believed to be
either promoting the nucleation of CdS or
breaking large particles into pieces and their
agglomeration, both of which would result in
the microstructure shown in Fig. 5(b).
As mentioned above, the XRD pattern of the
colloidal particles with ultrasonication showed
poor resolution. We think that many small
individual crystallites were agglomerated under
ultrasonication, and thus the poorly resolved
XRD patterns were obtained. So, the SEM
images coincide well with the XRD results
obtained from these particles. Figure 6 shows
the root-mean-square roughness measured by
AFM on films that were deposited under
45
Fig. 6. Surface roughness measured by AFM on CdS films
deposited under various CdAc concentrations.
2
Fig. 7. Transmittance of CdS films. Film thickness 1200 Å.
different Cd concentrations. Roughness
increased rapidly with increasing Cd concen-
tration, but there was much less increase under
ultrasonication. This result corresponds very
well to the SEM images in Fig. 4.
3.4. Transmittance and band gap energy
UV spectrophotometer measurements were
carried out on films of the same thickness of
120 nm (Fig. 7). Higher transmittance was
observed from the films with ultrasonication in
the long wavelength range (over 520 nm).
However, in the short wavelength region the
films made without ultrasonication showed
higher transmittance. With increasing film
thickness the difference diminished in the short
wavelength region, but it widened in the long
wavelength region. Absorption of light in the
longer wavelength region (l≥520 nm) is usually
caused by crystalline defects such as grain
boundaries and dislocations. High transmit-
tance values obtained from the films with ultra-
sonication imply that CdS grown under
ultrasonication has a lower defect density, and
thus in turn may have better electrical proper-
ties. Transmission of light in the shorter wave-
length region (l<520 nm, i.e. above the band
46
gap energy) happens when the films are not
thick or the thickness of the films is not uniform,
i.e. if pinholes exist in the film. A low transmit-
tance of ultrasonicated film indicates that the
film is of a denser and more uniform structure.
This result coincides well with the SEM results
in Fig. 4. The fact that the difference in transmit-
tance decreased in the short wavelength region
but increased in the long wavelength region
with increasing film thickness also supports the
argument given above.
From Fig. 7. we could obtain the plot of
absorbance of CdS films versus photon energy
and the band gap energy of CdS by using
Eqns (4) and (5), respectively. The plot of a2
versus Bv (photon energy) yields a straight
pt
line with energy intercept of E (direct band
Gd
gap energy) if a direct transition is involved.
The relation between the intensity of incident
light I and the detected intensity I is represented
o
by an exponential form, where a is the absorp-
tion coefficient and x is the penetration depth
of light.
I=I exp(−ax) (4)
o caused by the ultrasonic vibration itself (i.e. the
a3(Bv −E )1/2 (5)
pt Gd
We observed that the band gap energy of CdS
increased to 2.39 eV from 2.37 eV due to
ultrasonication.
3.5. Light absorbance of solution
Figure 8 shows the absorbance spectra mea-
sured on the CBD solutions by the spectropho-
tometer. We used a quartz cell
Fig. 8. Absorbance of the bulk chemical solution (a) during the reaction without ultrasonication, (b) with ultrasonication
at 83°C. In (a) the absorbance at 65°C is shown for comparison.
J. Y. Choi et al.
(1 cm×1 cm×4.5 cm) as a reaction bath and a
cell breaker (Branson@ Sonifier 450) for apply-
ing ultrasonication. Normally, CdS formation
starts at about 60°C, and then the CdS precipi-
tates cause the absorbance of the solution to
rise. Firstly, CdS solution was heated to 83°C
where the CdS films could be deposited uni-
formly, and then the absorbance of the solution
was observed with increasing time. The absor-
bance increased during the reaction over all the
wavelength range ( Fig. 8(a)). As expected, the
precipitation of CdS showed a shoulder at
520 nm (band gap energy of CdS). After
70 min, the absorbance no longer changed. We
applied ultrasonication to the solution while
heating the solution and fixed the temperature
of the solution at 83°C for 20 min ( Fig. 8(b)).
The absorbance, at this point, was much higher
than that measured after 30 min without ultra-
sonication, and even that after 70 min (refer to
Fig. 8(a)). Moreover, it was observed that a
noticeable change in the shape of the absor-
bance curves was shown in the wavelength
region between 250 and 400 nm. This could be
agitation of the solution may scatter the inci-
dent light).
Although we observed a change in absor-
bance of a pure water when ultrasonication was
applied, the magnitude was not large enough to
explain the above results. We think that the
formation of quantum-size CdS particles, which
would induce the absorption of light above the
band gap energy, may have influenced the shape
 Properties of cadmium sulfide thin films
of the slope at short wavelength region (Hobson
et al., 1994). In the other words, ultrasonication
could accelerate the formation of CdS in the
solution and make colloidal particles having
quantum sizes. This interpretation suggests that
ultrasonication should have a catalytic action
for the formation of CdS.
4. CONCLUSIONS
We investigated the influence of ultrasonica-
tion applied during the deposition of CdS films.
The results observed are as follows: (i) compact
and transparent films were produced under
ultrasonication; (ii) uniform films were obtained
even under non-optimal conditions such as at
excess precursor concentrations; (iii) deposition
rates were reduced by suppressing the formation
of the ‘‘B-quality’’ component and the growth of
CdS grains; (iv) the formation of CdS could
occur at low temperature in a short time, indi-
cating a catalytic action of ultrasonication; (v)
the grain size of the CdS films was reduced to
3–5 nm from 12–15 nm; (vi) the transmittance
of CdS films at long wavelengths (≥520 nm)
became higher by the effect of ultrasonication;
(vii) the band gap energy increased from 2.37 eV
to 2.39 eV.
Acknowledgement—This study was supported by the Korea
Science and Engineering Foundation under project
No. 961-0804-029-2.
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