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Chemically deposited ZnS thin films: application as substrate for chemically deposited Bi2S3,

CuxS and PbS thin films

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1992 Semicond. Sci. Technol. 7 239

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Semicond. Sci. Technol. 7 (1992) 23%244. Printed in the UK

Chemically deposited ZnS thin films:

application as substrate for chemically
deposited Bi,S,, Cu,S and PbS thin films

P K Nair and M T S Nair

Photovoltaic Systems Group, Laboratorio de Energia Solar, IIM. Universidad
Nacional Autonoma de Mexico, 62580 Temixco. Morelos, Mexico

Received 5 April 1991,in final form 9 July 1991,accepted for publication

7 August 1991

Abstract. Chemical deposition of good quality ZnS thin films from aqueous
Solutions containing zinc sulphate, NH,/NH,CI buffer (pH IO). triethanolamine and
thioacetamide is described. It is shown that the presence of these films on glass
substrates offers various advantages in the case of chemically deposited metal
sulphide thin films: (i) improved adhesion of Bi,S, thin films. which is vital for
growing films of thickness > 0.2pm for semiconductor applications and in metal
sulphide thin film (MSTF) photography based on photoaccelerated chemical
deposition: (ii) improved adhesion of Cu,S films, offering the choice of different
shades of colours for the same integrated transmittance in the visible region of
- 2 0 % in solar control coatings and the possibility of multiple-dip deposition of
Cu,S films to enhance the film thickness, enabling the realization of Solar
absorptance of -90% and (iii) reduced reflectance in the visible light which can
reduce the glare from PbS solar control coatings and improve the solar
absorptance i n thicker PbS coatings and offer better contrast in MSTF photography.

1 . lniroductlon
ZnS is a material with an optical bandgap 3.7 eV [I] and
a refractive index 2.37 for the visible region [2]. The
combination of these properties has led to a wide range of
applications for ZnS films: Mn-doped electroluminescent
panels, Ag-, Cu-, AI- or In-doped cathodoluminescent
panels, hetero-epitaxial ZnS films on Si, GaAs or Ge as
electro-optic modulators and blue luminescent diodes, in
ZnS-CdS superlattices and in multilayer optical coatings
requiring alternate layers of ZnS films of precisely con-
trolled thickness and flatness [3]. While the deposition of
ZnS thin films by thermal evaporation of the ZnS powder
samples containing the appropriate dopants, at a
vacuum of - Torr and at substrate temperatures of
50-250 "C, remains the most popular thin film technique
films. The presence of the ZnS films has been found to
solve the problem of poor adhesion of Bi,S, and Cu,S
film on the glass substrates, while offering optical charac-
teristics desirable for various applications in the
ZnS-Bi,S,, ZnS-Cu,S and ZnS-PbS multilayer struc-
tures. The details of optical, electrical and structural
characteristics of the ZnS thin films and the effect of post-
deposition processing on these characteristics will be
reported subsequently.
2. Experimental details
2.1. Deposition of the films

[4-61, a range of other vapour phase techniques-such
as electron beam evaporation, sputtering, spray pyroly-
sis, chemical vapour deposition, hot-wall epitaxy, close-
spaced epitaxy and molecular beam epitaxy-and liquid
phase techniques such as liquid phase epitaxy, chemical
bath deposition, electrochemical deposition and succes-
sive ionic layer adsorption and reaction process-have
also been reported [3].
In this paper, we shall report on the use of chemically
deposited ZnS thin films as a substrate film on glass for
the chemical bath deposition of Bi,S,, C u S and PbS
026&1242/92/020239+06 804.50 @ 1992 IOP Publishing Ltd
2.1.1. ZnS thin films. The solution composition found
suitable for the deposition of these films on glass sub-
strates at deposition temperatures ranging from 25 "C
(for duration of deposition of up to 36 h) to 75 "C (of up
to 4 h) is: 2.5 ml of 1 M zinc sulphate solution, 2.2 ml of
NH,/NH,CI (pH 10) buffer solution, 2.7 ml of 50%
triethanolamine (TEA) and 1 ml of 1 M thioacetamide
(TA) and the rest distilled water to make up to 50 ml by
volume.
The conditions of deposition for ZnS thin films used
in the present work, samples A-G, are listed in table 1.
239
P K Nair and M T S Nair

Table 1. Details of t h e chemical deposition of ZnS. ZnS-Bi,S,, 2nS-Cu.S and ZnS-PbS thin films
Thin film deposition Thickness (pn)
Substrate side
Sample Duration Temperature appearance in Substrate Top
label Substrate Material ( h , min) ("C) daylight ZnS film

A glass ZnS 3 40 bright silvery 0.06

B glass ZnS 4 40 brassy 0.09
C glass ZnS 16 25 purple 0.14
D glass ZnS 6 60 greenish yellow 0.18
E sample A ZnS 6 60 green 0.31
F sample C ZnS 3 50 purple 0.25
G sample C ZnS 8 50 bluish purple 0.44
H glass Bi,S, (Conc. C [7]) 7 25 brown 0.16
I sample B Bi,S, (Conc. 2C) 22 25 dark 0.09 0.28
J sample B Si$; (Conc. C) 22
+ Bi,S, (Conc. C) + 22 25 bluish 0.09 0.38
K sample A cu.s 22 25 golden-purple 0.07 0.30
L sample B cu;s 22 25 purple 0.09 0.30
M sample D cu,s 22 25 bluish green 0.18 0.30
sample A cu,s 22
+cu,s + 22 25 dark blue 0.07 0.65
glass PbS 1,45 25 brassy 0.08
sample B PbS 1,45 25 brassy 0.09 0.08
glass PbS 5 25 greenish blue 0.15
sample C PbS 5 25 dark blue 0.14 0.15
sample C Bi,S, 45 min photoaccelerated deposition under 750 W m -'solar radiation,
giving bluish purple image (0.12pm thick Bi,S, film) on brassy purple
background (0.09 pm Bi,S, film), over t h e ZnS substrate film
T sample C PbS 30 min photoaccelerated deposition as above, giving bluish image
(0.11 pm thick PbS film) on brassy background (0.06pm PbS film), over
the ZnS substrate film

The test samples of ZnS as well as ZnS-Bi,S,, ZnS-Cu,S
and ZnS-PbS films were deposited on 7 5 m m x
25 mm x 1 mm glass slides for optical transmittance and
reflectance measurements, hut the films were also depo-
sited inside pairs of sheet glass of 300 mm x 200 mm x
4 mm for assessing the uniformity of the films and for the
photographic technique to be described below.
2.1.2. Bi,S, thin films. Details of the deposition of these
films from bismuth nitrate solution in TEA and TA have
been described in ['I]. The major problem in the deposi-
tion of these films has been the detachment of the films
from glass substrates at durations of deposition > 7 h
at 25 "C, which corresponds to a film thickness of
-0.16p1. A greater film thickness of -0.28pm has
been obtained in double-dip deposition in which the
substrate, after deposition of a thin film, grown up to
terminal thickness, is transferred to a fresh solution for
further deposition, but with the persistent risk of the
detachment of the film during the second dip. This
limitation may be overcome if a thin film of ZnS is
present over the glass substrate, as seen in the case of
samples I and J in table 1.
2.1.3. Cu,S thin films. Details of the deposition of Cu,S
thin films from aqueous solutions of copper(I1) chloride,
TEA, NH, (as. 30%), NaOH and thiourea (TU)have been
discussed in [SI. Here again, the detachment of the film
from glass substrates at longer durations of deposition
has prevented us from achieving film thicknesses z
0.3 pm. Further, the use of a protective polymer coating
over the film, as required in the solar control and solar
absorber coating applications of the film, has been found
to transfer the film on to the polymer foil in peeling tests.
Deposition conditions stated for samples K-M in table 1
show that the presence of the ZnS substrate film provides
the necessary mechanical stability t o the Cuss films for
longer deposition periods and multiple dip depositions
so that higher film thicknesses may be attained. Samples
K-M have been air annealed at 150 "C for 1 h to reduce
the near infrared transmittance of these films following
the results in [S, 91.
2.1.4. PhS thin films. These films were deposited from
aqueous solutions of lead acetate, NaOH, TEA and TU, as
detailed in previous papers [lo, 111. While PbS films
show good adhesion to glass substrates, the reflection

240
 Chemically deposited Z n S thin films

Table 2.Effect of ZnS substrate film on the solar optical characteristics of ZnS-Cu,S (K-N)
and ZnS-PbS (P and R ) films.
Sample A (%)
__
21.5 5.0 6.5 17.0 15.0 12.5 72.5
22.0 5.5 8.5 15.0 15.0 12.0 73.0
19.0 4.0 5.5 23.5 12.5 15.5 72.0
3.0 0.0 4.0 15.0 1.5 10.0 88.5
26.0 53.0 32.0 32.5 40.5 32.5 27.0
27.5 52.0 19.0 35.0 40.5 28.0 31.5
10.0 45.5 18.0 29.0 29.5 24.0 56.5
14.0 45.0 6.0 27.0 30.5 17.5 52.0

Details of samples are given in table 1.

losses as high as 40% for the visible and near-infrared
spectra for substrate-side incidence reduce the sensitivity
in PhS photodetectors, produce strong glare from PbS
solar control coatings and reduce the upper limit of solar
absorptance to within 60% [ I l l . Samples P and R
(tables 1 and 2) show definite advantages in this direc-
tion.
absorptance in the solar spectral range, qai,R,,, and A
from the transmittance and reflectance curves and the
spectral irradiance values of air mass (AM) 2 solar spectra,
have been discussed in previous articles [9-121.
The computerized system used for the photocurrent
response measurement on Bi,S, thin films has been
discussed in [7, 131.

2.1.5. Photoaccelerated chemical deposition and metal

3. Results and discussion
sulphide thin film (MSTF) photography. Initial results on
this were based on chemically deposited PbS thin films
[12]. Here, the cumulative effect of an increase in temper- 3.1. ZnS thin films
ature due to photothermal conversion and photocarrier The transmittance and reflectance spectra of the ZnS
generation at a growing PbS thin film under illumination films A-G of table I are given in figures 1 and 2,
has been found to contribute to an increase in film respectively. The film thicknesses estimated from the
thickness, closely following the intensity distribution in
positions of the interference peaks in these spectra are
the illuminated region. This has led to the technique of listed in table 1. They vary from "0.06 pm for sample A
MSTF photography, where a growing thin film is suh-
to -0.44pm for sample G. It is seen from the spectra
jected to the intensity variations of an image, projected
that for films of thickness up to -0.15 pm (i.e. samples
from a slide projector or when illuminated through a
A-C), the scattering losses are almost negligible. How-
photographic negative of the image kept in contact with
ever, at greater film thicknesses, obtainable by multiple
the surface, which offers at the end of a 30-45 min
immersion, the scattering is a predominant process pro-
deposition a specularly reflective coloured image-the
ducing a smoky appearance of the film surface, which
colour arising from optical interference under daylight in
thin dielectric films of varying thickness. The presence of
-
reduces the transmittance to 50% (at 2. = 0.5 pm) in
the case of sample G.
a ZnS substrate film (sample B) on the sheet glass used in
the MTSF photography has been found to offer better
image contrast in the case of Bi,S, and PbS thin films
and better adhesion of the film in the former.

2.2. Characterization
For this, films from one side of the test samples were
removed with cotton swabs dipped in dilute acids. The
spectra were recorded on a Shimadzu 340 UV-VIS-NIR
spectrophotometer with air as reference for transmit-
tance measurements and a front-aluminized mirror as
reference for near normal (5") specular reflectance mea-
surement. In the case of ZnS-only coatings, the spectra
were recorded for film side incidence of the light beam, .5 Le 1.5 2.8 2.5
and in all other cases the incidence was from the glass Y."FiLngth cpm,
substrate side, bearing the intended applications in mind. Figure 1. Optical transmittance ( T % ) characteristics (film
The computations of the integrated transmittance side incidence) of chemically deposited ZnS thin films on
and reflectance in the visible region, Ki, and RVi,respec- glass substrates, obtained under different conditions of
tively, and the integrated transmittance, reflectance and deposition a s given in table 1

241
P K Nair and M T S Nair
R U 1 I I.BL.OI
c.-
.5 l.B 1 5 2.e
'.Y.lsngth +lml
Flgure 2. Near normal specular reflectance ( R % ) of
selected ZnS thin films of figure 1
We consider that optimization of the deposition bath
and temperature may make possible good quality ZnS
films of thickness >0.15 pm. In the present work, where
our intention has been to illustrate the application of
these films as a substrate for the chemical deposition of
other metal sulphide films, thickness <0.14 pm corre-
sponding to samples A-C has been found t o be sufficient.
3.2. ZnS-Bi,S, thin films
The opticaltransmittanceand reflectance spectra and the
photocurrent response of the us-prepurcdfilms (samples I
and J, table I) are shown in figures 3 and 4, respectively.
We have reported earlier that the as-prepared B~,s, films
are amorphous and can be transformed to crystalline
state with an accompanying enhancement of electrical
conductivity of up to lo7 times by annealing at 300 "Cin
a nitrogen atmosphere of Torr for c141, The
major attraction of Bi,S, thin films is the possibility of
,g
.5 1.8 1.5 2.0
Y."'lcng,h cpm,
Figure 3. T % and R % curves of Bi,S, films H and
ZnS-Bi& films (I, J) deposited under conditions given in
table 1. The reduction in R,,, and improved film thickness
with ZnS substrate film are the notable features.
242
1.8L.86
I C".)
I .BE.87
I . BL-m
I I . 8E.89
I.BE.I8
I.BE-* I
I-BE-IP
- -- -- -
2.5 B EBB 188 608
r,mc < I C s ,
Flgure 4. Photocurrent response of the as-prepared Bi,S,
samples H, I and J of Figure 3. under 1 V bias and
800 W m-' tungsten halogen illumination (during
10LL300 5) with silver print electrodes (length =
separation).
post-deposition processing of the film to make it suitable
for electronic device applications.
The estimated film thickness for the film J is
8 as compared with r 0 . 1 6 pm for the film H
~ 0 . 3 pm
obtained on a glass substrate. The main advantage of
having the ZnS substrate film on the glass substrate is
that the Bi,S, film does not peel off during rinsing at the
end of the deposition. There is also a reduction in the
reflection losses for substrate side incidence in these films,
which may be advantageous in photodetector Or solar
absorber (ZnS-Ri,S,-Cu,S) applications. The behaviour
of the photocurrent response in these films is essentially
the same as that of Bi,S,-only coatings: the photo- and
dark-currents increasing by many orders of magnitude
when the thickness increases by a factor of 2 or 3 [7].
This effect is attributed to the drastic enhancement of
carrier mobility with increasing thickness in films of
submicron range of thickness [l5].
3.3. ZnS-Cu,S thin films
Figure 5 shows the optical transmittance and reflectance
spectra of these films, and illustrates that:
(i) Cu,S films exhibiting nearly the same optical
transmittance but different shades of colours in reflected
daylight can be produced by using ZnS substrate films of
different durations of deposition, i.e. of thickness in the
0.05-0.1 pm range (e.g. samples A, B and C of figure 1
and table 1). The solar control characteristics of the films
K and L listed in table 2 suggest that a rejection of
2 6 7 % (i.e. 100 - T,,, - 2 A (reference [lo])) of the solar
radiation is achieved at a transmittance of -22% in the
7.5
visible region, which provides an adequate illumination
level.
(ii) The adhesion of the films to the ZnS substrate
films is very satisfactory, enabling multiple-dip deposi-
tion for obtaining thicker Cu,S films for absorber coat-
ing. For example, the double-dip coated sample N gives a

.~ ~. -?
~ ~
Figure 5. Optical characteristics (substrate side incidence)
of air-annealed (150 "C. 30 min) Zn!+Cu,S solar control
films (K, L and M) and absorber film (N) deposited as
described in table 1. Note that films K and L, with nearly
the same T % curves would produce different shades of
colours in reflected daylight.
solar absorptance of 88.5%, which makes it attractive
following the concept of an evacuated solar collector
proposed in [16] where the absorber coating is applied
inside the central tube of an all-glass evacuated tube solar
collector.
3.4. ZnS-PbS thin films
Figure 6 shows the optical transmittance and reflectance
characteristics of these films deposited for solar control
(sample P) and solar absorber or photodetector (sample
R) applications along with the corresponding PhS-only
coatings deposited on glass substrates. The reduction in
RVi,from 32% in the case of PbS-only sample 0 to 19 %
in the case of the ZnS-PbS coating means that the glare
~r
Figure 6. Comparison of the optical characteristics of Solar
control films 0 (PbS) and P (ZnS-PbS) and absorber films
0 (PbS) and R (ZnS-PbS) showing considerable reduction
in R,,, with the ZnS substrate film.
Chemically deposited ZnS thin films
from the latter type of solar control glazings is consider-
ably reduced. The infrared reflectance, on the other hand,
is only increased as seen in table 2. In the case of the
thicker film (sample R), R,,,is reduced t o 17.5 %.thereby
suggesting the possibility of developing ZnS-PbS-Cu,S
absorber coatings with solar absorptance >SO%, where-
as in PbS-Cu,S coatings the solar absorptance is <70%
[17]. The reduced reflection losses would also mean
higher sensitivity in the photodetector applications.
3.5. MSTF photography
The major problem with this photography reported
recently [lZ]. based on the photoaccelerated chemical
deposition of PbS-only coatings, has been the lack of
adeauate contrast. i.e. ourule image on a brassy purple
background or a bluish purple image on a purple back-
ground. Figure 7 shows the photograph of an MTSF
image obtained on ZnS-Bi,S, film (sample S, table 1). It
can be seen that the contrast is considerably improved in
the presence of the ZnS substrate film. It must be noted
that MSTF photography with Bi,S, thin films on un-
coated glass substrates does not yield a well developed
image due to the poor adhesion of the film as the
thickness in the illuminated region increases, causing it to
peel off from the substrate during rinsing at the end ofthe
deposition, The MTSF image with pbS film on zns
(sample T, table 1) ofiers still better contrast.
We have noted that the presence of the ZnS film
reduces the incubation period normally observed in
chemical deposition of thin films, by providing a ready
catalytic surface for the ion-by-ion condensation of the
Figure 7. Photograph 01 MSTF photographic image produced
in ZnS-Bi,S, film (sample S, table 1) giving a bluish purple
image on a brassy purple background. The tone variation
in the background is due to convective currents generated
in the chemical bath due to temperature distribution
arising from the photothermal conversion of solar energy,
causing some degree of thickness variation. (Height of the
image is lOcm in the MSTF photograph.)
243
P K Nair and M T S Nair
metal and sulphide ions. Further, the photocarrier gener-
ation in the ZnS film due to the ultraviolet component of
the radiation accelerates this condensation process in the
illuminated regions from the initial phases itself, without
requiring the formation of an initial thin film of the PbS
o r Bi,S,, as is the case in the absence of the substrate film
reported earlier [12]. The application of this photo-
graphic technique is still to be explored.
4. Concluslons
In this paper we have illustrated the use of chemically
deposited ZnS thin films as a substrate for chemically
deposited Bi,S,, Cu,S and PbS thin films offering defin-
ite advantages in applications ranging from solar control
and solar absorber coatings to electronic and photo-
graphic techniques. Further work on the characteristics
of the chemically deposited ZnS films themselves for the
various applications for which ZnS is well known will be
reported elsewhere.
Acknowledgment
The authors are grateful to M r 0 Gomez-Daza for
assistance in this work.
244
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