Chapterlo Conclusion

ChapterlO
Conclusion
10
CONCLUSION
In the present work, nanostructured nickel oxide samples having different

average grain sizes ranging from 2-3 nm to 18 nm were synthesized and their physical
properties were studied using different experimental techniques. For synthesizing
nanostructured nickel oxide, a two-step process involving controlled precipitation of
carbonate precursor followed by thermal decomposition and high temperature
annealing was employed.
The crystal structure and average grain size of the
nanostructured samples were determined using X-ray diffraction analysis. The particle
size obtained from Transmission Electron Micrograph of the nanostructured nickel
oxide sample of smallest average grain size agreed with the grain size estimated from
the XRD analysis.
DC and AC conductivity of nanostructured nickel oxide samples having
different average grain sizes ranging from 2-3 nm to 16-17 nm was found to be larger
by six to eight orders of magnitude than that of undoped NiO single crystal reported in
the literature. The large enhancement in the conductivity was attributed to the high
+
concentration of Ni2 vacancies primarily associated with the large volume fraction of
the defective interfacial region of the nanostructured samples. The dependence of ac
conductivity of the nanostructured samples on the frequency of the applied signal and
temperature was discussed on the basis of the Correlated Barrier Hopping (CBH)
model. The observed variation of DC and AC conductivity with average grain size of
the sample was explained by considering the combined effects of the grain boundaries
and triple junctions on electrical transport in nanostructured nickel oxide. The results
of the above studies lead to the conclusion that for nanostructured materials having
164
small average grain sizes (<10 nm), in addition to the grain boundaries, triple junctions
which form a very important constituent of the interfacial region play a significant role
in detem1ining the transport properties.
Dielectric dispersion in nanostructured nickel oxide samples having different
average grain sizes was studied as a function of frequency of the applied signal at
different temperatures. The dielectric relaxation mechanism was discussed considering
nanostructured nickel oxide as a carrier dominated dielectric with high density of
hopping charges. The observed ro
-I
dependence of the real and imaginary components
of E* was explained in the light of the 'Universal' model of dielectric response.

Ni 2p X-ray photoelectron spectra of nanostructured nickel oxide samples with
two different average grain sizes, viz., 2-3 nm and 16-17 nm were recorded. The most
important and striking features of the spectra of both the samples were the broadening
of the main line and large increase in the relative intensity of the satellite structure at
- 1.5 eV high binding energy side of the main line. Both these features were explained
on the basis of Ni7036 cluster calculations as due to an enhancement in the non-local
screening process in the nanostructured samples in comparison with the bulk NiO
crystals.
FTIR spectra in the far IR region of nanostructured nickel oxide samples having
different average grain sizes were found to be dominated by surface mode absorptions.
Infrared absorption coefficient, a, for nanostructured nickel oxide samples were
calculated as a function of frequency using a macroscopic approach. The effects of
optical constants, crystallite geometry, filling factor and increased damping on the
spectral features of the samples were analyzed. An analysis of simulated spectra
revealed that spectral simulations with a filling factor f = 0.1 and for cubical geometry
approximately reproduce the occurrence of a shoulder in the frequency region
- 530 - 550 cm- 1, though the position of the most intense absorption peak estimated
from these simulations lie almost 50 cm- 1 above the -experimentaliy observed
absorption maxima. It was shown that the experimentally observed sorption maxima
of the samples were in close agreement with those estimated according to a
165
microscopic theory based on the rigid ion model. It was inferred that for explaining the
spectral features of the nanostructured nickel oxide samples with very small average
particle sizes - 10 nm or less, the macroscopic approach alone is not sufficient and one
has to consider the microscopic approaci1 which takes into account the contributions
due to the large surface area to volume ratio of the crystallites at these size scales. The
weak absorption peaks in the frequency range 60 - 100 cm- 1 appearing in the spectra of
all the four samples were identified as the surface induced transverse acoustical modes,
corA, which become IR active due to the breakdown of translational symmetry in the
nanocrystallites.
Magnetic hysteresis of nanostructured nickel oxide having three different
average grain sizes were recorded at room temperature. The magnetic properties of
nickel oxide nanoparticles in this size range are markedly different from those of bulk
NiO crstals. It was observed that nanostructured nickel oxide sample with an average
grain size of 2-3 run was superparamagnetic with the magnetization curve defined by
the Langevin function.
Anomalously large uncompensated magnetic moment
associated with this sample was attributed to the multisublattice magnetic structure.
Samples with relatively larger average grain sizes of 12-13 nm and 18 nm exhibited
superantiferromagnetism with the magnetization curves varying linearly with applied
field and susceptibility values larger than that of single crystalline nickel oxide. The
remarkable change in the magnetization behavior of the nanosteructured nickel oxide
samples with change in the average grain size emphasized the importance of the surface
atoms and surface driven spin rearrangements in determining the magnetic property of
nanostructured nickel oxide.
Antiferromagnetic resonance (AFMR) of nanostructured nickel oxide samples
in the far infrared region was studied using Fourier Transform Infrared Spectroscopy
technique for different average grain sizes ranging from 2-3 nm to 16-17 nm. The well
defined absorption peak around 34 - 35 cm- 1 present in the spectra of all the samples
was attributed to the bulk AFMR. The low frequency absorption peak in the region 20
- 30 cm- 1 in the spectra of samples with relatively smaller average grain sizes of 2-3 nm
and 5-7 run was identified as a surface mode. The evolution of the spectral features
166
with change in average grain size of the samples was explained as due to the change in
the volume fraction of the surface atoms.
The results of thepresent study on nanostructured nickel oxide samples of
different grain sizes show that the physical properties of nickel oxide are drastically
altered on nanostructuring. Moreover, in the nanosize regime, the physical properties
of nickel oxide depend strongly on the average grain size. Also, the work highlights
+
the importance of the grain size, concentration of Ni2 vacancies, large surface area to
volume ratio, triple junctions, surface driven spin rearrangement, etc., in determining
the different properties of nano structured nickel oxide.

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Chapterlo Conclusion

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ChapterlO

In the present work, nanostructured nickel oxide samples having different

The crystal structure and average grain size of the

dependence of the real and imaginary components

of E* was explained in the light of the 'Universal' model of dielectric response.

Anomalously large uncompensated magnetic moment

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