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A STUDY OF THE GROWTH DEPENDANT PROPERTIES OF UNDOPED AND IN-

SITU DOPED CHEMICALLY DEPOSITED CdS THIN FILMS


A.J. Reynolds', S. Hinckley', K. Prince', and K. S h o d

"School of Engineering and Mathematics, Edith Cowan University, Joondalup Drive, Joondalup WA
'Australian Nuclear Science and Technology Organisation, Sydney, Australia

ABSTRACT

Cadmium Sulfide thin films have been produced by the chemical bath deposition method in order to study the
growth dependant properties and composition of the CdS. The specific categories of interest include deposition
temperature, in-situ indium doping, and post deposition annealing. The films were subjected to a number of
analysis techniques including Atomic Force Microscopy, Secondary Ion Mass Spectroscopy, and Environmental
Scanning Electron Microscopy with Charge Contrast Imaging. Results !?om this analysis reveal many interesting
details concerning the surface topography, the effect of deposition temperature on film, composition, and the
distribution of indium dopant throughout the film. Atter annealing in an air atmosphere, nodule like structures
have appeared, the indium dopant was found to have an inhomogeneous distribution through the depth of the
film and colloidal particulate deposition was found to increase at higher deposition temperatures.

1. INTRODUCTION

CdS, as a wide bandgap semiconductor, has many uses and applications in areas of industry including
photovoltaic power generation and optoelectronics. Heterojunction solar cells that consist of numerous types of
narrow band gap semiconductors such as CuInSe2,&Ins2, InP, and CdTe require a window layer. This is where
CdS can be used as a direct band gap 11-VI semiconductor. The solar spectrum absorption of the window layer,
which is directly related to the bandgap, can be controlled by changing the composition of the CdS thin film [I].
This material is also useful in imaging and visual displays, where the CdS thin films have been found suitable for
use in thin film transistors [2]. There are a multitude of processes available for producing CdS thin films,
including molecular beam epitaxy, thermal evaporation, sputtering, chemical vapour deposition, spray pyrolysis
and chemical bath deposition (CBD) [l]. Of these, CBD is the simplest and relatively cheapest available. The
method is particularly suited to large-scale depositions, and can produce near stoichiometric CdS due to growth
kinetics inherent in the method [3]. CBD CdS is a very versatile substance in that its properties can be tailored, to
some degree, by altering the conditions under which it is produced. However the inner workings of the
deposition of CdS in the CBD method are not well understood. Also, as-deposited CdS films are generally
slightly n-type, due to the presence of vacancies. There is a need to be able to alter the conductivity of the
deposited films, in order to extend their usefulness as semiconducting materials in industry. Three of the factors
that influence the properties of CdS have been investigated in this work deposition temperature, in-situ doping,
and post-deposition annealing.

2. EXPENMENTAL PROCEDURE

The CdS thin films were deposited onto standard glass microscope slides by chemical bath deposition [4], from a
solution composed of 2mMoIL cadmium acetate, 4mMom thiourea, and 1.8MoIL ammonia. Indium trichloride
was added in appropriate amounts'as the source of the indium dopant. Films were grown for a range of in-situ
Indium dopant concentrations, at deposition temperatures fiom 60 to 80°C for periods of up to one hour. The
newly deposited films were cleaned ultrasonically in de-ionised water to remove excess loose particulate CdS. A
selection of films was annealed in a furnace at 400'C in an air atmosphere for one hour. The CdS thin films were
then analysed using Secondary ion Mass Spectroscopy (SIMS), Atomic Force Microscopy (AFM), and Charge
Contrast Imaging (CCI)[5]. SIMS was performed using a Cameca IMSSF magnetic grid SIMS, using a Cs+ ion
source. The elements examined included oxygen, silicon, sulfur, arsenic, cadmium, and sulfur. AFM
measurements were conducted with a Digital Instruments Nanoscope IIIa, operating in contact mode. CCI
images were taken using an Electroscan Environmental Scanning Electron Microscope, for a chamber pressure
of 1.5 to 3.0 Torr, and accelerating voltage of 30keV.

0-7803-7571-8/02/$17.00 02002 IEEE 563


3. RESULTS AND DISCUSION

The SIMS data gives information on the relative quantities of elements present with respect to the probing depth.
A comparison of quantities of elements present betkeen samples can be made. The data also indicates the
relative film thickness between samples, as a product of how long it took to sputter through to the glass substrate.
Figure 1 shows the relative concentration of oxygen in the film before and after annealing. There is
approximately 10 times the oxygen present in the annealed films as compared to the as-deposited films. This
indicates that during the post deposition processing when the films were annealed in air, oxygen permeated the
crystal structure of the films. This would suggest the substitution of Oxygen for Sulfur in the CdS crystalline
lattice, and/or the formation of CdSO,.

7OC. O . l % l n , A n n e a l e d
l.E+05
70C. O . l % I n . As-deposited

1
x
6

1.E+03
0 200 400 600 800 1000 1200 1400
Tlme(a)

Fig. 1. Comparison of oxygen content as a function of depth (sputter time) for films deposited at 70
and SOT, before and after annealing.

Figure 2 shows the effect of in-situ indium doping. It can also be seen that the concentration of the Indium in the
thin film after deposition is concurrent with the concentration of the indium reactant in the chemical bath
solution during deposition. The concentration of indium in the films also varies as a function of depth. The
concentration of indium increases as we sputter deeper into the film. This is due to the concentration of Indium in
the chemical bath solution decreasing as it is being consumed in the deposition reaction. This is clearly shown
where the surface of the film is represented at a sputter time of 0 seconds and the concentration increases as the
film is sputtered away to where the CdS joins to the glass substrate. Annealing s e e m to have no appreciable
effect on the distribution of indium throughout the films.

I
I.E+03

P I.E+02
x
d
g6 l.E+01

I.E+00 I
0 200 400 600 800 1000 1200 1400
Time(s)

Figure 2 Comparison of indium component as a function of depth (sputter time) for films deposited at
70°C before annealing.

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When inspecting the images produced by AFM (see Fig. 3) one important aspect that recurs throughout the data
is the presence of nodule like structures on the surface of the annealed films. The nodules appear to he 5 l pm in
diameter and are a little over 200nm high. These nodules do not appear on the as-deposited films. This would
suggest that the nodules develop during the post deposition annealing process. The AFM analysis also indicates
that the annealed films tend to have an increased surface roughness characteristic and a much larger mean grain
size, due to the recrystallisation of the nodules.

Fig. 3. AFM image of (a) annealed and (b) as-deposited CdS thin films deposited at 70°C with 0.01%
Indium dopant. Images (a) and (b) are composed of two images; the left image is the surface profile
and the right image is a difference map of the surface profile data).

Figure 4 shows the images produced from CCI, indicating areas of varying charge distribution. The closer the
shade is to white, the higher the charge in that area. Areas that charge differently are usually composed of
differing materials, and materials that charge more usually have better conductivities, or are more electrically
active. The annealed films (shown in Figure 4b) have bright spots with an approximate size of 5 lfim covering
the surface of the films. These bright spots appear to be charging significantly more than the rest of the film. The
as-deposited films, illustrated in Figure 4% generally do not have these bright spots present at all. This indicates
that during the annealing process some crystalline structures have formed at the surface of the film, that may
have different compositions to the rest of the film, in agreement with the AFM measurements. Figure 5 shows
CCI measurements that indicate the presence of small particulates that are adhered to the surface of the films.
The concentration of these particulates tends to increase with increasing deposition temperature. This is due to a
change in the deposition mechanism from an ion by ion deposition that produces crystalline films, to a colloidal
particulate formation process.

Fig. 4. CCI image of (a) as-deposited and (b) annealed CdS thin films deposited at 70°C with 0.01%
indium dopant.

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(a) (b)
Fig. 5. CCI image of (a) film deposited at 70°C andI (b) deposited at 80°C, both mth 1% Indium dopant.

These nodule-like structures cannot be attributed to the indium doping, as the nodules occur in both the doped
and undoped films. This suggests that the structures are composed of CdO and/or CdS04, in agreement with the
SIMS measurements. CdO has an improved conductivity over that of CdS, and together with the films
recrystallising under annealing with increased oxygen quantities, would suggest that the nodules have CdO
present, which is suppolted by the CCI measurements. The small dimensions of the nodules has prevented
accurate determination of their explicit composition todate using standard techniques, such as SIMS and PKE.
However, the expected installation of a CAMECA NanoSIMS-50 at the Centre for Microscopy and
Microanalysis (Universityof Westem Australia), which will have a lateral resolution <IOnm, will facilitate these
measurements.

4. CONCLUSIONS

We have observed that several production aspects of the growth of CBD-CdS thin films have considerable sway
over the final properties of the films. Annealing of the CdS thin films in an air atmosphere increases the Oxygen
content of the films, and develops nodule like structures at the surface of the films. The annealing process also
decreases the smooth surface characteristicfound in the as-deposited CdS thin films. The dopant concentration in
the chemical bath solution is proportional to the dopant concentration in the CdS thin film after deposition,
although the indium dopant concentration is not constant with the depth of the CdS thin film and decreases with
increasing thickness. The In dopant used appears to have had no effect on the topographical and charging
characteristics of the CdS films examined using AFM and CCI. However further experimentationutilising more
accurate technology capable of very high resolution quantitative and qualitative measurements, such as a
NanoSIMS should reveal the interaction of the In dopant with a higher degree of precision that has previously
been unavailable.

5. ACKNOWLEDGEMENTS

This work was supported by an Australian Institute ofNuclear Science and Engineering (AtNSE) research grant.
The CCI measurements were performed at the Centre for Microscopy and Microanalysis, The University of
Westem Australia.

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