Characterization of NiO Thin Films Fabricated by Magnetron Sputtering

*L. Ghimpu. V. Suman

Institute of Electronic Engineering and Nanotechnologies, Academy of Sciences of Moldova, MD-2028, Chisinau, Moldova
E-mail: lidia.ghimpu@gmail.com
**I. Lungu
Department of Physics and Engineering, Moldova State University, Chisinau, MD-2009, Moldova
E-mail: ionlungu.md@mail.ru

Abstract - NiO thin films were deposited by RF
magnetron sputtering method under constant O2 (99.99%)
in the O2/Ar+O2 flow rate at 450oC substrate temperature
with different thicknesses. The surface and structural
properties of NiO thin films were investigated using
atomic force microscopy (AFM), X-ray diffraction (XRD).
The optical properties were studied by UV-VIS
spectroscopy. AFM studies show that the roughness
parameters of the NiO surfaces are influenced by the film
thickness. XRD measurement showed that the films were
crystallized in the zinc blende phase type. The grain size
was increased with increasing the film thickness. The
studies on the optical properties show that the direct band
gap value slightly changes from 3.48 to 3.43 eV when the
thickness varies from 150 nm to 350 nm.
Keywords - RF magnetron sputtering; NiO thin films;
roughness; grain size; band gap.
1. Introduction
NiO is considered an attractive candidate
for electronic and spintronic applications due
to its intrinsic p-type conductivity, high
refractive index, high melting temperature,
hardness, corrosion-resistant properties,
abundant availability, chemical stability,
non-toxicity and low-cost [1-3]. Both
optical and electronic properties of NiO
depends on its degree of structural defects.
NiO is often non-stoichiometric because of
micro-structural defects, such as nickel
vacancies and interstitial oxygen. There are
scarce reports on the NiO thin films prepared
by magnetron sputtering. Reports on NiO
films produced by magnetron sputtering
show that the optical and electrical properties
of these films depend on oxygen content in
plasma, RF sputtering power and on
substrate temperature. This study reports
the effects of the thickness on structural and
optical properties of NiO thin films
fabricated by magnetron sputtering keeping
constant the O2 content in the growing
atmosphere and substrate temperature.
2. Experimental Details
For sample preparation, a Ni target of 99.5%
purity was used in the sputtering process. The
sputtering chamber was evacuated down to 4×
10-5 mbar by a turbo molecular pump. The
distance between the target and the substrate
was kept constant at 7-8 cm. The magnetron
discharge was done under 3-4 sccm O2
(99.99%) in the O2/Ar+O2 flow rate at 450oC
substrate temperature with 45 ml/min via
independent mass-flow controllers. The
working total pressure was kept at 7.4 × 10-3
mbar. Before deposition, the glass substrates
were sequentially sonicated in acetone and
ethanol, followed by rinsing with distilled
water and drying. NiO thin films were
obtained at 210 W at different thicknesses:150
nm, 200 nm, 250 nm, 300 nm and 350 nm.
The surface morphology was investigated
using a multimode commercial atomic force
microscope (SOLVER Next – NT-MDT).
Cone-shaped tips from monocrystalline
silicon (tip radius ~ 10 nm) on cantilevers with
a stiffness of about 17 N/m were used to
perform the measurements. The AFM
measurements were successfully carried out at
two different scan sizes (10x10 um and 5x5
um) in tapping mode in which height
(topography) and phase signals were acquired
simultaneously. The crystal structures of NiO
thin films were measured by Ultima IV X-ray
Diffracrometer (XRD) in a θ-2θ configuration
with CuKα radiation (λ=0.154 nm). A double-
beam Perkin-Elmer Lambda 19 UV–VIS
spectrophotometer was used to record
transmission spectra in the 300 – 1000 nm
wavelength range.

3. Results and Discussion

A. Morphology and structural properties
The AFM study of the samples allows us to
determine the surface roughness. Local
morphology features were measured (length
and width of individual grains) and the
roughness parameters of the surfaces, RMS
and Ra, were calculated using an image
processing software (Nova Px) for
topography. The AFM 3D images for NiO
thin film deposited at an RF power 210 W
with different thicknesses are presented in
Figure 1 with scan area 5µm × 5µm. The
surface parameters of the NiO thin films are
shown in Table 1.

Table 1 The surface parameters of the NiO thin films

NiO thin RMS Standard Ra Standard

film
(nm) Deviation (nm) Deviation
thicknesses
(nm) (nm
150 nm 3.35 0.47 2.38 0.30

200 nm 5.30 0.30 1.25 0.22

250 nm 4.09 0.34 3.20 0.15

300 nm 5.43 0.25 3.24 0.21

350 nm 8.72 0.46 3.06 0.41

The results from Table 1 show that the

roughness parameters of the NiO surfaces
are influenced by the film thickness. The
surface roughness increases as the film
thickness increases up to 200 nm. As the
thickness reaches 200 nm, the RMS
roughness rises up to 5.30 nm. With further
increasing of the thickness the roughness
increasing and at d=350 nm reached 8.72
nm. These significant changes in roughness
with increasing NiO film thickness are due to
the reflecting nucleation, coalescence and Fig. 1 3D AFM images of NiO thin films with
continuous film growth processes [4]. The different thicknesses deposited at RF power 210 W
RMS value of the roughness is influenced
 by the degree of aggregation and grain size 350 - 900 nm wavelength range. At the 350
of the thin films. This is in agreement with nm thickness of the NiO film transmittance
the principle that different grain size affects decrease. For higher film thickness sufficient
the surface roughness of the thin films [5]. numbers of atoms are introduced to the
Therefore, the AFM results show that the deposited films so, the film homogeneity
increase of film thickness increases the mean increases and localized states or trapped
grain size, surface-to-volume ration and levels decrease. Hence, the order and the
RMS roughness. The diffraction patterns of crystallinity of the higher film thickness are
the as-deposited NiO thin films with improved. This leads to the increase of the
different thicknesses are shown in Figure 2. absorption in the region of 500 – 700 nm and
The peak positions are compared with the decreasing transmittance.
JCPDS file [6] and the corresponding Miller
indices were indexed. The X-ray diffraction T-NiO-210-150nm
75 T-NiO-210-200nm
(XRD) investigation of NiO films indicated T-NiO-210-250 nm
T-NiO-210-300 nm
the polycrystallinity of the films with the 60 T-NiO-210-350nm

(111), (200) and (222) reflections

corresponding to the cubic structure of NiO 45

T, %
thin films. 30

3
5x10 15
Intensity, arb.un

3
4x10
3
0
3x10 400 600 800 1000
(111)

3
2x10 λ, nm
3
(200)

1x10
(311)
(222)

Fig. 3 Transmission spectra of NiO thin films deposited at

150
I
nm different thicknesses
I 200 nm

I
250 nm The transmittance of the films varies
I
300 nm between 25% and 50% (the maximum of
I
350 nm 50% is for the film with 200 nm). The
10 20 30 40 50 60 70 80
2θ, degree differences in the shape of the transmittance
envelope are due to differences in film
Fig. 2 The XRD patterns of NiO thin films deposited at 210 thickness. The optical band gap of the films
W sputtering power with different thicknesses.
was estimated by using the relation (αhν)2
The full width at half-maximum (FWHM) =A(hν−Eg), where hν is the photon energy,
decreased with increasing the film thickness, Eg is the optical band gap and A is a constant
indicating that the crystallinity and grain size which does not depend on the photon energy
were enhanced with the film thickness. For [7]. The optical band gap of film is
the 150 nm film, the surface consisted of determined from the extrapolation of the
small grains with size of 27.35 nm. At the linear plots of (αhν)2 versus hν at α=0
350 nm thickness of the NiO thin film, grain illustrated in Figure 4. α is the absorption
size reached 30 nm. coefficient. In the case of varying the
thickness of the films at 210 W sputtering
B. Optical properties power, the curves of NiO with 150 nm and
The optical transmission spectra of the NiO 200 nm of plots of (αhν) 2 versus hν overlap,
thin films with different thicknesses are the Eg values are 3.48 eV. For NiO films
shown in Fig. 3. The transmittance of NiO with 250 nm 300 nm and 350 nm thicknesses
thin films increases with the increasing of the Eg equal to 3.43 eV…3.45 eV. The estimated
film thickness and the positions of the values of the band gap were relatively lower
interference peaks slightly change within the in comparison with 3.78 eV reported by
other authors [8, 9]. The direct band gap
values when the thickness varies from 250
nm to 350 nm are changing in the interval of
the experimental errors (0.02 - 0.03 eV).
Fig. 4 Dependence (αhν)2 = f(hν) of NiO thin films
deposited at 210 W RF power with different
thicknesses
The decrease of band gap values with
increasing the thickness could be attributed
to the increase in localized density of states
near the band edges and in turn decreases the
value of Eg with thickness [10].
Conclusion
The technological regime used in the
fabrication of NiO by the RF magnetron
sputtering method allowed us to obtain
uniform and higher quality thin films. XRD
studies reveal that the films exhibit cubic
structure with preferred orientation along
the (111) plane. The structural and optical
properties of the NiO thin films have been
found be influenced by the thickness of the
film. The optical transmittance of the films
decreases from 50% to 25%, while the
optical energy band gap of the films
decreased slightly from 3.48 eV to 3.43 eV
with increasing film thickness from 150 nm
to 350 nm. Remarkably, our thickness
dependence study of sputtered NiO films
indicate the optimum thickness for the better
structural and optical properties. We believe
that these sputtered undoped NiO films
would find its feasible applications in
optoelectronic devices.
Acknowledgments
The authors thank the Ministry of Education,
Culture and Research of Republic of
Moldova for funding the grant
15.817.02.08A.
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