Thin Solid Films, 235 (1993) 47-50 47

Solution growth technique for deposition of nickel oxide thin films

A. J. Varkey and A. F. Fort

Department of Physics, University of Swaziland, Private Bag, Kwaluseni (Swaziland)
(Received December 17, 1992; revised February 22, 1992; accepted March 30, 1993)

Abstract
A chemical method has been developed for the preparation of thin films of NiO and NiOOH on glass substrates
from solution containing the amine complexes of the metal ions. The film thickness was measured gravimetrically
and ranges between 0.06 gm and 0.12 gm. Some optical and electrical measurements have been carried out on these
films. The optical absorption spectra show that NiO and NiOOH have band gaps of 3.25 eV and 3.75 eV
respectively. The spectral variation of the optical constants has also been measured. NiO films are insulating;
NiOOH has an electrical conductivity of 0.125 ~-t m-l.

1. Introduction yield the oxide. To obtain continuous films, precipita-

In recent years, thin films of chalcogenides and ox-
ides have received much attention due to their wide
application in science and technology. The fact that the
use of materials as thin films in place of single crystals
results in a drastic cut in the production cost of the
devices has made thin film technology more attractive.
Various methods are available for preparation of thin
films, but chemical bath deposition is the cheapest
technique available at present.
Recently, there have been several reports on the
deposition of chalcogenide thin films by this method
[1-10]. The chemical aspects of the deposition of these
films is based on the formation of the respective metal
complexes with suitable ligands in a solution containing
chalcogen ions. Slow dissociation of the complex re-
leases the metal ions, and the chalcogenide is deposited
on substrates by i o n - i o n interaction. Oxides of metals
have a wide range of applications in opto-electronic and
thermal devices [ 11-13]. In particular, nickel oxide is
well known for its electrochromic property, and is used
as a cathode in alkaline batteries. Mostly, oxide films
are grown from the vapor phase, involving high tem-
peratures and complex equipment.
There have been reports on nickel oxide films pro-
duced anodically [14], electrochemically [15-17], by
sputtering [18-21], by electron beam evaporation [19]
and by oxidation of nickel at high temperatures [22].
We have developed a simple technique for deposition of
nickel oxide films from solutions. The basic principle of
the deposition procedure is that metal ions undergo
hydrolysis in an alkaline aqueous solution precipitating
its hydrous oxide, which decomposes on heating to
tion is slowed down by complexing the metal ions. This
paper gives details of the deposition procedure and the
results of some optical and electrical measurements
made on these films.
2. Experimental details
100ml of freshly prepared 0.1 M nickel sulphate
solution was mixed thoroughly with 50 ml of 25% am-
monia, by stirring. The resulting solution was dear and
blue in colour. 3 ml of this solution was placed in a
beaker, and 30 ml of distilled water was added. Glass
slides, cleaned by dipping them in a solution containing
l0 g of potassium dichromate, 10ml of concentrated
sulphuric acid and 100 ml of distilled water, were placed
vertically in the beaker. The solution, when heated at
3 3 0 - 3 5 0 K on a hot plate, slowly turned cloudy.
Within ~ 2 h it became clear again, and a green/grey
deposit of NiO was present at the bottom of the beaker.
The slides were covered with the same material, as a
continuous thin film. They were removed, washed in
distilled water and dried in hot air. The films were
further heated at 380 K to remove any water content.
On heating at ~550 K in air, the films turned into
black/grey NiOOH.
A Philips PM 3700 spectrophotometer was used for
optical measurements. For electrical measurements sil-
ver paste electrodes were placed on the films. Optical
data were used to calculate the spectral variation of the
refractive index and extinction coefficient of the materi-
als. The effect of annealing on the electrical conductiv-
ity and the optical properties of the films was

0040-6090[93/$6.00 1993 - - Elsevier Sequoia. All rights reserved

48 A. J. I/arkey, A. F. Fort / Deposition of nickel oxide thin films
investigated. Film thickness was calculated gravimetri-
cally from the mass of the deposit, bulk density and
film dimensions.
3. Results and discussion
The chemical aspect of the deposition technique is
based on the fact that when Ni(OH)2 is heated it forms
the NiO. When excess ammonia is added to the nickel
sulphate solution the hydroxide formed is dissolved in
it, and the solution turns blue, indicating the presence
of the nickel amine complex. Dissociation of the com-
plex ions, when heated, reversed the process, and slowly
released the hydroxide, which was then converted into
NiO. Phase change into NiOOH occurred at ~ 550 K.
At room temperature no deposit was found on the
slides. At higher temperatures the reaction was faster,
resulting in low terminal thickness. Film thickness was
found to increase with the concentration of the Ni ions
in the solution.
Figure 1 shows the absorption spectra of 0.08 lam
thick NiO and NiOOH fills in the UV and visible
regions. Extrapolation of the linear portion of the curve
to zero absorbance shows that the materials have opti-
cal band gaps of 3.25 eV and 3.75 eV respectively. Bulk
crystalline NiO has a band gap of ~4.0eV, much
higher than the 3.25 eV of the solution-grown films,
possibly as a result of impurity levels introduced during
deposition. D.c.-sputtered NiO films are reported to
have broad absorption in the visible region, with a peak
c,0-
b calculate the dispersion relation of the optical constants
~20zs,,
6;0
Wavetengfh(nm)
Fig. t. Optical absorption spectra of (a) NiO and (b) NiOOH film.
10T p
m
J
/
0.8-~
/
l
0.6-
0.~-
0.2
\
| I I
500 700 900
Wavetength {nml
Fig. 2. Transmittance (T) and reflectance (R) spectra of an NiO film
(broken line) and an NiOOH film (solid line).
at 2.3 eV [22]. However, in the NiO films under study,
the absorption shifts towards the UV, and has a sharp
peak at ,-~4.0 eV (Fig. 1). The difference could be as a
result of the structural variations.
Transparent NiO films, when heated at ~550 K in
air, had a phase change into the higher oxidation state
of NiOOH, accompanied by a colour change to dark
grey. Such a colour change has been reported in electro-
deposited NiO films on annealing in air at 520 K [ 17,
23]. Transmittance and reflectance spectra of the films
are shown in Fig. 2. These data have been used to
shown in Figs. 3 and 4. High transmittance in the
visible region of the spectrum suggests the possible use
of these films as glazing materials. It was noted that
annealing the NiOOH films in air at 570-720 K in-
creased their transmittance by 10%. There was no sig-
nificant change in NiO on annealing. The high
refractive index makes these films suitable for antirefiec-
tion multilayers. At 350 nm, the high refractive index
may be due to an exciton band. The wide band gap
suggests that NiO can be used as an interfacial layer in
heterojunction solar cells. NiOOH has electrical con-
ductivity of ~0.125Q -~ m -1, too low for use as a
transparent conductor. Doping could possibly increase
its conductivity.
 A. J. Varkey, A. F. Fort / Deposition o f nickel oxide thin films 49

S.O-

5.0

\
3.0

1' 0t~. ~,
k
1 | I
S00 700 900
Wavelength (nrnl

Fig. 3. Dispersion of the optical constants n, k of an NiO film. k

r i I
500 700 900
Wavelength (rim)

Fig. 4. Dispersion of the optical constants n, k of an NiOOH film.

Electrochromism is well known in oxides of transi-
tion metals. To investigate this property, the oxide is
incorporated in a multilayer structure with conducting trical conductivity of ~0.125 f~-~ m -I. Some possible
electrodes on either side. A possible approach is to use uses of these materials are suggested.
transparent conducting oxides (TCOs) such as ITO and
SnO2 as electrodes. Sputtered NiO films have been used
in such configurations [12]. Although no attempt was Acknowledgements
made to investigate electrochromism in the present
work, since the oxides were deposited on glass sub- The authors gratefully acknowledge the financial sup-
strates, we propose that the same technique could be port of this project by the Research & Publications
used to deposit conducting oxide films, for an all-chem- Committee of the University of Swaziland.
ically-deposited multilayer structure. We have utilized
the technique for deposition of silver oxide [24] and
cobalt oxide [25] thin films. Further work is in progress. References

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4. Conclusions
A simple chemical method has been developed for
preparation of thin films of nickel oxides, NiO and
NiOOH. Film thickness, optical absorption coefficient,
transmittance and reflectance have been measured in
the UV and visible regions. Dispersion of the optical
constants has also been calculated. NiO and NiOOH
have optical band gaps of 3.25 eV and 3.75 eV respec-
tively. NiO films are dielectric, while NiOOH has elec-
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