Applied Surface Science 140 Ž1999.

182–189

Cadmium sulphide growth investigations on different SnO 2

substrates
´
M.A. Martınez )
´ J. Herrero
, C. Guillen,
´ RenoÕables (CIEMAT), AÕda. Complutense 22, E-28040 Madrid, Spain
Departamento de Energıas
Received 20 August 1998; accepted 30 September 1998

Abstract

Optical, structural and morphological properties of chemical bath deposited cadmium sulphide, CdS, on different
commercial SnO 2rglass substrates have been analysed. Although CdS–SnO 2 bilayer optical behaviour is directly deter-
mined by tin oxide characteristics, cadmium sulphide optical features remain independent on substrates. CdS covers the layer
underneath in a continuous and homogeneous way, having a grain size between 100 and 300 nm, dependent on substrate
morphology. 4008C, 20 min air-annealing treatment has produced only a light decrease in the average visible transmission of
CdS–SnO 2 bilayers. q 1999 Elsevier Science B.V. All rights reserved.

Keywords: CdS; Polycrystalline; Thin film; Buffer layer

1. Introduction this kind of applications, because this technique of-

fers the advantages of a conformal coverage on
Superstrate-type CdTe and CuInSe 2-based photo-
rough surface at minimal thicknesses, easily and at a
voltaic solar cells are made on glass coated by
low cost w1,3,5x.
transparent conductive oxides, TCO, such as tin
The objective of this work is to study the CdS
oxide, SnO 2 , or indium tin oxide, ITO, over which a
growth on commercial glass and SnO 2rglass sub-
thin cadmium sulphide, CdS, layer is deposited w1,2x.
strates by CBD under different preparation condi-
The investigation on combined TCO–CdS window
tions. A high optical transmission is an essential
layers has recently been developed owing to the
requirement for window bilayers but, also, structure,
great interest in better understanding the effect of
morphology and grain configuration are very impor-
these bilayers on the final photovoltaic response
w3,4x. Although TCO-coated glass substrates are tant for junction formation, contacting and photon
engineering. Taking into account this fact, the influ-
commercially available with suitable photovoltaic
ence of the substrate and chemicals ratio on the
quality, CdS optimisation remains still in progress at
optical, structural and morphological properties has
laboratory scale. Chemical bath deposition, CBD, is
been evaluated.
the most adequate method to produce CdS films for
Considering the photovoltaic applications, in
which after CdS deposition subsequent device fabri-
)
Corresponding author. Tel.: q34-91-3466669; Fax: q34-91- cation processes involve heat treatments at high tem-
3466037; E-mail: calvo@ciemat.es peratures w1,2x, the effect of a typical air-annealing

0169-4332r99r$ - see front matter q 1999 Elsevier Science B.V. All rights reserved.
PII: S 0 1 6 9 - 4 3 3 2 Ž 9 8 . 0 0 5 8 7 - X
 ´ et al.r Applied Surface Science 140 (1999) 182–189
M.A. Martınez
treatment on CdS–SnO 2rglass window bilayers has
been also studied.
2. Experimental procedure
Cadmium sulphide thin films have been grown
both on uncoated sodalime glass and two commer-
cial tin oxide coatings, named A and B-type SnO 2 ,
with different characteristics. Previous investigations
on CdS growth process onto uncoated glass sub-
strates have allowed us to choose some of the depo-
sition parameters to obtain a good CdS quality with
an accurate thickness control w5,6x. Such parameters
have been maintained constant at: wCdSO4 x s 1 mM,
wNH 3 x s 2 M, 10 min deposition time and 708C bath
temperature. Only thiourea, SCŽNH 2 . 2 , named also
TU, concentration has been varied between 10 and
100 mM.
Film thicknesses have been measured by utilising
a Dektak 3030 surface profile measurement unit.
Optical transmission has been evaluated at room
temperature with unpolarised light at normal inci-
dence in the wavelength range from 300 to 1500 nm,
with a Perkin-Elmer Lambda 9 double beam spectro-
photometer. Crystalline structure has been analysed
by a Philips X’Pert Ž40 kV, 50 mA. X-ray diffrac-
tometer using the filtered K a emission line of cop-
per. Morphology has been studied by a JEOL-
JSM5800 scanning electron microscope. Topography
imaging and roughness quantification have been car-
ried out by a Topometerix TMX2000 atomic force
microscope. Samples have been studied as-grown
and also after an air-annealing at 4008C for 20 min
in a tubular furnace, in order to test and compare
their evolution.
3. Results and discussion
Preceding studies have indicated CdS deposited
on glass substrates, under deposition conditions men-
tioned in Section 2, presents simultaneously a very
accurate thickness, 70 " 10 nm and a good optoelec-
tronic, structural and morphological quality w5,6x.
Owing to this fact, CdS has been prepared in such
conditions on different SnO 2rglass substrates and
some typical optical transmission spectra can be seen
183
in Fig. 1. Considering its photovoltaic applications,
the study has been focused on the global CdS–SnO 2
bilayer optical behaviour, as more useful window
parameter than the minute aspects of the individual
or interface features. Data deduced from the optical
spectra have been analysed Žsee Fig. 2. in two
distinct intervals: visible Ž400–800 nm. and infrared
Ž800–1500 nm., in order to evaluate the influence of
CdS and SnO 2rglass substrates on each region. Ex-
perimental data have demonstrated CdS–SnO 2 bi-
layer transmission is more dependent on type of
SnO 2 substrates than on thiourea concentration used
during CdS deposition process. SnO 2 ŽA.rglass sub-
strate has shown a higher average transmission in the
visible range, about 10%, and in the infrared one,
about 5%. CdS–SnO 2 bilayers have maintained the
same average transmission ratios than SnO 2 sub-
strates. A light increase in the optical transmission,
not higher than 5%, appears with thiourea raise in
both SnO 2rglass substrates. This CdS transmission
increase with wTUx has been already observed on
uncoated glass substrates w5,6x and it has been at-
tributed to the growth process limitation on the glass
by enhancing the one in the bulk of the solution.
Taking into account that after CdS deposition
subsequent photovoltaic device fabrication processes
involve heat treatments at high temperatures w1,2x,
the influence of a typical 4008C air-annealing on
CdS–SnO 2rglass has been also tested. In this way,
4008C air-annealed CdS–SnO 2 bilayers have pre-
Fig. 1. Optical transmission spectra related to different
SnO 2 rglass substrates and the corresponding CdS–SnO 2 bilay-
ers. CdS has been prepared in the same conditions.
184 ´ et al.r Applied Surface Science 140 (1999) 182–189
M.A. Martınez

Fig. 2. Evolution of average transmission with thiourea concentra-

tion for CdS samples deposited on distinct SnO 2 rglass substrates. Fig. 4. XRD spectra associated with CdS grown on various
substrates: Ža. glass, Žb. SnO 2 ŽA.rglass and Žc. SnO 2 ŽB.rglass.

sented only a light decrease in the 400-800 nm
wavelength range associated with the bandgap nar-
rowing of the CdS w6–8x due to the out diffusion of
hydrogen and oxygen species w9x. Annealed samples
have exhibited a visually detected colour change
from light-yellow to brownish-orange. Fig. 3 illus-
trates this effect for a CdS sample made on B-type
SnO 2rglass substrate. Similar effect has been de-
tected for both uncoated glass w6x and A-type
SnO 2rglass substrates.
The most important conclusions obtained from
optical characterisation are that the type of SnO 2
substrate does not affect optical CdS properties, and
CdS–SnO 2 bilayer optical features are directly deter-
mined by tin oxide behaviour.
X-ray diffraction patterns related to CBD–CdS
thin films on glass and A and B-type SnO 2rglass
substrates are plotted in Fig. 4. Tin oxide substrates
present a mixture of phases corresponding with te-
tragonal 1 and cubic 2 systems, having A-type SnO 2
lower crystallinity than B-type and different prefer-
ential orientation. Three CdS diffraction peaks can
be identified on the glass substrate, corresponding
with 3.34 " 0.03, 2.05 " 0.01 and 1.75 " 0.01 A ˚
interplanar spacings. These experimental data may
be attributed to the hexagonal structure 3 , but the
three highest hexagonal peaks do not match with the
detected ones. Our experimental X-ray diffraction
positions are more close to the three main Ž111.,
Ž220. and Ž311. CdS cubic peaks 4 and, then, the
cubic structure has been assigned to these CBD–CdS
films. Unfortunately, Ž111. and Ž311. peaks are
screened by the more crystalline tin oxide structure,
but the detected Ž220. cadmium sulphide peak does
not show any variation neither with the thiourea
ˇ ´
concentration nor with the substrate used. Touskova
et al. w10x have reported, by using more sensitive
XRD measurements, also cubic structure for CBD–
CdS layers, independent both on substrate type and
bath solution. 4008C air-annealing treatment does not
modify the CdS–SnO 2 crystalline structure, thus in-

1
X-ray powder data file JCPDS no. 41-1445.
2
X-ray powder data file JCPDS no. 33-1374.
3
Fig. 3. Effect of the 4008C, 20 min air-annealing treatment on the X-ray powder data file JCPDS no. 41-1049.
4
average transmission of CdS–SnO 2 ŽB. bilayers. X-ray powder data file JCPDS no. 10-0454.
 ´ et al.r Applied Surface Science 140 (1999) 182–189
M.A. Martınez
dicating that any recrystallisation and interdiffusion
processes have not taken place significantly. Dis-
crepancies about the CdS structural changes by an-
nealing have been found in literature. Some authors
w11x have reported a structural variation in CdS,
taking place near about 3008C. On the contrary,
another experimental data w10,12x, more similar to
ours, have shown steady CdS structure following
annealing at 4008C in air atmosphere, even though
the optical bandgap and sample colour change, prob-
ably owing to compositional but not structural modi-
fication w6–9x.
CdS on SnO 2rglass substrates morphology as
analysed by means of SEM is illustrated in Fig. 5.
From these images, it has been proven that cadmium
sulphide covers the layer underneath in a continuous
Fig. 5. Frontal and cross-sectional SEM images of two different CdS–SnO 2 bilayers. Ža. CdS on SnO 2 ŽA.rglass and Žb. CdS on
SnO 2 ŽB.rglass.
185
and homogeneous way, having a grain size depen-
dent on substrate. In this way, while cadmium sul-
phide deposited on SnO 2 ŽA.rglass presents grain
diameters between 100 and 150 nm, these ones
increase up to 200–300 nm when a SnO 2 ŽB.rglass
substrate is utilised. Such grain size variation may be
attributed to the differently ordered topography of
the SnO 2 sublayers. The improvement of the CdS
grain size cannot be related with any XRD peak
modification, thus indicating that each grain ob-
served under the microscope could be a cluster of
submicroscopic crystallites. SnO 2 sublayer topogra-
phy influences CdS cluster size but not the submi-
croscopic crystalline structure.
In order to achieve more insight into surface
structural features of substrates and CdS–SnO 2 bi-
186 ´ et al.r Applied Surface Science 140 (1999) 182–189
M.A. Martınez

Fig. 6. AFM images of the distinct substrates: Ža. glass, Žb. SnO 2 ŽA.rglass and Žc. SnO 2 ŽB.rglass.
 ´ et al.r Applied Surface Science 140 (1999) 182–189
M.A. Martınez 187

Fig. 7. AFM images related to: Ža. CdS on glass, Žb. CdS on SnO 2 ŽA.rglass and Žc. CdS on SnO 2 ŽB.rglass.
188 ´ et al.r Applied Surface Science 140 (1999) 182–189
M.A. Martınez
layers, AFM images have been performed. This tech-
nique offers digital images which allow quantitative
measurements of surface features, such as root mean
square, RMS, or average roughnesses, R a , and the
analysis of images from different perspectives, in-
cluding three-dimensional simulation. Fig. 6 indi-
cates that the topography of the substrates used
during these investigations is very different, present-
ing the quantitative analysis values of RMS s 4 nm
and R a s 3 nm for glass, RMS s 12 nm and R a s 9
nm for SnO 2 ŽA.rglass and RMS s 39 nm and R a s
33 nm for SnO 2 ŽB.rglass. It is important to note the
values obtained are averages and there is a statistical
variation associated with them, which depends on the
location on the sample where the measurement is
performed. To minimise these errors, we have done
many measurements of each parameter. Fig. 7 shows
the influence of the distinct substrates on the final
CdS grain size and bilayer morphology and rough-
ness. A great difference in CdS grain diameter can
be detected depending on surface substrate and the
line analysis at various positions on each sample has
proven the grain size evolution is similar to the
observed in SEM images. Cadmium sulphide repro-
duces morphology and roughness related to the sub-
layer underneath, which act as a seed for enhancing
the CdS grain size. This CdS morphology improve-
ment is very important because not only its own
optoelectronic quality can be modified, but also that
of the following layers constituting the photovoltaic
solar cells. Thus, RMS s 6 nm and R a s 5 nm for
CdS grown on glass, RMS s 12 nm and R a s 10 nm
for CdS deposited on SnO 2 ŽA.rglass and RMS s 35
nm and R a s 28 nm when the substrate is
SnO 2 ŽB.rglass. Results are analogous to those re-
ported by Moutinho et al. w3x, for CdS made on
SnO 2-coated glass substrates. The fact that CdS
roughness values agree well with the ones for the
respective SnO 2 substrates indicates that the growth
is conformal and the CdS thickness is uniform.
4. Conclusions
Window coatings consisting on chemical bath
deposited cadmium sulphide onto different commer-
cial SnO 2rglass substrates have been optical, struc-
tural and morphologically studied for photovoltaic
applications.
Optical characterisation has proven CdS proper-
ties are not affected by type of SnO 2 substrate, and
CdS–SnO 2 bilayer features are directly determined
by the SnO 2 optical behaviour. The CdS cubic crys-
talline nature seems not to be significantly influ-
enced by the substrate polycrystalline structure. Nev-
ertheless, cadmium sulphide reproduces morphology
and roughness related to the sublayer underneath,
thus indicating that the growth is conformal and
uniform.
Acknowledgements
The authors would like to thank ‘BP Solar’ for
provision of tin oxide substrates, ‘ISOM-Grupo de
´
Dispositivos Magneticos’ ŽUPM-ESTIT. for SEM
characterisation and Dra. Paloma Dıaz ´ Aroca
ŽCIEMAT. for XRD measurements. This work has
been supported by the Spanish Ministry of Industry
and Energy through CIEMAT-DER Project: ‘Desar-
rollo de Materiales y Dispositivos Fotovoltaicos’, the
CICYT under Project TIC96-0479 and the European
Commission from JOULE III Programme Project
JOR3-CT97-0124.
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