Preface

Nanostructured materials are single phase or multi-phase polycrystals, the crystal size
of which is of the order of a few nanometers (typically 1 - 100 nm) in at least one dimension.
Nanostructured materials may contain crystalline, quasicrystalline or amorphous phases and
can be metals, semiconductors, ceramics or composites. These materials often show properties
vastly superior to those exhibited by single crystals, conventional coarse-grained polycrystals
and amorphous materials. More importantly, it has been observed that in the nanosize regime,
the physical and chemical properties of materials depend strongly on the average grain size.
Synthesis ofnanostructured materials and investigation oftheir exquisite properties is presently
one of the most active and emerging fields of materials research. Though nanostructured
samples of a wide range of materials have been synthesized and meticulously characterized, the
field still offers much scope for innovative experimental and theoretical work.
Nickel oxide is an important material due to its interesting electrical, optical and
magnetic properties, which find application in diverse fields such as smart windows, active
optical fibers, electrochromic displays and temperature sensors. The thesis entitled 'Synthesis
and Characterization of Nanostructured Nickel Oxide' is a detailed account of synthesis of

nanostructured nickel oxide samples having different average grain sizes ranging from 2-3 nm
to 18 nm and the study of their properties using different experimental techniques.
The thesis is divided into ten chapters. Chapter I is a general introduction to the field
of nanostructured materials. Details of synthesis of the samples of nanostructured nickel oxide
having different average particle sizes and the determination of the average grain sizes are
given in Chapter 2.
In Chapter 3, the study of dc conductivity of nanostructured nickel oxide is presented.

The observed enhancement of the dc conductivity of the samples in comparison with the
conductivity of single crystalline nickel oxide is attributed to the high density ofNi 2+ vacancies
primarily associated with the interfacial region of the nanostructured samples. A semiquantitative explanation for the observed variation of dc conductivity with average particle size
is presented taking into account the contributions due to grain boundaries and triple junctions.
Chapter 4 contains the details of the study of ac conductivity of the samples. The
experimentally observed dependence of ac conductivity on the frequency of the applied signal
and temperature is discussed on the basis of the Correlated Barrier Hopping (CBH) model. The
dependence of the ac conductivity on the particle size is also explained.

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The study of the variation of the real and imaginary components of the complex
dielectric function, E*, of nanostructured nickel oxide samples with the frequency of the applied
signal and temperature is presented ia Chapter 5. The dielectric relaxation mechanism, and the
frequency and temperature dependence of the real and imaginary components of E* are
discussed in the light ofthe 'Universal model' of dielectric response.
Chapter 6 contains Ni 2p XPS studies of the nanostructured nickel oxide samples. The
experimentally observed features in the photoelectron spectra of the samples are explained
based on Nh036 cluster model. This study underlines the importance of factors such as actual
local environment of the core hole site, and density and distribution of defects in determining
the core level X-ray photoelectron spectra of nanostructured nickel oxide.
FTIR spectroscopic studies of the samples in the far IR region are presented in
Chapter 7. The spectra are found to be dominated by surface modes. The effect of crystallite
geometry, numerical values of optical constants, filling factor and increased damping on the
spectral features are analyzed in detail by simulating the IR spectrum employing a macroscopic
approach.

Though the simulations approximately reproduced some of the features in the

experimental spectra, the most intense peak in the simulated spectra is found to be about

50 cm- 1 on the higher wavenumber side of the corresponding experimentally observed peak.
The experimentally observed absorption maxima of all the samples are in close agreement with
that determined using a microscopic theory based on the rigid ion model.
Chapter 8 presents the static magnetization behavior of the samples at room
temperature studied using vibrating sample magnetometer.

The sample with an average

particle size of 2-3 nm is found to be superparamagnetic while those with larger average
particle sizes exhibit superantiferromagnetism.
The study of antiferromagnetic resonance (AFMR) in the nanostructured nickel oxide
samples in the far IR region is presented in Chapter 9. A new resonance peak observed in the
spectra of samples with relatively smaller average particle sizes appearing at the lower
wavenumber side of the bulk AFMR peak is explained as a surface mode which becomes
observable due to the large surface to volume ratio of the nanostructured samples.
Chapter 10 gives a summary of the conclusions drawn from different experimental
analyses conducted in the present study.

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A major part of the work included in this thesis has been published/accepted for
publication in journals or presented at conferences/se:ninars.

Research papers published / accepted for publication in journals

1.

DC conductivity of consolidated nanopartic1es ofNiO.

V. Biju and M. Abdul Khadar, Materials Research Bulletin 36 (2001) 21-33.

2.

Analysis of AC electrical properties of nanocrystalline nickel oxide.

V. Biju and M Abdul Khadar, Materials Science and Engineering A 304-306
(2001) 814-817.

3.

AC conductivity ofnanostructured nickel oxide.

V. Biju and M. Abdul Khadar, Journal of Materials Science 36 (2001) 57795787.

4.

Electronic structure of nanostructured nickel oxide using Ni 2p XPS analysis.

V. Biju and M. Abdul Khadar, Jounal ofNanopartic1e Research (2002) (in press).

5.

Fourier transform infrared spectroscopy study ofnanostructured nickel oxide.

V. Biju and M. Abdul Khadar, Spectrochimica Acta Part A (2002) (in press).

Research papers presented at conferences/seminars

1.

Analysis of AC electrical properties of nanocrystalline nickel oxide.

V. Biju and M. Abdul Khadar, 10th International Conference on Rapidly Quenched
and Metastable Materials August 23- 27, 1999, Indian Institute of Science,
Bangalore.

2.

AC conductivity of nanostructured nickel oxide.

V. Biju and M. Abdul Khadar, Conference on Physics of Nanophase Materials,
December 18- 20, 2000, University of Pune, Pune.

3.

Complex dielectric studies ofnanostructured nickel oxide.

V. Biju and M. Abdul Khadar, National Seminar on Current Trends in Materials
Science CTIMS- 2001, March 23- 24, 2001, School of Pure and Applied Physics,
M. G. University, Kottayam.

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4.

Core level photoelectron spectra of nano structured nickel oxide.

V. Biju and M. Abdul Khadar, National Seminar on Spectroscopy, Optoelectronics
& Non- Destructive Evaluation SPENDE- 2001,May 25- 26, 2001, Department of
Optoelectronics, University of Kerala, Trivandrum- 695 581.

5.

FTIR study of surface modes in nanostructured nickel oxide.

V. Biju and M. Abdul Khadar, National Seminar on Solid State Spectroscopy
(NSSSS- 2001), August 29- 31, 2001, Department of Physics, Sri Venkateswara
University, Tirupati under UGC-DRS Programme.

6.

Ni 2p X-ray photoelectron spectroscopy ofnanostructured nickel oxide.

V. Biju and M. Abdul Khadar, National Seminar on Solid State Spectroscopy
(NSSSS- 2001), August 29- 31, 2001, Department of Physics, Sri Venkateswara
University, Tirupati under UGC-DRS Programme.