ELSEVIER Thin Solid Films 269 ( 1995) 117-120

On the electrical and optical properties of CdS films thermally deposited

by a modified source
A. Ashour, N. El-Kadry, S.A. Mahmoud
Physics Deparfment, Faculty ofScience, Minia UniversiQ, Minia, Egypt

Received 28 March 1995; accepted 27 June 1995

Abstract

CdS films were prepared by a physical vacuum deposition technique on an amorphous (glass) substrate using a modified evaporation
source. The effect of the processing conditions (the film thickness, substrate temperatureand the deposition rate) wereconsidered in comparison
with the normal evaporation source. A van der Pauw four-probe arrangement was used for measuring the electrical resistivity, which varies
between 0.1 X lo4 and 8.18 X 104 R cm. It decreases with increasing film thickness, and decreasing deposition rate and substrate temperature.
This was attributed to the effect of crystallite size, the degree of preferred orientation, internal microstrain and the stoichiometry. From
spectrophotometric measuring and using an approximate formula, the optical parameters (n, k, a ) were evaluated. The values of the refractive
indices and the energy gaps were evaluated and correlated with the preparation parameters.

Keywords: Cadmium sulphide; Deposition process; Optical properties; Resistivity

1. Introduction calculated. The energy gap is estimated from the optical

absorption spectrum.

In recent years there has been considerable interest in thin

film semiconductors for use in solar cell devices and thin film
transistors for flat panel displays [ l-31. Cadmium sulphide
(CdS) belonging to the II-VI group is one of the promising
materials. The deposition of CdS films has become increas-
ingly important due to the widened industrial applications
with a large number of uses [ 4-61. Films of CdS has been
the subject of intensive research because of its intermediate
bandgap, high absorption coefficient, reasonable conversion
efficiency, stability and low cost [7,8]. The knowledge of
the optical properties of CdS films is very important in many
scientific, technological, and industrial applications in the
field of optoelectronic devices, particularly solar cells. A
broad variety of deposition techniques [B-lo] permits the
deposition of CdS films with desirable optical properties.
Among these, spray pyrolysis, chemical bath deposition,
sputtering and vacuum evaporation are well established tech-
niques. The vacuum evaporation technique is known to be
suitable for preparation of CdS films for a wide range of
applications [ 6,8,11].
In this work, the electrical and the optical properties of the
CdS films, which deposited by a modified evaporation source
under various preparation conditions will be investigated.
The film resistivity as well as the optical constants (n, k) are
2. Experimental
CdS films were deposited by thermal evaporation from a
resistivity-heated quartz crucible containing high-purity CdS
powder and wrapped in a tantalum sheet. This arrangement
was found to facilitate the loading of the CdS powder and to
increase the lifetime of the heater. A small wad of quartz fiber
wool was placed in the neck of the quartz crucible to prevent
spattering of the CdS during outgassing and evaporation. The
vacuum system (Coating unit E306A Edwards Co.) having
a diffusion pump with a liquid nitrogen trap was used. Prior
to evaporation, the pressure inside the evaporation chamber
was maintained during evaporation at (1.3-2.0)~10-~ Pa
and outgassed at 150 “C. The starting material was obtained
from Fluka AG and was of high purity (5 N) .The thickness
and deposition rate were controlled by using a quartz thick-
ness monitor and calibrated with a mechanical stylus method
(Sloan Dektak, model 11A). The substrates which used in
the experiments were carefully cleaned microscope slides.
The electrical resistivity of the prepared films were meas-
ured by the four-point probe method of Van der Pauw [ 121
in conjunction with the corresponding correction tables [ 131.
The potential difference and the current were measured by a

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118 A. Ashour et al. /Thin Solid Films 269 (1995) 117-120

Keithly electrometer (model 616). Four small indium con-

tacts were deposited at room temperature on the CdS films
which were arranged symmetrically around the circumfer-
ence. Copper wire was attached to the contacts using silver
paste. All leads were shielded to minimize induced currents
and temperatures maintained at constant values across the
sample to eliminate Seebeck voltages. 0.8 nmls -
0.8 rim/s --__
The optical characteristics of the CdS films were measured 1.5 IlIIl/S -#+-
with a Shimadzu spectrophotometer (model UV-3101PC) in 0.8 rim/s--
the spectral range from 500 to 900 nm. The spectral variation
of the refractive index, n, and the extinction coefficient, k,
were calculated from the obtained transmission and reflection
values.

3. Results and discussion

180 “c 0.8 rim/s ----
The dark resistivity of the CdS films measured at room 180°C 2.2 nmls *-K-
ZOO? 2.2 nmls -
temperature is presented in Table 1. The resistivity values
range from 0.1 X lo4 to 8.2X lo4 fi cm for films with thick-
ness 1000 and 1500 nm, a deposition rate of 0.8-2.2 nm s-l j, , ,(b)

and a substrate temperature of 180-220 “C. GO0 700 800 900

The data show that the resistivity increased as the substrate Wavelength

temperature and deposition rate increased, but decreased with Fig. 1. Optical transmission of CdS films in different preparation conditions.
increasing film thickness. Similar behavior was observed by (a) t= 1000 nm, (b) t= 1500 nm.
other workers [ 14,151. For nearly the same specification
(film thickness, deposition rate and substrate temperature) The variation of electrical properties as a function of the
of the films, the resistivity is higher in the case of the modified preparation parameter was highly correlated with structure
source than the normal one [ 141. On the other hand, the characteristics of the prepared films [ 16 1. Thus, the decrease
structural features and the morphology of the films prepared in resistivity values as the thickness increases is a result of
with the modified source were studied and published in a the increase of both the crystallite size and the degree of
separate paper [ 161. The results showed that CdS films pre- preferred orientation of the films. On the other hand, the
pared with the modified source possessed a larger crystallite increase of resistivity with the increase of the deposition rate
size with lower microstrain values relative to films prepared is due to the increase in the internal micro-strain and the
with the normal evaporation source and the same preparative decrease in both the crystallite size and the degree of preferred
conditions. This means that the increase in the electrical resis- orientation. Finally, the improvement of stoichiometry as the
tivity values mentioned above cannot be attributed neither to substrate temperature rises leads to an increase of the resis-
the effect of the crystallite size nor to the strain [ 14,161, but tivity. Thus, the dependence of resistivity is most probably
most probably is due to the better stoichiometry of the CdS the result of changes in the structure of the films.
film prepared by the modified source. The optical transmission for CdS films is shown in Fig. 1
for samples prepared at different preparation parameters. It
Table 1
can be observed that, in general, the transmission is high,
Values of the electrical resistivity of CdS tilms with different deposition
parameters which can be attributed to the improvement in perfection and
stoichiometry of the films.
Substrate Film Deposition Dark The refractive indices (n) were determined from the reflec-
temperature thickness rate resistivity tance (R) data using [ 171:
Ts t R (Xl04ncm)
(“C) (nm) (rims;‘‘’ R=[(n-l)*]l[(,+l)*] (1)
180 1000 0.8 0.40
As shown in Fig. 2, the refractive indices of the films are
200 1000 0.8 0.70
220 1000 0.8 5.50 greatly influenced by the deposition rate and substrate tem-
200 1000 1.5 8.18 perature. The refractive indices increase as the deposition rate
180 1000 2.2 5.20 increases. This is in agreement with results reported by Ash-
180 1500 0.8 0.10 our [ 181 and Gottesman and Ferguson [ 171. On the other
180 1500 2.2 1.00
hand, the indices decrease as the substrate temperature
200 1500 2.2 3.00
increases.
 A. Ashour et al. / Thin Solid Films 269 (1995) I1 7-120 119

3
T=(l-R)*exp(-at)/[l-R*exp(-2at)] (2)

where t is the thickness and a is related to the extinction

coefficient by
2

a =4rrklA (3)

Fig. 3 shows the variation in k, as a function of the wave-

1
length, which is found to increase with decreasing deposition
; 0.5 (a)
rate, and increasing substrate temperature in contrast as the
g 3.5 behaviour of refractive index. Fig. 4 shows the wavelength
- 180 % 2.2 rim/s
.c_
- 18O’C 0.8 nmk dependence of the absorption coefficient of CdS films. From
.>
v 3
* zoo’c 2.2nmls this data, the energy gap was estimated as shown in Fig. 5.
z
e The curves revealed that absorption coefficient of these films
F
(L is in the order of lo4 cm-’ and decreases as the deposition
2 rate increases and the substrate temperature decreases. This
variation of the optical constant of the films can be correlated
with their structural characteristic [ 161. The decrease of n
and increase of k is due to the improvement of stoichiometry
1 [ 201, the increase in crystallite size [ 2 1] and the decrease in
(b) internal strain [ 161.
0.5 7 I
F ioo 600 700 800 , The absorption coefficient, a, of CdS was found to follow
Wovelength the relation [ 19,21,22],
Fig. 2. Wavelength dependence of the refractive index of CdS films in
different preparation conditions. (a) I= 1000 nm, (b) f= 1500 nm. aE=A(E-E,)“,5 (4)

0 220°C 0.8 nub/r.

- 200°C 0.8 rim/s
-+- zoo*c 1.5 n&s

- li?OO”C 0.8 rim/s

\ -8-
- 2o0°c
18O’C 2 2 nmk
Inm/s

500 600 700 800

Wavelength

Fig. 3. Absorption index characteristics of CdS films in different preparation

conditions. (a) t= 1000 nm, (b) I= 1500 nm.

The absorption coefficient, a, and the extinction coeffi- 500 600 700 800 9&l l(
cient (absorption index), k, were obtained from the trans- Wavelength
mittance, T, and reflectance, R, using the approximate Fig. 4. Absorption coefficient characteristics of CdS films in different prep-
formula [ 191: aration conditions. (a) r= 1000 nm, (b) t= 1500 nm.
120 A. Ashour et al. /Thin Solid Films 269 (1995) 117-120

deposition rate decrease. On other hand, it increases with

increasing thickness.
The optical investigations based on the spectrophotometric
characteristics have confirmed that the CdS films grown on
glass show high transparency.
The determined refractive index was smaller than that of
the bulk material. The deduced extinction coefficient was
relatively smaller than those reported in the literature and
increased sharply at the bandgap region.
The films exhibited a direct transition in the range 2.23-
2.30 eV. This bandgap value is smaller than those obtained
by other thin film techniques. No difference is expected in
the Eg value for the examined thickness; this can be assumed
to be a continuous film so the surface effect is negligible.

6-I
1 Acknowledgements

The authors would like to thank Prof. Dr. K. Abdel-Hady,

Minia University and Prof. Dr. A.A. Ramadan, Helwan Uni-
versity for their help and useful discussions.

2 2.2 24 2.6
-I
2.8
EnergyCeVl
Fig. 5. ( a E)* versus E plot of CdS films at different preparation conditions.
(a) t=lOOOnm, (b) t=l5OOnm.
where A is a constant, E is the photon energy and Eg is the
bandgap. The energy dependence of the absorption coefli-
cient (Fig. 5) indicates that these materials are of direct band-
gap. The optical energy gap is defined by extrapolating the
linear portion of the absorption spectrum to E= 0. Fig. 5
shows the plot of ( a E)’ versus E for different preparation
parameters. The plots of CdS films show a straight line por-
tion intercepting the energy axis at 2.23 and 2.30 eV indicat-
ing a direct bandgap material. Also, as shown in Fig. 5, at
higher thickness (t= 1500 nm) no effect of the rate and Ts
on the energy gap was noticed. On other hand, at a relatively
small thickness (I = 1000 nm) the rate has an effect on the
energy gap.
Thus, using the modified evaporation source produces
films of smaller energy gap than the normal evaporation
source. However, it is worth mentioning that the prepared
films possess higher resistivity, indicating a change in the
structure, i.e. better stoichiometry.
4. Conclusion
The electrical and optical investigations prove that the used
modified evaporation source (a heated quartz tube covered
with a small wad of quartz fiber wool) produces films of
higher resistivity and smaller energy gap than the normal
evaporation source (molybdenum boat). The results show
that the resistivity decreases as the substrate temperature and
References
[ 1] K.L. Chopra and 1.1.Kaur, in K.L. Chopra and T.C. God (eds.), Thin
Film Device Application, Plenum Press, New York, 1983.
[2] S. Chandra, R.K. Pandley and R.C. Agarwal, J. Phys. D: 13 (1980)
1757.
[3] K.L. Chopra and S.R. Das, Thin Film Solar Cells, Plenum Press, New
York, 1983.
[4] R. Hill, in T.J. Coutts (ed.), Thin Solid Film Active and Passive
Devices, Academic Press, New York, 1987, p. 487.
[5] M. Ueno, H. Minoura, T. Nishikawa and M. Tsuiki, J. Electrochem.
Sot., 130 (1983) 43.
[6] J. Santamaria, I. Martil, E. Iborra, G. Gonzalez Diaz and F. Sanchez
Queada, Solar Energy Mater., 28 (1990) 31.
[7] F. El Akkad and M. Abdel Naby, Solar Energy Mater, 18 ( 1989) 151.
[8] S.N. Sahu and S. Chandra, Solar Cells, 22 (1987) 163.
[9] L.P. Desmukh, A.B. Palwe and V.S. Sawant, Solar Energy Mater, 20
(1990) 341.
[lo] A. Bennouna, E.L. Ameziane, A. Haouni, N. Ghermani, M. Azizan
and M. Brunel, Solar Energy Mater., 20 (1990) 405.
[ 111 J.W. Orton, B.J. Goldsmith, J.A. Chapman and M.A. Powell, /. Appl.
Phys., 53 (1982) 1602.
[12] L.J. Van der Pauw, Philos. Res. Rep., 13 (1958) 1.
[ 131 A.A. Ramadan, R.D. Gould and A. Ashour, Thin Solid Films, 239
(1994) 272.
[ 141 A.A. Ramadan, R.D. Gould and A. Ashour, ht. J.Electron., 73 ( 1992)
717.
[15] S. Ray, R. Banerjee and A.K. Barua, Jpn. J. Appl. Phys., 19 (1980)
1889.
[ 161 A. Ashour, N. El-Kadry and S.A. Mahmoud, Vacuum ( 1995). in press.
[ 171 J. Gottesman and W.F.C. Ferguson, J. Opt. Sot. Am., 44 (1954) 368.
[18] A. Ashour, Physical properties of cadmium compound solar cells,
Ph.D. Thesis, Minia University, Minia, Egypt, 1989.
]19] A. Ashour, H.H. Afifi and S.A. Mahmoud, Thin Solid Films, 248
(1994) 253.
[201 K. Yamaguchi, N. Nakayama, H. Matsumoto and S. Ikegami, Jpn. J.
Appl. Phys., 16 (1977) 1203.
I21 I F. Tepehan and N. Ozer. Solar Energy Mater. Solar Cells, 30 (1993)
353.
[22] O.P. Agnihotri and B.K. Gupta, Jpn. J. Appl. Phys., 18 (1979) 317.