Materials Science in Semiconductor Processing 27 (2014) 1042–1049

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Materials Science in Semiconductor Processing

journal homepage: www.elsevier.com/locate/mssp

Preparation of rod shaped nickel oxide thin films by a novel

and cost effective nebulizer technique
V. Gowthami a, M. Meenakshi a, P. Perumal a, R. Sivakuma b, C. Sanjeeviraja c,n
a
Department of Physics, Alagappa Govt. Arts College, Karaikudi 630003, India
b
Directorate of Distance Education, Alagappa University, Karaikudi 630004, India
c
Department of Physics, Alagappa Chettiar College of Engineering and Technology, Karaikudi 630004, India

a r t i c l e in f o abstract

Nickel oxide thin films have been deposited from 0.3 M aqueous solution of nickel chloride
Keywords: onto microscopic glass substrates, which were chemically and ultrasonically cleaned before
NiO thin films coating. The film depositions are carried out with 1 ml, 2 ml, 5 ml and 10 ml. The substrate
Nebulizer technique temperature, spray rate, distance between substrate and nozzle and air flow rate were fixed
Structural, optical and electrical properties at 400 1C, 0.5 ml per min,
7 cm and 1.2 kg/cm2 respectively after optimization of these
SEM deposition parameters. The effect of the volume of sprayed solution on structural, optical
EDAX properties and surface morphology of the films was investigated using X-ray diffractrom-
eter, UV–vis–NIR spectrometer, photoluminescence spectrometer, Raman spectrometer,
scanning electron microscope and liner four probe resistivity set-up respectively. The
diffraction peak along (1 1 1) plane at 2θ¼ 37.21 for all the films was observed. Besides this
other low intensity peaks were observed along (2 0 0) and (2 2 0) Miller planes. The peaks
indicated that this corresponds to cubic structure of NiO thin films. Optical transmittance
and absorption spectra are recorded using a UV–vis–NIR spectrometer. When the quantity
of sprayed volume increased, the transmittance decreased, consequently the band-gap
energy wanes from 3.64 to 3.21 eV. From PL spectra, the samples show sharp and strong UV
emission around 376 nm corresponding to the near band-edge emission of NiO under
excitation of 275 nm. The surface morphology of the films was carried out using SEM to find
the smooth, uniform and pin hole free surface. The composition of the films was estimated
using EDAX spectrum of the films. The resistivity results show that the activation energy
decreases with increase in the sprayed volume solution.
& 2014 Elsevier Ltd. All rights reserved.

1. Introduction multilayer devices [1]. The electrochromic (EC) effect occurs in

many transition metal oxide materials as well as in some
Nowadays thin film science and technology plays an organic molecules and polymers. The main advantage of an
important role in microelectronics, communications, optoe- electrochromic device is that it can regulate the throughput of
lectronics, integrated optics and photovoltaic devices. Many solar energy. All of the interesting materials are oxides that are
transition metal oxide films exhibit an electrochromic (EC) employed into thin films. Nickel oxide (NiO) is an attractive
effect as they change their optical transmittance upon charge material for use as an antiferromagnetic layer [2], p-type
insertion or extraction. These materials may be integrated into transparent conducting film [3], electrochromic devices [4,5],
and functional sensor layer for chemical sensors [6].
n
It has an excellent chemical stability and shows p-type
Corresponding author. Tel.: þ 91 94870 37305; fax: þ 91 4565
224970.
conductivity due to Ni vacancies and/or O interstitials [7].
E-mail address: sanjeeviraja@rediffmail.com (C. Sanjeeviraja). It is a semitransparent material of pale green color and has

http://dx.doi.org/10.1016/j.mssp.2014.09.014
1369-8001/& 2014 Elsevier Ltd. All rights reserved.
 V. Gowthami et al. / Materials Science in Semiconductor Processing 27 (2014) 1042–1049 1043

a wide band gap in the range of 3.5–4.3 eV [8]. Nickel increase as it passes through a constriction to satisfy the
oxide thin films are very interesting for a variety of principle of continuity, while its pressure must decrease to
applications, for instance, as active material in chemical satisfy the principle of conservation of mechanical energy.
gas sensors [9], as anode in oxygen fuel cells [10], as Thus any gain in kinetic energy of a fluid may accrue due
counterelectrode in smart windows due to its p-type to its increased velocity through a constriction is negated
electrochromic property [11], and in other optoelectronic by a drop in pressure [16]. The schematic diagram of the
devices such as elements for information display, light nebulization is shown in Fig. 1.
shutter and variable reflectance mirrors [12].
Among the electrochromic materials, nickel oxide thin
film has been mostly produced by several techniques like 3. Materials and methods
spray pyrolysis, sputtering, vacuum evaporation, chemical
deposition, sol–gel and pulse laser deposition [13,14]. The Nickel oxide thin films have been deposited using 0.3 M
advantage of chemical spray pyrolysis is manifold: nanos- aqueous solution of nickel chloride (NiCl2  6H2O) by a
tructure of the film (compact or porous) can be altered nebulizer technique onto pre-cleaned microscopic glass
depending on the spray condition, repeatability, adherent substrates, which were chemically and ultrasonically
of deposits and cost effective [15]. Spraying is performed in cleaned before coating. This technique has some advan-
an ambient atmosphere using air as driving gas and in tages such as an atomization based on hydraulic pressure
most cases aqueous precursor solutions were used. The without using any carrier gas, intermittent spraying and
present work focuses on the effect of various sprayed fine atomization. The films are having more uniform
volume of solution for the preparation of NiO film using thickness and there is no pinhole. During the film deposi-
a simple nebulizer spray technique and its effect on tion, the sprayed volume was kept at 1, 2, 5 and 10 ml for
structural, optical and electrical properties. the preparation of uniform NiO thin film. The substrate
temperature for each deposition was kept at 400 1C in the
air atmosphere. Only the small amount was consumed in
2. Experimental this nebulization and 10 min taken for spraying 5 ml of
precursor solution i.e. the nebulization rate is 0.5 ml per
The most commonly used nebulizers are jet nebulizers, min. The nozzle to substrate distance was fixed at 7 cm
which are also called ‘atomizers’ Jet nebulizers are con- and the optimized compressed carrier gas as air flow rate
nected by tubing to a compressor, that causes compressed was optimized as 1.2 kg/cm2. After deposition, the films
air or oxygen to flow at high velocity through a liquid were allowed to cool slowly to room temperature. The rate
chemical to turn it into an aerosol, which is then sprayed of cooling was 100 1C per hour.
on the substrate through the optimized ‘U’ type glass tube
which has small tapering at the substrate side to transmit
the fine droplets. Fig. 1 presents the schematic diagram of 3.1. Mechanism for the preparation of nickel oxide thin films
the simple nebulizer.
The venture effect is the reduction in fluid pressure that Nickel chloride solution was sprayed onto the pre-heated
results when a fluid flows through a constricted section of glass substrates, which undergoes evaporation, solute pre-
the tube. It is a jet effect; as with a funnel velocity of the cipitation and pyrolytic decomposition. The overall reaction
fluid increases as the cross sectional area decreases, with process can be expressed as heat decomposition of nickel
the static pressure correspondingly decreasing. When a chloride to clusters of nickel oxide in the presence of water
fluid flows through a tube that narrows to a smaller and air. The following chemical reaction took place on the
diameter, the partial restriction causes a higher pressure substrate at elevated temperature.
at the inlet than that at the narrow end. According to the
laws governing fluid dynamics, a fluid's velocity must NiCl2  6H2O-NiOþ 2HCl↑ þ5H2O↑

Fig. 1. Schematic diagram of the simple and cost effective nebulizer technique.
1044 V. Gowthami et al. / Materials Science in Semiconductor Processing 27 (2014) 1042–1049

Uniform and specular reflected NiO thin films were and the thickness of the films increases with sprayed
prepared by the process corresponding to a heat decom- solution.
position of nickel chloride to nickel oxide in the presence The XRD patterns of NiO thin films were recorded for
of water and air. The deposited films may be disorder Ni different films deposited onto glass substrate by varying the
(OH)2 structure or crystalline NiO structure according to solution volume as 1, 2, 5 and 10 ml corresponding with the
the following reactions [17]: substrate temperature at 400 1C and are shown in Fig. 3.
Ts From Fig. 3(a), NiO thin film was observed as an amorphous
NiCl2 þ 2H2 O-2HCl þNiðOHÞ2 in nature, it indicates of poor crystallinity of the films. This is
Ts
NiCl2 þ2H2 O-2HCl þ NiO þ H2 O also due to the incomplete formation of the NiO at 1 ml
sprayed volume solution. To improve the crystallinity of the
films, the volume of the solution was increased at 400 1C
Kamal et al. [17] had shown that the formation of Ni as the substrate temperature. Fig. 3(b–d) shows a major
(OH)2 is more probable at higher temperature (420 1C) diffraction peak along (1 1 1) plane and the area under the
than the one used in the present work (400 1C). Moreover, peak is slightly ameliorates with increase in film thickness
while there are two oxygen atoms in nickel hydroxide for at 2θ¼37.21 for different sprayed volumes. Besides this
one in nickel oxide. In this process, the growth rate of other low intensity peaks were observed along (2 0 0) and
the films increases with the sprayed volume. Hence, the (2 2 0) planes. These peaks indicate that NiO thin film
efficiency of rearrangement of the arriving material is corresponds to cubic structure [19]. As the thickness of film
small and the thickness of the films increases with sprayed increases, the diffraction intensity increases due to more
volume i.e., after microparticles land on the film surface, crystallites grown in the structure [20]. The crystallinity of
decomposition of chlorides and desorption of chlorine and the films was found to increase for increased sprayed
material rearrangement should take place. volume. The intensity of the diffraction peaks gradually
The NiO thin film properties were studied for various increases with increase in sprayed volume and the observed
sprayed volumes such as 1, 2, 5 and 10 ml keeping the
substrate temperature at 400 1C. The film thickness was
measured by stylus profilometer (Mitutoyo SJ-301, Japan).
The crystallinity of film was determined using an X'pert
PRO PANalytical powder X-ray diffractometer. The optical
transmittance and band gap were demonstrated by a
Ocean Optics HR-2000 UV–vis–NIR spectrophotometer.
A photoluminescence spectrum was taken by a Cary
Ellipse Fluorescence Spectrophotometer (VARIAN). Raman
spectra were measured at room temperature using a
100  microscope objective using a micro-Raman spectro-
meter (M/s Seki, Japan) equipped with an argon laser
(514.5 nm). The spectral signal was dispersed by the
2400 grooves/mm grating onto a cooled ( 70 1C) CCD
detector. The Raman spectra were acquired with a laser
excitation power of 100 mW. The surface morphology of
the films was examined by scanning electron microscopy
operated at 20 kV. Four probe resistivity measurements Fig. 2. Variation of thickness with different sprayed volumes.
were carried out using a Keithley 2000 electrometer in the
temperature range from 303 K to 423 K.

4. Results and discussion

Thickness of the deposited films was measured by stylus

profilometer. The variation of the film thickness with various
sprayed volume of films deposited at the substrate tem-
perature of 400 1C is shown in Fig. 2. It is found that film
thickness is increased from 1070 to 2720 nm while the
sprayed volume is maintained in the range between 1 and
10 ml. 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 be resulted from the
diminished mass transport to the substrate and due to gas
convection pushing the droplets of the precursor away [18].
Hence, at the quite small pyrolysis temperature used, the Fig. 3. XRD patterns of NiO thin films obtained at the different sprayed
efficiency of rearrangement of the arriving material is small volume solutions.
 V. Gowthami et al. / Materials Science in Semiconductor Processing 27 (2014) 1042–1049 1045

peak positions are in agreement with the reported value to ½ and 2 for direct and indirect transitions respectively
(JCPDS card no:78-0429). and A is a proportionality constant. From the plots of
The crystallite size (mean crystallite diameter) was (αhυ)2 versus hυ, direct band gap was found (Fig. 5) by
calculated using the full width at half-maximum (FWHM) extrapolating the linear portion of the curve to energy axis
of (1 1 1) peak from Scherrer's formula [21] and is pre- for (αhυ)2 ¼ 0. The curves indicate the values of the direct
sented in Table 1 band gap (Εg) as 3.21, 3.36, 3.42 and 3.64 eV for NiO thin
films prepared with 1, 2, 5 and 10 ml respectively.
kλ
D¼ ð1Þ Hosny [25] reported as Eg ¼2.45–3.12 eV for NiO thin
β cos θ films derived from different precursors. The band gap values
where k¼0.94 is the shape factor, λ is the X-ray wave- suggest that NiO nanoparticles are semi-conductors. Also,
length of CuKα radiation (1.5406 Å), θ is Bragg's angle and these values of Eg are in the same range as those of highly
β is the full width at half-maximum of the peak with efficient photovoltaic materials. So, the present compounds
instrument corrections. The microstrain (ε) is calculated could be considered as potential materials for harvesting
using the relation solar radiation in solar cell applications.
Varkey and Fort [26] reported as Eg ¼3.25 eV for NiO films
β cos θ prepared by a solution growth technique and Eg ¼3.6 eV was
ε¼ ð2Þ
4 reported for NiO films deposited using a spray pyrolysis
technique with nickel nitrate as precursor solution. Many
The dislocation density (δ) can be calculated from δ¼1/D2, researchers have studied the absorption of photon energy
the number of crystallites/unit area (N) is found out from value for NiO [27]. Extrapolation of linear portion to the hυ
N¼t/D3 [22] andp the lattice constant ‘a’ is calculated using axis yields a band gap values, which is in good agreement
ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2 2 2
the relation a¼d h þk þ l which will elucidate the nat- with the reported band gap values of 3.54 eV [28].
ure of the prepared NiO films. This suggests that the optical transition in nickel oxide
The variation of structural parameters of NiO films coated takes place through direct inter-band transition. Change in
on various sprayed volumes is summarized in Table 1. From the optical band-gap energy with thickness may be attrib-
the table, the crystallite size of NiO thin films can be tuned uted to the changes in homogeneity and crystallinity of the
between 12.5 and 22.45 nm by adjusting the sprayed solu- film, caused by difference in experimental conditions,
tion volume. It is observed that strain and dislocation density mainly the amount of spraying solution, spray rate and
decrease as there is an increase in the crystallite size. cooling of the substrates during deposition.
The measurements of optical spectrum for NiO thin
films have been done using a UV–vis–NIR spectrometer.
The optical transmittance spectra of the NiO films are
shown in Fig. 3. The optical transmittance spectra are
recorded in the wavelength range from 300 to 900 nm for
the films prepared at 400 1C.
Fig. 4 indicates that the transmittance decreases as film
thickness increases. The transmittance is increased from
low wavelength to higher wavelength region. The thinner
film has higher transmittance. At a wavelength of 450 nm,
the transmittance varies from 95% to 38% as the film
thickness increases. Thicker films have low transmittance,
which is due to the presence of bigger crystallite sizes and
increased the light scattering due to the surface roughness
[23]. The transmittance value is decreased due to the
reduction of O of NiO films prepared for different volumes
of solution.
The optical band gap of the film was estimated using Fig. 4. Transmittance spectra of NiO thin films for different sprayed
Tuac's equations [24]: (αhυ) ¼Α(hυ  Εg)n, where n is equal volumes.

Table 1
Crystallographic parameters of NiO thin film prepared by different volumes of solution keeping the substrate temperature at 400 1C.

Precursor Reflecting d-Spacing (Å) Lattice constant (Å) Cell volume D δ  1015 ε  10  3 N  1015/m2
(ml) plane (Å3) (nm) (L/m2) (L  2 m  4)
(h k l) Observed Standard Observed Standard

1 – – – – – – – – – –
2 (1 1 1) 2.4192 2.4116 4.1903 4.177 73.58 12.51 6.39 2.89 5.93
5 (1 1 1) 2.4197 2.4116 4.1910 4.177 73.61 16.52 3.66 2.19 3.02
10 (1 1 1) 2.4176 2.4116 4.1911 4.177 73.62 22.45 1.98 1.69 2.40
(2 0 0) 2.0939 2.0885
(2 2 0) 1.4843 1.4768
1046 V. Gowthami et al. / Materials Science in Semiconductor Processing 27 (2014) 1042–1049

Fig. 5. Variation of (αhυ)2 versus hυ plots for all samples.

Fig. 6 indicates the photoluminescence emission spec-

tra of NiO thin films for different precursor volumes. From
PL spectra, the samples show sharp and strong UV emis-
sion at 376 nm (3.29 eV) corresponding to the near band
edge emission of NiO under the excitation of 275 nm.
Furthermore, it also exhibits a UV emission peak centered
at 376 nm, and it may come from the band-edge emission
[29]. From the spectra, it may be observed that the
intensities of the PL spectra are increased by the sprayed
volume. The results of energy band gap obtained from PL
studies are in good agreement with those obtained from
UV–vis–NIR spectrometer measurements.
Most of the reports about the dominating peak indicate
that it usually lies in the visible range [30]. It confirms that
the better crystallinity of sample is linked to its near-
stoichiometric ratio. According to our experience, some
oxygen atoms may be separated out from NiO films at high Fig. 6. Variation of PL spectra of NiO thin films for all samples.
temperature and the annealing can lead to a change in the
composition of the film. As a result, the ratio of Ni/O can
achieve the stoichimetric proportion. Thus, pure NiO can
result in a higher ultraviolet/visible rejection ratio [31].
Fig. 7 shows the Raman spectra of the NiO thin films
prepared at different volumes of sprayed solution with the
laser excitation power as 100 mW and the source wavelength
as 514.5 nm. The samples show the phonon scattering in the
range from 200 to 1300 cm  1. The photon and magnon
related bands are indicated. Fig. 7 shows typical resonant
Raman scattering spectra for all the samples. Raman peaks
located at 510 and 1100 cm  1 were observed for thin film
samples and are due to Ni–O stretching mode [32]. The two
peaks could be assigned to the first-order transverse optical
(TO) and longitudinal optical (LO) phonon modes of NiO.
It was suggested that the first-order LO phonon scattering
occurred in NiO may be due to nickel vacancy defects [33].
Mironova-Ulamane et al. reported the room temperature
Fig. 7. Raman spectra of NiO film for all samples.
micro-Raman spectra of nano-powders and are similar to
those of micro-crystalline NiO [34]: there are five vibrational remain in the antiferromagnetic phase at RT even for such
bands – one-phonon (1P) TO at 440 cm  1 and LO at small grains size as 13 nm. Besides, the one-phonon band at
560 cm  1 modes, two-photon (2P) 2TO at 740 cm  1, about 200 cm  1 can also be observed in the rhombohedral
TOþLO at 925 cm  1 and 2LO at 1100 cm  1 modes; a two- phase. A new Raman band at 500 cm  1 has been found in
magnon (2M) band at
1500 cm  1. The presence of the nano-sized NiO: its temperature and size dependence sug-
two-magnon band at 1500 cm  1 indicates that the powders gested magnetic origin [35].
 V. Gowthami et al. / Materials Science in Semiconductor Processing 27 (2014) 1042–1049 1047

Fig. 8 shows the SEM images of the NiO thin films as a and it was confirmed by a hot probe technique. The four-
function of various solution volume as 1, 2, 5 and 10 ml. It can probe resistivity setup is having the temperature range of
be seen that the increase of sprayed volume solution of the 303–423 K. The variation of resistivity with temperature is
film is accompanied by a strong microstructure transforma- shown in Fig. 10. It has been observed that, in general, the
tion. From Fig. 8(a), it was observed that the NiO films exhibit resistivity decreases with increase in sprayed volume solution
irregular shape of grains which may be due to the incomplete and supports the semiconducting nature of NiO films. How-
formation of the NiO at 1 ml sprayed volume solution. Fig. 8 ever, with the increase in film thickness, the resistivity has
(b–d) shows the 2, 5 and 10 ml sprayed volume solution of been found to decreases. A graph between ln(ρ) and 1000/T is
NiO films with agglomerated rod like structures. It shows a plotted as shown in Fig. 10. The above plot has been used to
uniform grain size distribution and grain size is also becoming obtain the activation energy using Arrhenius equation
larger. A correlation between film morphology and preferred  
Ea
orientation was also observed. The film growth along (1 1 1) ρðTÞ ¼ ρ0 exp ð3Þ
KBT
preferred orientation showed similar grain structure.
The energy dispersive spectroscopy (EDS) was employed where ρ(T) is the resistivity at temperature T, Ea is the
to identify the composition of the different sprayed volume thermal activation energy, and KB is the Boltzmann constant.
solutions of NiO films at 400 1C substrate temperature. EDS The thermal activation energy (Ea) is calculated using Arrhe-
results revealed that the films consist of nickel and oxygen. nius equation (3). The estimated activation energy was found
The films contained excess oxygen at the sprayed volume to depend on the material form (single crystal or polycrystal)
solution of 1 ml and 2 ml. The quantity of the nickel in the and its values are 0.874 and 0.832 eV for 5 and 10 ml of
films increased with increasing sprayed volume solution as sprayed volume solution. In the case of oxides, the activation
well as the film thickness. This reveals that there is certain energy is the thermal energy required to hop the charges
nickel deficiency which is more severe in thinner films. (electrons or holes) from one site to the other. Estimated
Fig. 9 shows the EDS spectra of NiO films deposited at values of ‘Ea’ are comparable to the reported values for NiO
various sprayed volume solutions. films [36]. It is observed that the activation energy decreases
The resistivity measurements using a four-probe technique slightly with an increase in the film thickness. This decr-
have been done for all films but 5 ml and 10 ml NiO thin films ease in ‘Ea’ may be attributed to varying dislocation and
are presented. The type of conductivity of the film is p-type stoichiometry, caused by difference in experimental

Fig. 8. SEM images of NiO films at different sprayed volume solutions.

1048 V. Gowthami et al. / Materials Science in Semiconductor Processing 27 (2014) 1042–1049

Fig. 9. EDS spectra of NiO films at different sprayed volumes.

the present work, nickel oxide thin films were deposited on

glass substrates at temperature 400 1C. The XRD results show
that all the prepared films were NiO (cubic phase) of high
crystalline quality with the (1 1 1) preferred orientation. The
average crystallite size is around 22–12 nm. The optical
transmittance decreases with the film thickness and the
optical band gap energy of NiO film decreases from 3.64 eV
to 3.21 eV with increase in film thickness. Band gap of the thin
films was estimated as 3.29 eV using photoluminescence
measurements and is comparable with the UV–vis–NIR result.
Raman spectrum indicates that the NiO film has fewer nickel
vacancy defects after increasing the film thickness. The resis-
tivity shows the semiconducting nature of the NiO thin films.

Fig. 10. Electrical resistivity as function of temperature. Acknowledgment

conditions, viz. amount of sprayed solution, spray rate and
One of the authors (Prof. C. Sanjeeviraja) deeply thanks
cooling rate of the substrates after deposition.
the Council of Scientific and Industrial Research, New
Delhi, India for sanctioning Emeritus Scientist Scheme.
5. Conclusion

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