Applied Surface Science 199 (2002) 211–221

Preparation and characterization of spray pyrolyzed

nickel oxide (NiO) thin films
P.S. Patil*, L.D. Kadam
Department of Physics, Thin Film Physics Laboratory, Shivaji University, Kolhapur 416 004, India
Received 3 April 2002; accepted 18 June 2002

Abstract

A simple and inexpensive spray pyrolysis technique (SPT) was employed to deposit nickel oxide (NiO) thin films from
hydrated nickel chloride salt solution on to glass substrates. The thermogravimetric analysis (TGA) and differential thermal
analysis (DTA) techniques were used to study the thermal characteristics of the precursor salt. The effect of the volume of
sprayed solution on structural, optical and electrical properties was studied using X-ray diffraction (XRD), infrared (IR), optical
absorption, electrical resistivity and thermoelectric power (TEP) techniques. It is found that increase in the volume of sprayed
solution leads to the increment in film thickness and amelioration of crystallinity of the film, consequently the band-gap energy
wanes from 3.58 to 3.4 eV. It also affects resistivity and TEP of the film.
# 2002 Elsevier Science B.V. All rights reserved.

Keywords: Spray pyrolysis; Nickel oxide; Thin films; Characterization

1. Introduction or substituting Li for Ni at Ni sites [6]. Most attracting

Nickel oxide (NiO) is the most exhaustively inves-
tigated transition metal oxide. It is a NaCl-type anti-
ferromagnetic oxide semiconductor. It offers promis-
ing candidature for many applications such as solar
thermal absorber [1], catalyst for O2 evolution [2],
photoelectrolysis [3] and electrochromic device [4].
Nickel oxide is also a well-studied material as the
positive electrode in batteries [5].
Pure stoichiometric NiO crystals are perfect insu-
lators [6]. Several efforts have been made to explain
the insulating behavior of NiO. Appreciable conduc-
tivity can be achieved in NiO by creating Ni vacancies
*
Corresponding author. Tel.: þ91-231-693579;
fax: þ91-231-691533.
E-mail address: patilps_2000@yahoo.com (P.S. Patil).
features of NiO are: (1) excellent durability and
electrochemical stability, (2) low material cost, (3)
promising ion storage material in terms of cyclic
stability, (4) large span optical density, and (5) pos-
sibility of manufacturing by variety of techniques.
Nickel oxide thin films have been prepared by
various techniques that involve: vacuum evaporation
[7], electron beam evaporation [8], rf-magnetron sput-
tering [9,10], anodic oxidation [11], chemical deposi-
tion [12–14], atomic layer epitaxy [15], sol–gel [16]
and spray pyrolysis technique (SPT) [17–19].
Although SPT has been employed in the past to
deposit NiO films through acetylacetonate [17] and
nitrate [18] routes, their characterization have sparsely
been carried out. Aqueous solutions are commonly
used in SP system to deposit thin films due to ease of
handling, safety, low cost and availability of a wide

0169-4332/02/$ – see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 1 6 9 - 4 3 3 2 ( 0 2 ) 0 0 8 3 9 - 5
212 P.S. Patil, L.D. Kadam / Applied Surface Science 199 (2002) 211–221
range of water-soluble metal salts. The solute must
have high solubility to increase the yield of the
process. Metal chlorides have highest water solubility
relative to other metal salts and are used for the
industrial production of several oxides and ferrites.
The corrosive nature of the product gases and the
adverse effect of residual chlorine on properties
decrease the general attractiveness of these salts but
the technology for handling such systems is available.
Other metal salts such as nitrates, acetates and
sulfates can also introduce impurities, which may
adversely affect subsequent processing or properties
and phase development. The low solubility of metal
acetates and high decomposition temperature of metal
sulfates limit the use of these salts.
With the previously mentioned effect, the present
paper focuses on use of aqueous solution of nickel
chloride to deposit NiO thin films on glass substrates
by spray pyrolysis technique, and their structural,
optical and electrical properties studies. Thin films
of variable thickness were grown by changing the
volume of sprayed solution.
Thickness of the thin film plays an important role in
determining the film properties unlike a bulk material
and almost all film properties are thickness-dependent.
Adler et al. studied thickness-dependent magnetic
properties of NiO epitaxial film grown on MgO
(1 0 0). The Neel temperature strongly reduced from
the bulk value even for the 20 monolayer films [20].
Reproducible properties are achieved only when the
film thickness and the deposition parameters are kept
constant. In many applications, particularly in the case
of optical devices such as interference filters, anti-
reflection coating, etc., the success of fabrication
depends only on the deposition of specific thickness.
In other cases even though a specific thickness may not
be strictly necessary, a good control of it will still be
imperative. Consequently, this paper focuses on the
effect of volume of sprayed solution on NiO film
thickness and its effect on structural, electrical and
optical properties.
2. Experimental procedure
Nickel oxide thin films were prepared by spraying a
0.05 M solution of nickel chloride in doubly distilled
water onto the pre-heated amorphous glass substrates
kept at 350 8C. The spray rate was kept constant at
8 ml/min. Films of various thickness were obtained by
spraying 30, 45, 60 and 75 ml, 0.05 M solution of
nickel chloride and the films were denoted as samples
N30, N45, N60 and N75, where subscripts denote the
volume of the solution sprayed. Film thickness was
measured by using weight difference method consid-
ering the density of the bulk nickel oxide. As the
density of thin films was certainly lower than the bulk
density, the actual film thickness would be larger than
the estimated values.
Thermogravimetric analysis (TGA) and differential
thermal analysis (DTA) of the nickel chloride
((NiCl26H2O), AR grade, purity 98%) was carried
out using TA instruments (USA) SDT 2960 (simulta-
neous DCS–TGA). The structural, optical and elec-
trical characterization of the films deposited at
optimized preparative parameters was carried out.
The X-ray diffractometer (Philips PW 1710) with
Cu Ka radiation was used for structural studies in the
range of 2y ¼ 10–1008. The infrared (IR) spectrum of
as-deposited films was recorded using a Perkin-Elmer
IR spectrophotometer model 783 in the spectral range
400–4000 cm1. The pellets were prepared by mixing
KBr with nickel oxide powder collected by scratching
of the film from glass substrate in the ratio 300:1 and
then pressing the powder between two pieces of
polished steel. To determine band-gap energy of the
films, optical absorption study was carried out in the
wavelength range 300–850 nm, using a Hitachi 330
spectrophotometer. A two-probe resistivity unit was
used to measure the electrical resistivity of the films in
the temperature range 300–550 K. The thermoelec-
tromotive force (thermo-emf) was measured as a
function of temperature in the range of 300–475 K.
3. Results and discussions
3.1. Thermal decomposition of NiCl26H2O
The decomposition behavior of the precursor for
NiO films (NiCl26H2O) was studied by TGA and
DTA at a scan rate of 10 8C/min, in the temperature
range 0–1000 8C. Fig. 1A and B shows the TGA and
DTA analysis of NiCl26H2O, respectively, in air
atmosphere. It is clearly depicted that the loss of water
takes place in four endothermic peaks at 66, 132.5,
 P.S. Patil, L.D. Kadam / Applied Surface Science 199 (2002) 211–221 213

chloride into nickel oxide. This continues up to

590 8C. The calculation of the amount of residue
(31.5%) clearly indicates the formation of NiO phase,
which remains stable up to about 1000 8C. Therefore,
in the study, the decomposition temperature for NiO
film was selected such that it is greater than 280 8C.
Reports on decomposition of nickel acetate, nickel
nitrate and nickel sulfate were given by others [21] and
stated that decomposition characteristics depend on
initial ingredient. The onset of formation of NiO also
depends on other parameters such as particle size, total
mass taken for the characterization, temperature scan
rate and ambient atmosphere.

3.2. Formation of nickel oxide thin films

Nickel chloride solution was sprayed onto the pre-

heated glass substrates, which undergoes evaporation,
solute precipitation and pyrolytic decomposition,
thereby resulting in the formation of nickel oxide thin
films according to the following reaction:
350  C
NiCl2  6H2 O ) NiO þ 2HCl " þ 5H2 O " (1)

The as-prepared films were gray in color, uniform

Fig. 1. (A) Thermogravimetric analysis of NiCl26H2O; (B)
differential thermal analysis of NiCl26H2O.
195.5 and 242 8C. The weight loss at 66 8C is due to
expulsion of physisorbed water, whereas above
100 8C the weight loss is mainly due to removal of
water of crystallization. The total weight loss corre-
sponding to removal of water is calculated to be about
46%.
The regular weight loss starts at about 280 8C,
which is due to the slow decomposition of the sample
and can be related to the transformation of nickel
and strongly adherent to the substrates. The thickness
of the films was varied from 0.028 to 0.26 mm. The
values of the film thickness are given in Table 1. It is
observed that the thickness of the film increases with
volume of the sprayed solution. However, this increase
in thickness is not exactly proportional to the volume
of sprayed solution. This may be due to the variation in
deposition efficiency, which may have resulted from
the diminished mass transport to the substrate and due
to gas convection, pushing the droplets of the pre-
cursor away.
The nickel oxide films thus formed were further char-
acterized by X-ray diffraction (XRD), IR spectroscopy,

Table 1
Effects of volume of sprayed solution on film thickness and properties of NiO thin films prepared by spray pyrolysis technique

Serial Volume of sprayed Thickness Grain Band-gap Electrical resistivity Activation Thermoelectric
no. solution (ml) (mm) size (nm) energy Eg (eV) at 300 K (104 O cm) energy Ea (eV) power (mV/K)

1 30 0.028 14 3.58 1.0 0.35 101

2 45 0.048 14.5 3.55 1.9 0.36 89
3 60 0.10 15 3.49 3.0 0.38 85
4 75 0.23 17 3.40 9.0 0.39 76
214 P.S. Patil, L.D. Kadam / Applied Surface Science 199 (2002) 211–221
optical absorption, electrical resistivity and TEP mea-
surement techniques.
3.3. XRD studies
The nickel oxide thin films were analyzed by X-ray
diffraction technique to study structural identification
and changes in the crystallinity. The XRD patterns
of nickel oxide thin films of different thickness are
shown in Fig. 2. It is found that all the samples were
polycrystalline consisting of NiO cubic phase, com-
prising a strong reflection along (1 1 1) plane and a
Fig. 2. XRD patterns of NiO thin films of various thickness.
weak reflection along (2 2 0) plane. The ‘d’ values of
the XRD reflection were compared with the standard
‘d’ values taken from the ASTM diffraction data file
(no. 4-0835). Good agreement between the observed
and standard ‘d’ values confirms that the material
deposited is NiO (cubic).
The magnitude of major XRD peak corresponding
to (1 1 1) plane and value of area under the peak
slightly ameliorates with increase in film thickness.
No other additional peaks corresponding to other
phases have emerged. This suggests that NiO phase
is stable and its formation is independent of film
thickness. It is also seen that the positions of (1 1 1)
diffraction peaks change among samples by about
0.278. This may be due to the change in internal stress
of the films of various thickness during film growth.
The grain size of the crystallites (mean crystallite
diameter) was calculated for major reflex (1 1 1) using
the well-known Scherrer’s formula (Eq. (2)), by
assuming the factors, viz. instrumental broadening,
distortion of lattice, etc. are common among all the
samples:
0:9l
D¼ (2)
b cos y
where l is wavelength (1:5406  1010 m), b the full
width in radian at half maximum of the peak, and y is
Bragg’s angle of the XRD peak. The grain size was
found to vary between 14 and 17 nm as the film
thickness was changed from 0.028 to 0.23 mm. The
values are given in Table 1.
3.4. Infrared spectroscopy
Nickel oxide thin films were studied by means of IR
spectroscopy, which gives information about the phase
composition and the way in which oxygen is bound to
the metal ions.
IR transmission spectrum of the sample N75 of the
nickel oxide thin film in the range between 400 and
4000 cm1 is shown in Fig. 3. It consists of four
intensive bands at 470, 1020, 1600 and 3420 cm1.
The band at 470 cm1 can be assigned to nickel–
oxygen interaction. The existence of other bands
clearly indicates that the sample N75 consisted of
chloride ions, water molecules and/or hydroxide ions.
The results of thermal analysis already indicated that
NiCl26H2O can be completely decomposed to NiO at
 Fig. 3. The IR spectrum of powder scratched from NiO thin film (N75).

Fig. 4. Variation of optical density (at) vs. wavelength (l) for all the samples.
216 P.S. Patil, L.D. Kadam / Applied Surface Science 199 (2002) 211–221

temperatures higher than 590 8C. Hence, at the pyr-
olysis temperature (350 8C), thermal decomposition
proceeds imperfectly and NiCl2 thereby remains in the
film, leading to evolution of transmission band at
1020 cm1. The presence of water molecules or
hydroxide ions (at 1600 and 3420 cm1) at 350 8C
deposition temperature were not anticipated from the
thermal analysis results as both physisorbed and che-
misorbed water molecules expel well below this tem-
perature. Therefore, their presence in IR spectrum
may be due to absorption of water during mixing
and pelleting with KBr.
3.5. Optical absorption
The variation of optical density (at) with photon
energy (hn) for the NiO films with different thickness
is shown in Fig. 4. It is found that absorption
coefficient decreases with decrease in photon energy,
with sharp decrease near the band edge in the visible

Fig. 5. Variation of (ahn)2 vs. hn for all the samples.

 P.S. Patil, L.D. Kadam / Applied Surface Science 199 (2002) 211–221 217

region. For all the samples, absorption coefficient was
of the order of 104 cm1.
Nickel oxide is a high band-gap semiconductor
with the absorption edge in the UV region and no
absorption in the visible region. The presence of Ni3þ
ions in the oxide lattice shows charge transfer transi-
tion, with the consequent absorption in the visible
region [22]. NiO films deposited by us also show
absorption in the visible region. There may be three
possible explanations for the above process. The first
one is that the main stoichiometry of the film is NiO
and Ni2O3 is present as a minority phase that could not
be detected by XRD. The second possibility is that two
adjacent divalent nickel ions become Ni3þ due to
charge transfer process caused by presence of nickel
vacancy. Third possibility is that the stoichiometry of
the film is NiO, but excess oxygen together with the
hydrogen may be present in the film as OH groups.
Recorded optical data were further analyzed to
calculate the band-gap energy of the NiO films using
classical relation. Fig. 5 shows the plot of (ahn)2
versus hn for NiO films with different thickness.
The optical band-gap is obtained by extrapolating
the straight-line portion of the plot at a ¼ 0. The value
of the optical band-gap shifts towards lower energy
and the slope of the plot decreases when the film
thickness increases. The value of band-gap energy
changes from 3.58 to 3.4 eV with increase in the film
thickness. Varkey and Fort reported Eg ¼ 3:25 eV for
NiO films prepared by solution growth technique [13]

Fig. 6. Variation of log r vs. 1/T for all the samples.

218 P.S. Patil, L.D. Kadam / Applied Surface Science 199 (2002) 211–221

and Eg ¼ 3:6 was reported for NiO films deposited
using spray pyrolysis technique with nickel nitrate
solution. Many researchers have studied the absorp-
tion of photon energy for NiO [12,18]. Reported band-
gap energy value for the nickel oxide is in the range of
3.4–3.8 eV, which is in good agreement with our
report. This suggests that the optical transition in
nickel oxide takes place through direct inter-band
transition. Change in the optical band-gap energy with
thickness may be attributed to the changes in homo-
geneity and crystallinity of the film, caused by dif-
ference in experimental conditions, mainly the amount
of spraying solution, spray rate and cooling of the
substrates during deposition.
3.6. Electrical resistivity
The room temperature electrical resistivity was
calculated and found to vary from 1  104 O cm for
N30 to 9  104 O cm for N75. Increase in the resistivity
with increase in thickness of the film may be attributed
to non-stoichiometry of the NiO films and surface
states. Nominally pure and stoichiometric nickel
oxide has room temperature resistivity of the order

Fig. 7. Variation of log r vs. (T0/T)1/4 for all the samples.

 P.S. Patil, L.D. Kadam / Applied Surface Science 199 (2002) 211–221 219

of 1013 O cm [25]. Low electrical resistivity in our
nickel oxide thin film may be due to formation of non-
stoichiometric film with excess oxygen or less oxygen,
which produces doped sample. In these cases, an
increase in resistance can be expected with increase
in thickness [24]. Electrical resistivity of nickel oxide
thin films have been studied by many researchers
[9,12,13,19,20,23], and reported resistivity is in the
range of 10–106 O cm.
Fig. 6 shows the variation of electrical resistivity
with temperature for NiO films with different thick-
ness. For all the samples, it is observed that resistivity
decreases with increase in temperature and supports
the semiconducting nature of NiO films. The thermal
activation energy (Ea) is calculated by using Arrhenius
equation. The estimated activation energy was found
to depend on the material form (single crystal or
polycrystal) and on the temperature range and its
value ranges from 0.6 to 1.9 eV [24]. In case of oxides,
the activation energy is the thermal energy required
to hop the charges (electrons or holes) from one site to
the other. Estimated values of ‘Ea’ are comparable to
the reported values for NiO films [9,10].
It is observed that the activation energy increases
slightly with an increase in the film thickness. This
increase in ‘Ea’ may be attributed to varying disloca-
tion and stoichiometry, caused by difference in experi-
mental conditions, viz. amount of spraying solution,
spray rate and cooling of the substrates during deposi-
tion.
Fig. 7 shows the variation of log r with (T0/T)1/4.
This plot yields a straight line, which suggests that the

Fig. 8. Variation of thermo-emf vs. temperature difference (dT) for all the samples.
220 P.S. Patil, L.D. Kadam / Applied Surface Science 199 (2002) 211–221
temperature dependence of electrical resistivity is
consistent with the relation
 a
T0
r ¼ r0 exp (3)
T was varied from 30 to 75 ml. The XRD studies show
where, T0 ¼ 7  107 K and a depends on kind and
degree of disorder of the considered system and on
temperature. In doped crystalline semiconductor, the
values of a are 0.25 and 0.5 [24,26]. This result evinces
for variable range hopping of charge carriers between
randomly distributed localized electronic states in the
NiO samples. Since the material NiO has not been
prepared as pure stoichiometric, extrinsic conduction
dominates rather than intrinsic conduction. Impurity
or vacancies present in the material creates carriers in
NiO.
3.7. Thermo-emf measurement
Thermo-emf measurement was used to evaluate
thermoelectric power (TEP) and nature of the material
being studied. From the sign of thermoelectric-emf it
has been found that all the samples exhibit p-type
conductivity. Fig. 8 shows the variation of thermo-emf
with temperature difference. The plot shows that
thermo-emf increase with increasing temperature dif-
ference. This may be attributed to the increase in
mobility and/or concentration of charge carrier with
rise in temperature.
Small change in induced emf is observed with
increase in film thickness. This may be due to slight
change in average grain size of crystallite with increase
in film thickness [27]. The values of thermoelectric
power are given in Table 1. In general, the small values
of TEP (<30 mV/K) indicate that electronic state is
metallic and large values of TEP ( 100 mV/K) are
related to localized electronic state for the oxides. In
case of present samples, the values of TEP lie close to
100 mV/K, thus confirming the polaron hopping con-
duction mechanism in these samples.
4. Conclusions
Nickel oxide thin films of various thickness were
deposited, by varying the volume of sprayed solution,
onto the glass substrates using a simple and inexpen-
sive spray pyrolysis technique at 350 8C. The pyro-
lytic decomposition characteristic (TGA and DTA) of
a precursor NiCl26H2O was used to derive the deposi-
tion temperature. The film thickness increases from
0.028 to 0.23 mm as the volume of spraying solution
that all the films deposited were NiO (cubic phase)
with orientation along (1 1 1) direction. Increase in
film thickness leads to a slight improvement in the
crystallinity. The IR studies of a typical film indicated
presence of NiO phase with some amount of hydration
and chloride ions.
The optical band-gap energy of NiO film decreases
from 3.58 to 3.4 eV with increase in film thickness.
The room temperature electrical resistivity of all the
samples was of the order of 104 O cm, thicker film
being more resistive. Thermo-emf measurements
showed that NiO films were of p-type nature.
Acknowledgements
The authors wish to acknowledge the support by
UGC-DRS (SAP) project sanctioned by the University
Grants Commission, New Delhi, India.
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