Chapter-1

Introduction

The elements in the periodic table have been classified into four blocks which are named
as s, p, d and f. Among them, transition metals are considered as d block element. These metal
elements have the ability to exhibit variable oxidation states. Their interaction with oxygen
anions forms a group of oxide materials which could be found within one complex structural
family such as perovskite, spinel, wurtzite, rutile etc. They show different kinds of physical
properties such as optical, electrical, magnetic, transport etc. along with good hardness, high
thermal stability and chemical resistance [1]. Among the group of Transition metal oxides,
ferrites have studied a lot over a decade owing to its excellent electric, dielectric and magnetic
properties. Ferrite materials are insulating/semiconductor metal oxides. Generally, it exhibits
moderate saturation magnetization, moderate coercivity, low electrical resistance, low eddy
current and dielectric loss with moderate permittivity [2-6]. Ferrites are classified into three
categories depending on its crystal structure. They are named as garnet, hexagonal and spinel
ferrite. Garnets have strong applications in microwave systems. Its general formula is M 3+Fe5O12
where M stands for trivalent cations such as Y, Sm, Eu, Gd, Tb etc [7]. The hexagonal ferrites
are represented by the general formula Me2+Fe12O19 where M stands for divalent cation such as
Ba, Sr, Ca etc. [8]. The spinel ferrites are represented by the general formula MFe2O4 where M is
the divalent cation M = Co, Mn, Zn, Ni, Cd etc [9]. These materials over a decade have been
explored for vast applications in various fields like transducers, activators, recording media,
permanent magnets, microwave devices, transformer core, computer technology, biomedical
application etc [10-13]. The spinel ferrites exhibit dielectric properties and do not conduct
electricity easily. Therefore ferrites became an alternative for the metal magnets like iron, nickel
which conduct electricity readily [14]. Hence, ferrites are extensively used in high-frequency
application. The interesting feature of these ferrite materials is, its properties can be modified by
tailoring its chemical composition without altering its crystal structure. Hence, the processing of
these materials is important in order to get desired properties for applications. Among the ferrite
family, spinel ferrite (MFe2O4) has received considerable attention in scientific community due
to its promising magnetic, electrical and dielectric properties. These materials cover a wide range
of technological application such as microwave devices, high-density magnetic information

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storage, biomedical applications, sensors etc. A review of ferrite materials with spinel structure,
its properties and brief literature review on nickel ferrite has been presented in this chapter. The
motivation and objective of the present work has been outlined at the end of this chapter
1.1. Spinel Ferrites
The compound MgAl2O4 is known as spinel. Any material whose crystal structure is
similar to compound spinel is regarded as spinel structured material which is represented by a
general formula AB2O4 where A and B stands for metal cations. The compound ferrites
crystallize to spinel structure possessing cubic symmetry is termed as spinel ferrite. The one unit
cell of spinel ferrites consists of 8 formula unit i.e. 56 ions. Out of 56 ions, there are 32 oxygen
anion which are closed packed in such a way that it give rise to 96 interstitial sites. Out of 96
interstitial sites, there are 64 tetrahedral sites (called A-site) and 32 octahedral sites (called B-
site). Out of 64 tetrahedral and 32 octahedral sites, only 8 and 16 sites are occupied by divalent
and trivalent metal cation. Hence, large numbers of interstitial sites remain empty which is
conducive for cation migration inside the structure. The interesting feature of this compound is
that its physical properties depend upon the cation distribution without any change in its crystal
structure. On the basis of occupancy of cations at A-sites (i.e. tetrahedral site) and B sites (i.e.
octahedral site), the spinel ferrites are classified as normal, inverse and random spinel ferrite. In
the normal spinel structure, the 8 divalent metal ions go into the A sites, and the 16 trivalent
metal cations have preference for B sites. In inverse spinel all the divalent ions are on B-site and
the trivalent ions are equally divided between A- and B-sites. If divalent and trivalent cations are
present on both A and B site, it is termed as mixed spinel. Hence the general formula of spinel
ferrite on the basis of cation distributions can be represented
as where δ depends on the preparation technique and
annealing temperature. Here δ = 1 for normal spinel ferrites, δ = 0 for inverse spinel ferrites, and
for mixed spinel ferrites the value of the δ lies between 0 and 1[7, 9, 15]. A remarkable
characteristic of spinel structure is its ability to form wide range solid solutions. It means that the
composition of a particular ferrite can be strongly modified, while the basic crystalline structure
of the material remains the same. An example is the Zn-Ni system, with general formula
ZnxNi1-x Fe2O4, where 0 ≤ x ≤ 1. In this example, the two extreme end is NiFe2O4 (for x = 0) and
ZnFe2O4 (x = 1) respectively. NiFe2O4 corresponds to inverse spinel whereas ZnFe2O4 leads to
normal spinel structure. The physical properties of these two compounds are very different to

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each other. NiFe2O4 is ferrimagnetic oxide with a Curie temperature around 858 K, whereas
ZnFe2O4 possesses anti-ferromagnetism, with Neel temperature around 9 K [16]. This means that
the general properties of the ferrite can be easily “tailored” just by varying the composition. The
cation distribution in spinels was an interesting problem for some time; currently, it has been
established that it depends essentially on various factors. First the elastic energy (the lattice
deformation produced by cation radii differences) has to be considered. It refers to the degree of
distortion of the crystal structure, as a result of differences in dimensions of the several cations
within the specific spinel. Generally, there is tendency that smallest site i.e tetrahedral site is
occupied by smaller cations while larger cations occupy octahedral sites which is larger than
tetrahedral sites. However, trivalent cations are generally smaller than divalent ones, leading to
some tendency to the inverse structure. In general, divalent ions are larger than trivalent ions.
The nuclei of trivalent cation exhibits stronger electrostatic attraction. As an effect, their electron
orbits contract. The octahedral sites are larger than the tetrahedral sites and, thus, the divalent
ions are localized in the octahedral sites, whereas trivalent ions are in the tetrahedral sites [16].
The next factor to be considered is electrostatic energy (Madelung energy), which has to do with
the electrical charge distribution. In a simple way, cations with high electrical charge should
occupy the sites with larger coordination number (octahedral), and cations with smaller valency
should be more stable when occupying the tetrahedral sites. Another very important factor is
crystal field stabilization energy which determines the site preference for cations. This energy is
associated with the geometry and arrangement of d orbital’s within the crystal structure. The
degeneracy of the five d orbitals is lifted and it leads to splitting due to the distribution of electric
field which is established by anions on the particular site of the crystal. The energy difference is
due to electrostatic repulsion between the orbitals of the surrounding p orbital’s of anions and the
d electrons. The above discussion can be summarized as; the cations preference over interstitial
sites is determined by ionic radius of the cation, radius of the interstitial sites and orbital
preference for specific coordination. There exist two kinds of structural symmetries inside the
crystal structure of spinel ferrite. It is determined by the factors such as size and charge of the
metal ions, which ultimately balance the oxygen anions charge and their relative amounts [16].
In one unit cell, there are 32 oxygen ions, which are arranged in a close packed array leading to
64 tetrahedral and 32 octahedral sites respectively. The positive charge would be very much
greater than the negative charge, if all of these were filled with metal ions, of either +2 or +3

3
valence leading to electrically non-neutral structure. Hence in order to satisfy charge neutrality
out of 64 tetrahedral sites, only 8 are occupied whereas out of 32 octahedral sites, only 16 are
filled. For example, let us take the case of normal spinel ferrite where divalent and trivalent
cations occupy tetrahedral octahedral sites respectively. Therefore the total positive charge can
be expressed as 8x (+2) = (+16) + (16x +3) = +48 = +64. It requires the negative charge
32x (-2) = -64 (for the oxygen ions) to balance the net positive charge. Above argument conclude
that eight formula units of MO.Fe2O3 or MFe2O4 would be present in a one unit cell. The O
atoms in the spinel structure are not generally located at the exact position of the sub lattice.
Their details position is determined by a parameter u, which reflects adjustment of the structure
to accommodate differences in the radius ratio of the cations in the tetrahedral and octahedral
sites. The oxygen position parameter is represented by u. Its value is reported to be 0.375 for an
ideal spinel structure [7, 9, 15].

Fig 1.1: Crystal structure of a cubic spinel ferrite

The ideal situation is almost never realized, and u value of the vast majority of the known spinels
ranges between 0.375 and 0.385. Interatomic distances are given as a function of the unit cell
parameter a and u parameter which is listed in table 1.1 [7, 9, 15, 17].

The average radius of the cations affects primarily the lattice parameter (a), while the
ratio between the tetrahedral and octahedral cation radius determines mainly the oxygen
positional parameter (u) value. If the lattice parameter is taken as a weighted average of the

4
projections of the octahedral and tetrahedral bond lengths in the unit cell, the lattice parameter
can be expressed as [7]

(1.1)

Above expression, accounts for 96.7 % of the variation in the lattice parameter of 149 spinel
oxides [7]. The separation of atoms between A-A (tetrahedral) sites, B-B (octahedral) sites and
A-B sites, the radius of interstitial sites and deformation factor u in spinels AB2O4 compound
depends on a unit cell edge “a” which has been expressed in Table 1.1.

Table 1.1: Interatomic distance as a function of unit cell edge a and deformation factor u

Tetra – Tetra Separation (A-A)

Tetra – Octa Separation (A-B)

Octa – Octa Separation (B-B)

Tetra – O Separation (A-O)

Octa – O Separation (B-O)

Tetrahedral Radius

Octahedral Radius

Physical properties of the spinel ferrites not only depend on the kinds of cation present on the
lattice but also their distribution over the crystal sites. So it is important to know the factors
influence the site occupancy. However, the prediction of the distribution of cations over the
interstitial sites is an interesting and challenging problem in crystal chemistry. According to the
crystal field theory, the charge density of the d orbital’s (shown in Fig 1. 2) interacts with the

5
charge distribution of the environment in which the transition ion placed. The five d orbital’s dxy,
dyz, dzx, dz2 and dx2-y2 split according to the symmetry of the electrostatic field produced by the
anions of the particular lattice site. The physical basis for the splitting of ‘d’ orbitals is the
electrostatic repulsion between the d electrons and the electrons of the orbitals of the surrounding
anions [18]. The energy level of the d orbital splits into two groups in an octahedral field. The
lower triplet formed by the dxy, dyz, and dzx orbital’s, and a higher doublet with the dz2 and dx2-y2
(shown in Fig 1.4). The energy of the doublet is increased as these orbital’s points directly to the
anions while the triplet energy decreases because the orbital’s point to regions of low electron
density. The energy difference between the triplet and the doublet is given as ∆. The splitting is
reversed in case of tetrahedral sites. Therefore doublet has the lower energy in comparison to
triplet. The energy difference in tetrahedral environment is a fraction (4/9) of that for the
octahedral environment [18]. In ferrites, the arrangement is dependent on the divalent cation
because Fe3+ has no crystal field stabilization energy. When the divalent cation has also no clear
preference, then δ value takes in between the zero and one. According to Hund’s law, an
electronic state with the higher spin state are the most stable so the high spin states like d1, d2, d3
especially d3 (Cr3+, Mn4+, V2+) occupy the octahedral site.
The half-filled d orbital’s (Mn2+, Fe3+) in the high spin state have d5 spherical configuration with
no particular preference for either coordination. The degree of inversion δ is not exactly zero for
many ferrites. The mechanism of redistribution of the cation is a more complex process. It can be
significantly affected by the presence of Fe2+ [18].

Fig 1.2: Transition metal cation in an octahedral field [16]. Fig 1.3: Spatial geometry of d
orbitals of spinel [18].

Spinel ferrites are well-known ferrimagnetic materials that consist mainly of ferrimagnetic
oxides and, therefore, are electrically insulating. Ferrites are widely used in high-frequency

6
applications because an alternating current (AC) field does not induce undesirable eddy currents
in an insulating material [19, 20]. Ferrites are generally magnetic ceramics possessing the
property of ferrimagnetism. It is a derivative of iron oxides as well as oxides of other metals. It is
usually non-conductive. Like most other ceramics, ferrites are hard and brittle. It is extensively
used in devices which work on high-frequency because in an insulating material an AC field is
unable to induce undesirable eddy currents. Based on the response to the applied magnetic field,
ferrites are classified as soft and hard ferrites as shown in Fig 1.5.

Fig 1. 4: Energy level diagram for‘d’ level splitting in crystal field [19].

1.2. Soft Ferrites

Soft ferrites exhibit a low value of coercivity. They yield low hysteresis loss at high
frequency. They are widely used in electromagnetic cores of transformers, switching circuits in
computers and radio-frequency (RF) inductors, e.g. lithium ferrite, nickel ferrite and manganese–
zinc ferrite [19].

Fig 1.5: Hysteresis loop for (a) soft and (b) hard ferrites

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1.3. Hard Ferrites
The ferrites having comparatively high coercivity (2 kOe or higher) are called as hard
ferrites. The high coercivity means the materials are very resistant to becoming demagnetized, an
essential characteristic for a permanent magnet. Hard ferrites exhibit a large value of retentivity
and coercivity after magnetization. They also have high magnetic permeability and there find
applications as permanent magnets, magnetic data storage devices, loudspeaker, an automotive
system, and so on, as permanent magnets. Fig 1. 5. (b) Shows a representative M-H loops of soft
and hard ferrites. Hard- Barium ferrite (BaFe12O19) and cobalt ferrite (CoFe2O4) are some
typical examples of hard ferrite. Iron oxide and barium or strontium carbonate are used in the
manufacturing of hard ferrite magnets [19].
1.4. Electrical properties of ferrites
Spinel ferrites compound have low electrical conductivities when compared to other
magnetic materials and hence they find wide range of frequency such as microwave frequencies.
Spinel ferrites, in general, are semiconductors with their conductivity lying in between 102 and
10-11 Ohm-1 cm-1. The conductivity is due to the presence of Fe2+and the metal ions (Me3+). In the
presence of Fe2+ ion results in n-type behavior and Me3+ in p-type behavior. The conductivity
which is arises due to the mobility of the extra electron or the positive hole through the crystal
lattice. The movement is described by a hopping mechanism, in which the charge carriers jump
from one ionic site to the other. In such a process the mobility of the jumping electrons or holes
-E/kT
are found to be proportional to e where E is the activation energy, k is Boltzmann’s
constant, T is the temperature in degree absolute. The dielectric property of ferrite is important
to physicists. These properties are strongly dependent on frequency, orientation, pressure and
molecule structure of the material. A material is said to be dielectric if it has the ability to store
energy when an external electric field is applied. If an ac sinusoidal voltage source is placed
across the same capacitor, the resulting current will be made up of a charging current and a loss
current that is related to the dielectric constant. Here we are interested only in the dielectric
constant (K) of the material and the loss (tanδ). Dielectric constant (K) describes the interaction
of a material with an electric field. The relative dielectric constant is given by equation Kr =ε/ ε0
the complex relative dielectric constant is given by

8
 (1.2)

where ε0 is the dielectric constant of free space, which is equal to 8.854 x 10-12 f/ m.The real
part of dielectric constant (Kr) is a measure of how much energy from an external electric field is
stored in a material. The imaginary part of the dielectric constant (K'') is called the loss factor
[21-30]. Any material that supports charge without conducting it to a significant degree is
known as a dielectric material. These materials are electrical insulators that can be polarized by
an applied electric field. Dielectric materials are the building blocks of functional electronic
circuits, capacitors, gate dielectrics, and transmission lines. The dielectric properties of materials
are used to describe electrical energy storage, dissipation, and energy transfer. One of the
important electrical properties of dielectric materials which are generally referred to as the
dielectric constant. For most materials, the dielectric constant is independent of the electric field
strength, below a certain critical field. The dielectric constant depends strongly on the frequency
of the alternating electric field or the rate of change of the time-varying field. It depends on the
chemical structure and the imperfections (defects) of the material, as well as on other physical
parameters including temperature and Frequency etc [21-30].
1.4.1. Dielectric phenomenon in static electric fields
It will be useful to consider first the much simpler mechanism of electric polarization in
the static electric field. From the basics of electrostatics and the Gauss’s law, one can explain the
dielectric phenomenon resulting from the electric polarization. Consider a simple system
consisting of two parallel metal plates each with an area A and separation d, which is much
smaller than the linear dimension of the plates. The system is connected to a steady AC voltage
supply which introduces a positive charge +Q and a negative charge –Q of the same magnitude
on the two plates. These charges on the plates will create a potential difference V between the
plates that is proportional to Q. Thus, the relation can be written as:

(1.3)

(1.4)

where C is the proportionality constant, generally called the capacitance. By denoting the surface
charge density on the plates as  s, the charge Q can be expressed as

A (1.5)

9
where E is the electric field strength, which is simply equal to V/d.

(1.6)

(1.7)

where ɛ is the permittivity or dielectric constant of the material filled between the two plates, and
equal to the ratio [21-30].

1.4.2. Dielectric Phenomenon in Time-Varying Electric Fields

In the previous section, the static response of dielectric materials under static electric
fields has been discussed. However, the dynamic response under time-varying electric field
provides much more information about the structure of the material and its dielectric behavior for
fundamental studies, as well as for technological applications. When a time-varying electric field
is applied across a parallel-plate capacitor with the plate area of one unit and a separation of d
between the plates, then the total current is given by

(1.8)

where J is the conduction current density and ɛ* is the complex permittivity, which is introduced
to allow for dielectric losses due to the friction accompanying polarization and orientation of
electric dipoles. This may be written as,

(1.9)

in which e is called the dielectric constant and Kis the loss factor.
An arbitrary time-varying field can be resolved into sinusoidal AC fields of a spectrum of
frequencies by means of the Fourier transformation. For simplicity
(1.10)

Substitution of eqns. 1.8 and 1.9 into eqn. 1.7 yields

(1.11)

where  is the electrical conductivity of the material (see the equivalent circuit depicting the
response of the parallel plate capacitor shown in Fig 1.6 ). The first term on the right (in eqn.
1.10) is a loss component due to the inelastic scattering of conducting charge carriers during their

10
migration, which is present at all frequencies, including   0 (AC fields). The second term (eqn.
1.10) is also a loss component due to the friction in the polarization processes, which disappears
when   0 and the third term is a lossless component which is, in fact, the displacement current
[21-30].

Fig 1. 6: The response of a parallel plate capacitor with unit plate area and its equivalent circuit
under an alternating electric field.

For dielectric materials,  is normally very small, and the contribution of the first term can be
neglected. By ignoring the first term, the tan δ is given by

= (1.12)

which is generally called the loss tangent, as shown in figure 2.3. If / << 1 then

(1.13)

This is generally called the loss angle.

1.4.3. Various Types of Electrical Polarization
Electric polarization (P) refers to a phenomenon of the relative displacement of the
negative and the positive charges of atoms or molecules, the orientation of existing dipoles
toward the direction of the field, or the separation of mobile charge carriers at the interfaces of
impurities or other defect boundaries, caused by an external electric field. Therefore, electric
polarization can also be thought of as charge redistribution in a material caused by an external
electric field. The work done for charge redistribution and the energy loss involved in the
redistribution process requires energy [21-30]. The polarization process is performed at the
expense of the potential energy released from this process because the total potential energy of
the system in an electric field is smaller after electric polarization than before it. Typically, the

11
polarization produced in a dielectric material is approximately proportional to the applied electric
field E (as long as E is not too strong):
P= (1.14)
The constant of proportionality  is called dielectric polarizability of the material. The various
mechanisms of electric polarization in a dielectric medium (low conducting at moderate fields)
can be categorized as:

1. Electronic polarization,
2. Atomic or ionic polarization,
3. Dipolar or orientational polarization,
4. Spontaneous polarization,
5. Interface or space charge polarization.

As each type of polarization requires time to perform, the degree of the overall polarization
depends on the time variation of the electric field as shown in Fig 1.7 [21-30]. The polarization
due to the elastic displacement of electron cloud of atoms and molecules requires a very little
time, while the polarization involving the orientation of permanent dipoles or the migration of
electrons or ions, and requires a much longer time to perform. All types of polarization encounter
inertia, counter acting the change and involve some dielectric loss.
1. Electronic polarization (also called optical polarization): It arises when the electric field
causes deformation or translation of the originally symmetrical distribution of the electron cloud
of atoms or molecules. This is essentially the displacement of the outer electron cloud with
respect to the inner positive atomic core.
2. Atomic or ionic polarization: It arises when the electric field causes the atoms or ions of a
polyatomic molecule to be displaced relative to each other. This is essentially the distortion of
the normal lattice vibration, and this is why it is sometimes referred to as vibrational
polarization.
3. Orientational polarization: It occurs only in materials consisting of molecules or particles
with a permanent dipole moment. The electric field causes the reorientation of the dipoles toward
the direction of the field.
4. Space charge polarization: The induced electronic, atomic and orientational polarization
discussed above are due to the bound positive and negative charges within the atom or molecule
itself, which are linked intimately to each other and which normally cannot be separated.
However, the electric polarization can also be associated with mobile and trapped charges. In this

12
case, there is a migration of charge carriers to form space charges at interfaces or grain
boundaries. This type of polarization is called the space charge polarization.
The electronic polarization is always present in atoms or molecules of all kinds; ionic
polarization is present only in materials consisting of two or more different kinds of atoms that
form ions due to the sharing of the valence electrons of one or more atoms with the others. For
both electronic and ionic polarizations, the dipole moments are induced by electric fields, so they
are classified as induced dipole moments. In short, both electronic and ionic polarizations are due
to the translation (or deformation) of the valence electron cloud from its original thermal
equilibrium state to a new equilibrium state.

Fig 1.7: Variation of polarization as a function of applied AC field

These types of polarization are only slightly dependent on temperature because they are
intramolecular phenomena. However, orientational polarization occurs only in the materials
composed of molecules with an asymmetrical structure in which the centroid of the negative
charge (mainly electrons) and that of the positive charge (mainly nuclei) are not coincident, so
they possess permanent dipole moments in the absence of external fields. The directions of these
permanent dipole moments are randomly distributed in the material. An electric field will cause
them to reorient toward the direction of the field, resulting in orientational polarization. The net
polarization will return to zero after the removal of the external field because thermal agitation

13
tends to randomize the alignment. This is why orientational polarization decreases with
increasing temperature and Frequency.

The total polarizability of a material comprises four components [21-30],

+ + + (1.15)

where and are the polarizabilities due to electronic, atomic, orientational, and
space charge polarizations, respectively.
Charge carriers (electrons, holes, or ions), which may be injected from electrical contacts,
may be trapped in the bulk or at the interfaces, or may be impeded to be discharged or replaced
at the electrical contacts leads to the formation of space charge in polycrystalline solids. In these
materials there are two possible ways by which space charge polarization can take place i.e.
hopping polarization and interfacial polarization.
1.4.4. Hopping polarization
In a dielectric material, localized charges (ions and vacancies, or electrons and holes) can
hop from one site to the neighboring site, creating so-called hopping polarization. These charges
are capable of moving freely from one site to another site for a short time, then becoming trapped
in localized states and spending most of their time there. Occasionally, these charges also make a
jump surmounting a potential barrier to other sites. In fact, the movement of ions or vacancies in
ionic crystals and the movement of electrons and holes in glasses and amorphous semiconductors
are due to the hopping process [21-30].
1.4.5. Interfacial polarization
Interfacial polarization is produced by the separation of positively and negatively charged
mobile particles under an applied field, which form positive and negative space charges in the
bulk of the material or at the interfaces between different materials. These space charges, in turn,
modify the field distribution. This is also relevant for composite dielectric like a specimen
comprising layers of different materials. The polarization of this kind is basically a classical
Maxwell - Wagner two-layer systems [24].
1.4.6. Maxwell - Wagner Interfacial Polarization
In case of the dielectric constant measurement of a complex oxide system, a capacitor
structure has to be made so that an AC electric field can be applied to it. The response to the

14
electric field will contain at least one capacitive (dielectric) term and one resistive (leakage) term
[24].

Fig 1.8: Capacitor systems with Maxwell-Wagner behavior: (a) homogeneous material with
charge-depleted interfacial layers, (b) superlattice, and (c) clustered material or fine-grained
ceramic with depleted grain boundaries. (d)All can be modeled by two leaky capacitors in series
Since the work functions of the electrode and dielectric material are rarely identical, band
bending may occur near the electrode-dielectric interfaces, causing charge injection from the
electrode into the dielectric or vice versa (charge depletion). In either case, the outcome would
be the formation of a layer near the electrode interface with a different density of charge carriers,
and hence different resistivity than that of the core. If the dielectric is not a very good insulator,
this can cause the electric field to be mostly dropped in the charge depleted interfacial area rather
than in the core of the material, yielding artificially high apparent dielectric constants. This effect
has been documented in several oxide materials, including manganites and may happen not only
at dielectric-electrode interfaces but also at grain boundaries in ceramics and inter slab interfaces
in superlattices [21-30].The dielectric properties of this kind of heterogeneous materials can be
described by the Maxwell - Wagner capacitor model. This effectively consists of two leaky
capacitors in series Fig 1.8.
1.4.7. Dielectric Relaxation
All types of polarization may be grouped into two major regimes: the resonance regime
and the relaxation regime. Polarizations associated with vibrations of electrons (i.e., electronic or
optical polarization) or with vibrations of atoms or ions (i.e., atomic or ionic polarization) belong
to the resonance regime because in the polarization a resonance will occur when the frequency of

15
the excitation field is close to the natural frequency of the vibration or oscillation of the system.
Polarizations involving the movements of charges either by orientation (i.e., orientational
polarization) or through the migration of charge carriers (i.e., hopping or interfacial polarization)
belong to the relaxation regime because during the polarization or depolarization processes, a
relaxation phenomenon occurs due to the time required for the charge carriers to overcome the
inertia arising from the surrounding medium in order to proceed in their movement [21-30].
It is likely that not all dipoles in a solid are situated in the same environment, so some are
more free to move than others. Even in a single crystal, dipoles may find certain orientations
more favorable than others and certain transitions between orientations easier than others. The
variation of such local transition probabilities reflects the variation of the activation energy for
dipole orientation and hence owes different relaxation times (τ).
1.4.8. Debye and Non-Debye Type Relaxation
Debye relaxation is the relaxation response of non-interacting dipoles to an alternating
external electric field. Materials that exhibit a single relaxation time constant can be modeled by
the following Debye equations
(1.16)

(1.17)

where Ks and Kea are the static and instantaneous dielectric constant respectively.

Fig 1.9: Debye curves for K and K as a function of frequency for a dielectric with a single
relaxation time.
In Fig 1.9, the quantities and are represented as a function of τ and it is observed that
(ω) exhibits a maximum for τ =1, i.e., for an angular frequency equal to 1/τ. Also, for
frequencies appreciably less than, 1/τ, the real part of dielectric constant (ω) becomes equal to
the static dielectric constant. In general, the dielectric constant and loss does not obey eqns. 1.16
16
and 1.17 except in some liquid dielectrics and departs seriously in solids [21-30]. This is because
Debye equations were derived on the basis of the internal local field rather than the reaction
field. The Debye equation is in poor agreement with experiments for solid dielectrics, due to the
fact that for solids the Lorentz internal field is not applicable.
Consequently, the interpretation of experimental results on solid dielectric materials
frequently requires a distribution of relaxation times rather than a single one as assumed in the
above discussion [40]. Therefore these materials possess non Debye type of relaxation and one
then employs the following equations

(1.18)

(1.19)

where F(τ) is the distribution of the relaxation times, such that

(1.20)

where F (τ) dτ represents the probability density of F (τ) in the interval between τ and τ  dτ.

1.4.9. Koops Model

In a different way, C. G. Koops [28-30] proposed a phenomenological theory to explain
the observed dispersion behavior of Ni ferrite system, where electrodes were not influential on
dielectric properties.

Fig 1.10: Grain structured conductor. Poorly conducting layers separate the grains
According to Koops, a dielectric solid consists of well-conducting grains separated by poorly
conducting layers, while the current is assumed to flow along the parallel alignments of the
grains, as shown in fig 10. In his study the theoretical frequency dispersion of e and tan, were

17
calculated by taking proper values to the parameters namely thicknesses, resistivities and
dielectric constants of conducting and non conducting regions, and assuming solid consists of the
distribution of relaxation times. The results obtained suggest a good agreement between
theoretical and experimental dispersions. Moreover results also indicate that a rather good
agreement can also be obtained with values of the above parameters differing by 10 or 20 percent
from the original values, which means more than two relaxation time constants and even
distribution of relaxation time constant in the investigated spinel oxides.
1.4.10. Real Dielectric Material
In reality, there is no perfect dielectric material. All real dielectric materials contain more or less,
some mobile charge carriers.

Fig 1.11: Equivalent circuit of a real dielectric material

For the dielectric material of low conductivity, an equivalent circuit (shown in the Fig 1.11) can
be used to describe the response of the material under the applied field between the two charged
metal plates [28].If such a real material has the total charge carrier’s n per unit volume, each
carrying a charge q and having an average mobility v, then the conductivity of this material  is
nqv. RC  d is the leakage resistance of the material where  is the resistivity; C  K/d is the
capacitance per unit area, Rd is the resistance per unit area. Both K and Rd varies with time, and
are derived directly from the polarization process. Thus, at t = 0, just after the insertion of the
material into the vacuum space, K  K (high-frequency dielectric constant) and Rd → ∞, and
at t = ts,  Ks (static dielectric constant) and Rd → ∞. The value of the resistance Rd is finite
only during the period 0 < t < ts. But the leakage current through the leakage resistance RC will
continue to drain the charge between the plates, making s decay with time. By expressing the
voltage between the two plates as

= (1.21)

18
 (1.22)

using the boundary condition s (t = 0) = ( ) the solution of eqn. 1.21 gives

(1.23)
where is the dielectric relaxation time and  is the resistivity of the material. is the
time required for the originally induced charge to decay 35.7% of its original value. can be
very large for materials with a very high resistivity (i.e., low conductivity).
1.4.11 AC Conductivity
A dielectric material, when charged under an AC voltage, will have some loss current due
to ohmic resistance or impedance by heat absorption. If Q be the charge in coulombs due to a
potential difference of V volts between two plates of a condenser of area A and interpolate
distance d then AC conductivity (σac) due to AC voltage V (VO ) is given by the relation
(1.24)

where J is the current density and E is the electric field strength vector. But we know that the
electric field vector D is the displacement vector of the dipole charges and ε is the

complex permittivity of the material. It is also known that for a parallel plate capacitor the
electric field intensity (E) is the ratio of potential difference between the plates of the capacitor to
the inter plate distance.
i.e. (1.25)

Since the current density but q is given by

So, (1.26)

(1.27)

substituting for E and J in the eq 1.25

since ε being a complex quantity

= (1.28)

19
In order that AC conductivity may be a real quantity the term containing j has to be
neglected hence

(1.29)

In any dielectric material, there will be some power loss because of the work was done to
overcome the frictional damping forces encountered by the dipoles during their rotation. If an
AC field is considered, then in an ideal case the charging current IC will be 90° out of phase with
the voltage as shown in Fig 1.12.

Fig 1.12. Phasor diagram representing the phase difference between the current and applied
voltage.

However, in real dielectric materials due to the absorption of electrical energy, some loss current
IL will also be produced, which will be in phase with the voltage. The charging current IC and the
loss current IL will make angles δ and θ respectively with the total current I passing through the
capacitor. The loss current is represented by sin θ of the total current I.
The two components K and K of the complex dielectric constant K are frequency dependent
and given by

(1.30)

(1.31)

since the displacement vector in a time-varying field is not in phase with E hence, there will be a
phase difference δ between them.

From equation 1.30 and 1.31 we have

20
 (1.32)

Substituting the value of (ω) from the above equation in the (1.28) then it can be written as
(1.33)
where ω = 2πf and K = is the relative permittivity of the material and ɛ0
the permittivity of the free space.
So, (1.34)

This equation is used to calculate the ac conductivity using the dielectric constant and the tan δ at
a given frequency. It is to be noted that the value of tan δ is available from dielectric
measurements [28-30].
1.4.12 Jonscher Power Law
The frequency dependence of AC conductivity spectrum exhibits three distinct regimes [21-28]
1. A low-frequency dispersion
2. A frequency intermediate region
3. A conductivity dispersion at high frequency [42 – 45].

The variation of the conductivity in the low-frequency region may be attributed to the
polarization effects at the electrode interface. At low frequencies, more charge accumulation
occurs and hence, there is a drop in the conductivity. In the intermediate and high-frequency
region, the conductivity increases with frequency. The frequency dependence of electrical
conductivity of solid samples is explained by a simple expression given by the Jonscher power
law [46, 47]. The power law relates the frequency dependent conductivity or the so-called
universal dielectric response (UDR) of the conductivity and frequency by the following relation
(1.35)
where a-c is the AC conductivity,  is the limiting zero frequency conductivity, B is a pre-
exponential constant,   2  f is the angular frequency and n is the power law exponent where
0< n <1.
1.4.13. Debye relaxation
This relaxation model was introduced by and named after the physicist Peter Debye
(1913). It is characteristics for the dynamics polarization with only one relaxation time. Debye
relaxation is the dielectric relaxation response of an ideal, non-interacting population of the

21
dipoles to an alternating external electric field. It is usually expressed in the complex permittivity
(ε) of a medium as a function of the field’s frequency (ω)
ε
ε ω ε (1.36)
ωτ

where ɛ is the permittivity at high-frequency limit, Δɛ = ɛs - ɛ

Where ɛs is the static low-frequency permittivity and Ƭ is the relaxation time of the medium.
Separating the real and imaginary parts of the complex dielectric permittivity yields.

And (1.37)

The dielectric loss is also represented by:

ɛ
δ (1.38)
ɛ
ε ε
ε ɛ ɛ (1.39)
ωτ

when ω << , ɛ = εs

If frequency increases (with ω < ), Dipoles begin to “lag” behind the field and ε slightly

decreases. When ω = 1/τ, the dielectric constant, drops (relaxation process). When ω >> 1/τ,
dipoles can no longer follow the field, and = ε . The momentary delay in the dielectric
constant of the material. This is usually caused by delay in polarization w.r.t changing electric
field in a dielectric medium.
1.4.14. Physical Properties of Nickel Ferrite (NiFe2O4)
Nickel ferrite crystallizes to Fd m space group. This compound is represented as
iδ Fe1 δ i1 δ Fe1 δ where cations inside the round and square brackets occupy
A-sites and B-sites, respectively, and δ (degree of inversion) depends on thermal history and
preparation condition [31]. The nickel ferrite NiFe2O4 (see fig 13) crystallize to an inverse spinel
structure. Ni2+ prefers octahedral sites which can be labeled as Ni (Oh), and Fe3+ is equally
distributed between octahedral (Fe (Oh)) and tetrahedral sites (Fe (Td)). The complete structure
crystallizes in a cubic system h space group Fd m (# 227); oxygen atoms occupy the 32e
positions, Fe (Td) atoms occupy the 8a positions and the Ni (Oh) and Fe (Oh) atoms are
distributed on the 16d positions, using Wyckoff notations. It is most versatile centrosymmetric
magnetic materials. It has high electrical resistivity, along with good mechanical hardness and
excellent chemical, thermal and structural stability at high temperature. Lattice parameters such

22
as a = 8.35 Å and u = 0.38 have been determined using X-ray diffraction. The cubic unit cell
thus contains 56 atoms, of which 24 are magnetic transition metals. In the magnetic properties of
this compound are ferrimagnetic, and where its resulting magnetic moment was measured at 1.5–
. μB. NiFe2O4 possesses p-type conductivity when the material contains cation vacancies and,
consecutively, a corresponding amount of Ni3+ will be available at octahedral sites, apart from
the cations Ni2+, and Fe3+, which are located at the octahedral sites. NiFe2O4 tend to attract
oxygen during heating, and thus it is generally known as a p-type semiconductor with cation
vacancies. It shows ferrimagnetism that originates from magnetic moment of anti-parallel spins
between Fe3+ ions at tetrahedral sites and Ni2+ ions at octahedral sites. The nickel ferrite in the
ultra-fine form exhibit noncollinear spin structure and the magnetic moment at low temperature
is appreciably lower than the value for the bulk material. The magnetic character of the
nanoparticles used in various industries depends crucially on the size, shape, purity and magnetic
stability [31] (e.g. blocked unblocked state at particular operating temperature).

Fig 1.13. NiFe2O4 inverse spinel unit cell. Oxygen

atoms have been added in order to complete
the Ni (Oh) and Fe (Oh) first coordination shell. Ni
atoms are shown in blue, Fe ones in green and O
atoms in red [Ref-31].

These particles should be in single domain state, of pure phase, having high coercivity and
moderate magnetization. From the application point of view, the superparamagnetic blocking
temperature of the nanoparticles used for recording devices should be well above the room
temperature in order to have a stable data recording in these devices. In medical applications, the
magnetic nanoparticles are used as drug carriers inside the body where conventional drug
delivery systems may not work. Its magnetic ordering temperature is around 600 0C, which is far
above than room temperature [31].It is also known to be photo magnetic materials which show
an interesting light-induced coercivity change due to optically assisted charge transfer. It has

23
magnetocaloric properties that can achieve local hyperthermia. It has a high magnitude of
magnetostriction. It has large magnetocrystalline anisotropy energy with positive anisotropy
constant. In nickel ferrite they have large magnetic anisotropy which is primarily due to the strong
spin - orbit coupling (i.e. LS coupling) in Ni2+ ions at the octahedral sites (B-site). The trigonal
field (crystal field) is not capable of removing the orbital degeneracy of Ni2+ ion at octahedral
sites. Therefore, the orbital magnetic moment is not quenched and there is strong spin-orbit
coupling which produces large magnetocrystalline anisotropy energy [18]. This large
magnetocrystalline anisotropy energy makes it a hard magnetic material [18]. The physical
properties of nickel ferrite could be tuned by changing the distribution of cations among the
interstitial sites (A-sites and B-sites) by tailoring its chemical composition [18]. However,
controlling the size of the nanomaterials is difficult as their size depends upon the synthesis
method and condition. The growth rate of the nucleation of the particle could be restricted by
creating a large strain at the lattice site by introducing suitable substituent element. The Ni has
larger ionic size than that of Fe and Ni ions. Substituting various trivalent and divalent cations at
the Ni and/or Fe site will create a high strain at the lattice site due to the mismatch in their ionic
radius. Hence one could control the size of the particle with modified properties which has
motivated several researchers to study the modified physical properties of Nickel ferrite. A brief
review on Nickel ferrite and its derivative compound are presented in this section.
Several researchers have studied extensively the physical properties of both bulk and
nanoparticles of nickel ferrite. For example, Khan et al. [32] synthesized nickel ferrite by the sol-
gel combustion and coprecipitation method and reported the structural, optical and magnetic
properties. Sivakumar et al. [33] have prepared NiFe2O4 by the simple and cost-effective
Polyvinylpyrrolidone assisted sol-gel auto-combustion method and observed single phase inverse
spinel structure and super-paramagnetism. Joshi et al. [34] have synthesized NiFe2O4 ferrite
nanoparticle via wet chemical co-precipitation method and observed doublet – like peak behavior
in Raman Spectrum indicating the presence of mixed spinel structure. They have explained the
dielectric permittivity, loss tangent and ac conductivity in terms of feeble polaron hopping
between Fe3+/ Fe2+ ions. The room temperature UV – Vis Diffuse spectra shows that NiFe2O4
ferrite is an indirect band gap material with band gap ranges from 1.27 to 1.47 eV with varying
sintering temperature. Yadav et al. [35] have synthesized NiFe2O4 ferrite nanoparticles by using
honey-mediated sol-gel combustion method and observed octahedral morphology. The XPS

24
analysis determined the occupation formulae. Dielectric constant; dielectric loss tangent and Ac
conductivity were dependent on frequency (1-107 Hz) and grain size. Sivakumar et al. [36] have
studied the structural and magnetic properties of nickel ferrite nanorods synthesized by the
polymer assisted co-precipitation method using polyethylene oxide as a capping and a polymer
structure directing reagent. Sen et al. [37] have synthesized nickel ferrite nanoparticles through a
sol-gel method using urea as a fuel and observed the FT-IR absorption bands related to B-site
and A-site (tetrahedral and octahedral sites) in the range of 400-600 Cm-1 The band gap of
NiFe2O4 ferrite sample is 5.5 eV determined by UV spectroscopy. Younas et al. [38] have
investigated the electrical and magnetic properties of NiFe2O4 ferrite synthesized by sol-gel
method and discussed the decrease in electrical resistance and change in conduction mechanism
due to activated hopping carriers between Fe3+ - Fe2+ and Ni2+ - Ni3+ ions. The semiconducting to
metallic transition temperature is observed around 358 K. The decrease in dielectric constant
with temperature has been discussed in the terms of the depletion of space charge layers due to
the repulsion of delocalized eg electrons from the grain and grain boundary planes. Batoo et al.
[39] studied the nanoparticles of polycrystalline Cu substituted NiFe2O4 ferrites and reported the
variation of dielectric properties (ԑ’, ԑ’’ tan δ) and ac conductivity (sac). Tirupanyam et al. [40]
studied Mn-Ni ferrite systems and reported the variation of D.C.Electrical conductivity with
cation distribution. Prasad et al [41] studied the conductivity (σ) and thermoelectric power (S) of
cadmium substituted Nickel Ferrites and observed a transition near the Curie temperature. The
transition temperature is found to decrease with the increase of Cd content. Selvan et al. [42]
studied the structural and electrical properties of magnesium-substituted nickel ferrite and
reported the variation of dielectric constant (ἐ) and loss tangent (tan δ) as a function of frequency
in the range 50 Hz to 10 kHz at room temperature. According to Maxwell’s–Wagner interfacial
polarization its follows dielectric constant and the relaxation peaks were observed in the
dielectric loss properties and FT-IR spectra which is show the characteristic peaks of ferrite
sample. Bharathi et al. [43] reported the improved dielectric constant and observation of
ferroelectric loop in Dy substituted nickel ferrite. The substitution of a small amount of Gd and
Nd for Fe in nickel ferrite has improved both the dielectric constant and magneto-capacitance as
reported by Bharathi et al. [44]. Sapna et al. [45] synthesized NiFe2O4 nanoparticles by chemical
co-precipitation method and reported the detail X-ray analysis. Shobana et al. [46] synthesized
the Cr substituted NiFe2O4 by sol-gel combustion method and reported the decrease in

25
conductivity with increase in the concentration of chromium. Baykala et al. [47] reported the
magnetic and cation distribution of Mn-Co doped NiFe2O4. Naidu et al. [48] reported the
structural, magnetic and electrical properties of nickel ferrite synthesized by hydrothermal
method and the observed low dielectric constant of 6.79 at 5 MHz. Karthigayan et al. [49]
reported the NiFe2O4 as potential anode material in Li-ion battery. Ahlawat et al. [50] reported
the effect of laser power in Raman spectra of NiFe2O4 in its bulk, thin film and nanoparticle
form. Sutka et al. [51] reported the electrical properties of p-type and n-type nickel ferrites.
Ahlawat et al. [52] synthesized the NiFe2O4 via Sol-Gel auto-combustion method and reported
the super paramagnetic properties with the average crystallite size i.e. 9 nm. Kamali et al. [53]
synthesized the NiFe2O4 with the substitution of Al by the magnetic Compton Scattering
measurements, together with the parallel first-principles computation and reported the extracting
the cation distributions in the ferrite system.
1.4.15. Motivation and Objective of the Present Report
The extensive literature review enlightens that; one could achieve the required physical
properties of nickel ferrite materials by varying its size and tailoring its chemical composition
with the introduction of the strain at the lattice site. The magnetic properties of nickel ferrite
have been studied extensively over a decade. However, the electrical properties of nickel ferrite
and its derivative compound still need to be explored. The present report is aimed to synthesis
the single-phase spinel nickel ferrite using the chemical route and investigates its detail structural
and electrical properties at room temperature.
The objective of the present report is as follow:
1. To synthesized single phase NiFe2O4.
2. To characterize with powder X-ray diffraction for phase analysis.
3. To extract the structural parameter from powder X-ray diffraction pattern employing
Rietveld refinement technique.
4. To study the lattice dynamics using Raman Spectroscopy.
5. To study the morphology of the sample using FE - SEM.
6. To characterize with Impedance Analyzer for electrical properties.
7. To calculate the energy band gap using UV spectroscopy.

26
 Chapter-2
EXPERIMENTAL TECHNIQUES
This chapter deals with the description of the synthesis methods to prepare nanocrystalline nickel
ferrite (NiFe2O4) and their characterization techniques. The samples were characterized by XRD
(X-ray Diffractometer), Raman Spectroscopy, FESEM (Field Emission Scanning Electron
Microscopy), UV Spectroscopy and Impedance analyzer. Details of the synthesis of the present
sample along with above mentioned experimental techniques are presented here.
2.1. Synthesis of Nickel Ferrite (NiFe2O4)
In the present thesis work, Nickel ferrite compound with empirical formula NiFe2O4 has been
synthesized by the citrate-gel method. Nickel nitrate (Ni (NO3)2.6H2O), Iron nitrate (Fe
(NO3)3.9H2O), and citric acid (C6H8O7.H2O) supplied with 99.9% purity were used as starting
materials. The aqueous solution of nickel nitrate, iron nitrate and citric acid were obtained by
dissolving it in deionized water. An aqueous solution of citric acid was mixed with the above
metal nitrates solutions. The mixed solution was kept on a hot plate with a continuous stirring at
80oC. The citric acid plays two important roles: on one hand, it provides fuel for the reaction, as
decomposition of citric acid in the solution liberates heat (exothermic process) which implies
that the heat required for chemical reaction is provided by the reaction itself. Among all the fuels
citric acid is best because it has better complexing ability, low ignition temperature (i.e. 200-250
o
C) and controlled combustion reaction with nitrates. Thus citric acid acts as a ligand to stabilize
metal ions. In the present thesis work, the molar ratio of metal nitrates to citric acid was taken as
1:3.The mixture solution became viscous during evaporation and finally formed a very viscous
colored gel. This viscous gel was dried in a heating oven at 100 0C for 10 hours in order to
remove excess water. After that it was heat treated in air atmosphere at 200 0C for 1 hour. The
ashes were grinded and annealed at 700 0C for 2 hours. The advantage of this method is easy
control of the stoichiometry as this method does not involve any precipitation and the probability
of phase segregation.
2.2. Characterization Techniques
The present samples have been characterized by Powder- XRD, Raman, FE-SEM, UV and
Impedance analyzer. These characterization techniques have been discussed here in brief.

27
2.2.1. Powder XRD (X-ray Diffractometer)
X-ray diffraction method is a fast and non-destructive analytic technique which gives first-hand
information about the materials prepared in the laboratory. It is used to measure the structural
properties such as lattice parameters, crystallite size, lattice strain, preferred orientation, phase
composition, etc. The X-ray powder diffraction data can be used for identification of crystal-
phase of the materials, determination of the crystal structure of unidentified materials and unit-
cell calculations for crystalline materials. A powder sample is composed of a very large number
of crystallites that have random orientations and hence all possible orientations of the crystals are
simultaneously present. In XRD, a collimated beam of X-ray with a single wavelength is incident
on a specimen. If the magnitude of the atomic spacing of the specimen is comparable to the
wavelength of the X-ray, the X-rays are scattered in random direction. At a specified angle, X-
rays reflected from a particular set of crystallographic plane gives a diffracted pattern. However,
the only central maximum is observed in the XRD pattern as other diffraction intensities are
comparable for the background signal. Crystallographic diffraction is explained by Bragg’s law
which is expressed as,
2dhklSinθB = nλ (2.1)
Here λ is the wavelength of X-ray, n is an integer known as order of diffraction, dhkl is the
Interplaner spacing within the same family of planes that cause constructive interference and θ B
is the glancing angle [54].
Many industrially important materials, ranging from ceramics to catalysts to
pharmaceuticals, are polycrystalline and cannot be grown as single crystals. To understand the
properties of these materials, structural information on an atomic level is essential. However, if
an approximate structure is not known and one has to be determined, it is not a trivial matter if
only powder diffraction data are available. In principle, the diffraction pattern from a
polycrystalline material is simply a superposition of millions of single-crystal diffraction patterns
oriented randomly. Unfortunately, peaks with similar diffraction angles, which are well separated
in the single-crystal pattern, lie on top of one another in the powder pattern, and their individual
intensities cannot be determined. If there are too many of these overlapping reflections, attempts
to structure solution will fail. In addition, other factors affecting the powder diffraction pattern
are anisotropic reflection-profile broadening, specimen displacement, graininess, instrumental
errors etc. gives the information content of a powder diffraction pattern [55].

28
 In this thesis, the powder X-ray diffraction pattern at room temperature was recorded by
rotating anode based Rigaku (TTRX-III) X-ray diffractometer operating at 50 kV and 100 mA.
The measurements were performed using the Cu-K radiation (λ=0.15 nm). A layer of sample
powder was spread onto a planer substrate, which is often a non-diffracting material such as
glass. It is positioned to receive the X-rays at an angle θ with the surface and the reflected x-rays
are detected at a specular angle θ. Powder X-ray data of the present samples were obtained from
100 to 1000.
In powder diffraction technique, material is in the form of very small crystallites. The
drawback of this conventional powder method is that the data grossly overlaps, thereby
preventing proper determination of the structure. The “Rietveld Method” creates an effective
separation of these overlapping data, thereby allowing an accurate determination of the structure.
In the present thesis the obtained XRD patterns were analyzed by employing the Rietveld
method to describe the crystal structure parameter which is discussed in the next section.
2.2.2. Rietveld Method
The Rietveld method is a powerful technique devised by Prof Hugo Rietveld to extract
detailed structural information’s of the polycrystalline materials from the powder diffraction
data. Rietveld analysis is not a method of structure solution. It can only be applied when unit cell
dimension, space group and a reasonable model exists for the structure. The Rietveld method is
based on least-squares fitting where Bragg intensities and calculated intensities are compared for
a possible structural model. Crystallites are in random orientation in a polycrystalline sample. As
an effect there might be systematic overlapping of independent diffraction peaks in the powder
pattern due to symmetry conditions. So, information’s may be lost. Rietveld developed a
refinement method by using profile intensities. In this method there is a full pattern profile
refinement and simultaneous crystal structure refinement in one step which gives the structural
information even when the diffraction peaks are not well separated in the powder pattern. In this
method, a set of variable parameters are refined by fitting the calculated powder pattern to the
observed one by a non-linear least square method. The refined parameters in the Rietveld method
are scale factors, background, lattice parameters, zero error, peak shape parameters and peak
width parameters, asymmetry parameters, isothermal parameters, fractional atomic coordinates,
preferred orientations and site occupancies. The non-refinable parameters in the Rietveld method

29
are: space group, chemical composition, analytical function describing the shape of the
diffraction profile, origin of the polynomial function describing the background [55].

Incident Beam of X-rays

Background Reflections

Sample Other sources Position Intensity Profile

Compton
Lattice Atomic Instrument
scattering
Scattering from parameters positions function e.g.
scattering sample holder, Zero error
Thermal
air etc.
diffuse Occupancy
scattering Space group

Temperature Sample
Amorphous function e.g.
fraction Factors domain size,
strain etc.

Fig 2.1: Schematic showing the Information content of powder pattern.

The fitting quality of the experimental data is assessed by computing the parameters such as the
“goodness of fit” χ2, and various R-factors such as Rp (profile factor), Rwp(weighted profile
factor), Rexp(expected weighted profile factor), RB(Bragg factor) and RF(crystallographic
factor)[55]. When these parameters reached to non-oscillatory and accepted minimum values, the

30
best fit to the experimental diffraction data is achieved and the crystal structure is regarded as
satisfactory [55]. In the present thesis all the powder XRD patterns were refined with the help of
a free software Fullprof_suite programme release 2009. The FullProf Suite software is devoted
for Rietveld refinement of powder X-ray diffraction data collected at variable step or constant in
scattering angle θ (structure profile refinement) or of neutron (nuclear and magnetic scattering
time of flight and constant wavelength). The input files for Rietveld analysis known as PCR file
of the present sample is given in Appendix A. The first step of refinement is the refinement of
the global parameters such as scale factors and background. In the next step, the structural
parameters such as lattice parameters, profile shape, width parameter, preferred orientation,
asymmetry, isothermal parameter, atomic coordinates and site occupancies were refined in
sequence.

2.2.3 Estimation of Crystallite Size

In addition to phase identification and structural parameter determination, X-ray
diffraction can also be used for determination of crystallite size. The analysis of the crystallite
size has been carried out using the broadening of the X-ray diffraction peaks. Peak broadening
comes from several sources, i.e. effect of instrument, finite size of the crystallite and the
presence of strain at the lattice site of the crystal [56]. The crystallite size can be calculated by
using Scherrer’s formulae, Williamson- Hall plot and Rietveld method. Scherrer’s has derived a
relationship, which was later modified by Bragg between the broadening of diffraction peaks and
the average crystallite size. The Scherrer’s formula is given as [56],

(2.2)

Where constant k depends upon the shape of the crystallite size (=0.89, assuming the circular
grain), λ is the wavelength of the X-ray, θ is Bragg’s diffraction angle and t is the crystallite size.
β = Full width at Half Maximum (FWHM) of Intensity (a.u.) vs. 2θ profile which is defined as
[53],

   obs
2
  ins
2
(2.3)

Here βobs is the FWHM of observed pattern. βins can be observed by recording XRD pattern of a
well crystallized material with crystallite size > 10 nm. It is a powerful tool for nanocrystalline
material as here the crystallite size is equal to grain size. Both crystallite size and strain

31
properties can be analyzed by using Williamson-Hall method. According to Williamson- Hall
method individual contributions to the broadening of reflections can be expressed as [56]

(2.4)

Here, 4εSinθ is the strain effect on the crystallites.

2.2.4 Field Emission Scanning Electron Microscopy (FE-SEM)
FE-SEM is a new generation of SEM which is a versatile instrument available for the
study of the topography, morphology and composition of the bulk as well as nanomaterials with
much higher resolution. The FE-SEM is composed of a source of electron, series of
electromagnetic coil, vacuum system, detectors and a display device. A series of electromagnetic
coils are used as lenses to focus and manipulate the electron beam. Under vacuum electrons
generated by a field emission source are accelerated in a field gradient. The high energetic
electron beam passes through electromagnetic lenses, focusing onto the specimen. The electron
beam is scanned over the specimen surface by deflection coils. As a result, there is interaction of
electron with the atoms that make up the sample and produces signals that contains information
about the sample’s surface topography and morphology. The type of signals produced includes
secondary electrons (ejected by low energy electron striking), backscattered electrons (ejected by
high energy electron striking) and photons. The secondary electron is emitted from one of the
orbitals of the incident atom and has energy less than 50 eV. As the energy of secondary electron
is less, it is responsible for the topological contrast which provides information mainly about the
surface morphology. The backscattered electrons are the high energy beam electrons (incident
electrons) that are elastically scattered from the sample [57].For imaging sample in the FE-SEM,
surface of the sample must be electrically conductive, otherwise there would be accumulation of
charges at the surface and images become blurred. Therefore, surface of the insulating samples
are usually coated with an ultrathin coating of electrically-conducting material (graphite or gold
or platinum) to make the sample conducting. In the present thesis samples are non-conducting.
Hence, FE-SEM micrographs have taken by making a pellet with coating gold on it. Hitachi S-
4800 machine has been used to record the morphology of samples for present thesis. The
instrument operates in the range of 0 keV to 30 keV.

32
2.2.5. Raman Spectroscopy
Raman spectroscopy is a non-destructive material characterization technique which is
used to study vibrational, rotational, and other low frequency modes in a system. It is sensitive to
structural disorder. It relies on inelastic scattering, or Raman scattering of monochromatic light,
usually from a laser in the visible, near infrared, or near ultraviolet range. The interaction of laser
light takes place with phonons or other excitations in the system, leading the energy of the
photons of laser being shifted down or up. The shift in energy gives information about the
phonon modes in the system. Raman spectroscopy is a form of vibrational spectroscopy, much
like infrared (IR) spectroscopy. Both the techniques are complementary to each other. However,
there is little difference between these two techniques. The Raman bands arise from a change in
the polarizability whereas IR bands arise from a change in the dipole moment of a molecule. In
many cases, transitions that are allowed in Raman are forbidden in IR, so these techniques are
often complementary.
Photons are absorbed by the material and get scattered when a beam of light is incident
upon a sample. The vast majority of these scattered photons has exactly the same wavelength as
the incident photons and is known as Rayleigh scattering, but a tiny portion (approximately 1 in
107) of the scattered radiation is shifted to a different wavelength. These wavelength shifted
photons are called Raman scatter. Most of the Raman scattered photons are shifted to longer
wavelengths (Stokes shift), but a small portion are shifted to shorter wavelengths (anti-Stokes
shift). Raman scattering consists of Rayleigh scattering, Stokes Raman scattering, and anti-
Stokes Raman scattering. In each case, the incident photon excites an electron into a higher
“virtual” energy level (or virtual state) and then the electron decays back to a lower level,
emitting a scattered photon. In Rayleigh scattering the electron return back to the same level
from which it started. In both types of Raman scattering the electron decays to a different level
than that where it started. Stokes Raman scattering occurs when the final energy level is higher
than the initial level, while anti-Stokes Raman scattering occurs when the final energy level is
lower than the starting level. Stokes scattering is much more common in any material in
comparison to anti-Stokes scattering. It is explained as follow: at any given time, an electron is
most likely to be in its lowest energy state in given range of temperature which is in agreement
with the Boltzmann distribution. Only Stokes Raman scattering is commonly used in
spectroscopy. Raman spectroscopy falls in the category of vibrational spectroscopy. This means

33
that transitions of energy arise from vibrations of molecule. Because these vibrations involve
identifiable functional groups, when the energies of these transitions are plotted as a spectrum,
they can be used to identify the molecule. A Raman spectrum is a plot of the intensity of Raman
scattered radiation as a function of its frequency difference from the incident radiation (usually in
units of wave numbers, cm.-1). This difference is called the Raman shift which is independent of
the frequency of the incident radiation [58]. Typically, only the Stokes region is used (the anti-
Stokes spectrum is identical in pattern, but much less intense). Raman spectroscopy is useful for
chemical analysis for several reasons: it is compatible with aqueous systems, it exhibits high
specificity, the timescale of the experiment is short and no special preparation of the sample is
needed . In the present thesis Raman spectra were measured in the backscattering geometry using
confocal micro-Raman spectrometer (Seki Technotron Corp Japan) with the 514.5 nm laser line
as excitation source by STR 750 RAMAN spectrograph. A 100× microscope was used to focus
the laser beam and collects the scattered light.
2.2.6. UV-Visible Spectroscopy
UV-VIS spectroscopy is one of the oldest methods in molecular spectroscopy. The
definitive formulation of the Bouguer-Lambert Beer law in 1852 created the basis for the
quantitative evaluation of absorption measurements at an early date. This led firstly to
colorimetry, then to photometry and finally to spectrophotometry. The wavelength of UV is
shorter than the visible light. It ranges from 100 to 400 nm. In a standard UV-V is
spectrophotometer, a beam of light is split; one half of the beam (the sample beam) is directed
through a transparent cell containing a solution of the compound which is being analyzed, and
one half (the reference beam) is directed through an identical cell which does not contain the
compound but it contains the solvent. The instrument is designed so that it can make a
comparison of the intensities of the two beams as it scans over the desired region of the
wavelengths. If the compound absorbs light at a particular wavelength, the intensity of the
sample beam (IS) will be less than that of the reference beam [57]. Absorption of radiation by a
sample is measured at various wavelengths. It is plotted by a recorder to give the spectrum. It is a
plot of the wavelength of the entire region versus the absorption (A) of light at each wavelength.
And the band gap of the sample can be obtained by plotting the graph between ( hν vs hν) and
extrapolating it along x-axis.

34
2.2.7 Impedance Analyzer
The measurements of dielectric properties can provide valuable information of the
material for technological application. It can be studied with the help of impedance analyzer.
Impedance analyzer works on the principle of sweep measurement. This technique is for
observing the characteristics of the object under test while varying the measurement frequency
and measurement voltage through a continuous range of values. Therefore, the impedance is
measured not only at a single frequency but also in a certain frequency range, allowing for
determining the impedance as function of frequency. This is achieved by sweeping the
stimulation frequency fO and measuring the current response at the respective frequency. In the
present thesis, powder sample is compressed to small disc of diameter 10 mm and cross sectional
area of 7.85 cm2 using KBr press by employing two ton of pressure. After that it is heat treated at
700 OC to obtained high density materials. Materials were found to be hard after heat treatments.
The disc shape pellets were made smooth and polished well with combination of silver paint and
epoxy on both the edges. It acts as an electrode for connecting wires during electrical
measurements. Again the disc was heated to 300 OC for 1 hour to burn out the content of epoxy
from the sample to make it pure. Lastly, the disc was put in sample holder in which two wires
were connected. The working methodology of N4L impedance analysis interface (PSM1735
NumetriQ) was selected to LCR measurements mode. The sample set up comprised of parallel
plate capacitor with nickel ferrite material as dielectric. The input of 2 Volt ac signal was used in
the circuit using N4L impedance analysis interface via PSM1735 NumetriQ for taking the
measurements. The impedance, phase, parallel capacitance and loss tangent measurements were
recorded as a function of frequency (10Hz – 10MHz) at room temperature. On the basis of these
measurements all the required electrical measurements are derived out to understand the
electrical transport properties. The grain and grain boundaries also contribute to overall electrical
properties. The impedance spectroscopy studies are helpful in this regard because both grain and
grain boundaries have different relaxation time.

35
 Chapter-3
Structural, Optical and Electrical properties of nickel ferrite (NiFe2O4)
This chapter describes about the structural, optical and Electrical properties of NiFe2O4
ferrite at room temperature. The results of XRD, Rietveld refinement, Raman, FE-SEM, UV and
Electrical and their analysis have been presented in this chapter.
3.1. Powder X-ray diffraction analysis
The XRD pattern recorded at room temperature for the sample NiFe 2O4 is shown in Fig 1.The

diffraction patterns consist of well resolved peaks which have been indexed to Fd3m space group
in cubic symmetry. All the diffraction peaks are well matched with the JCPDS card no PDF
44-1485.
(311)
Intensity(A.U)

(440)
(220)

(400)

(511)
(222)
(111)

(731)
(533)
(422)

(800)
(620)

(642)
(444)

10 20 30 40 50 60 70 80 90 100
2(Degree)
Fig 3.1: XRD pattern of NiFe2O4sample
The observed diffraction peaks corresponding to diffraction planes (111) (220) (311) (222) (400)
(422) (511) (440) (620) (533)(444) (642) (731) and (800) at angles 18.41, 30.29, 35.68, 37.26,
43.36, 53.84, 57.40, 63.02, 71.53, 74.59, 79.53, 87.48, 90.47 and 95.34 provides the clear
evidence for the formation of single phase face-centered cubic spinel structure for NiFe2O4.Also

36
one could observe closely from the above XRD patterns that the each peak has a finite width
which indicates the presence of lattice strain and finite crystallite size. Within the detection limit
of XRD, no unreacted constituents or impurity phases were traced in the samples. Similar
observation for NiFe2O4 have been reported in literature [34]
The XRD patterns have been analyzed employing Rietveld technique with the help of the
Fullprof Suite programme based on a refinement using Fd m space group. The initial model
and atomic coordinates are taken from literature. The X-ray diffraction pattern along with
Rietveld refined data for the present sample has been depicted in Fig 3.2.

Fig 3.2: Rietveld refined XRD pattern for the sample NiFe2O4. The circles represent
experimental points and the solid lines represent Rietveld refined data. The bottom line shows
the difference between the experimental and refined data. The marked 2 positions are the
allowed Bragg peaks.

It could be seen that the profiles for the observed and calculated ones are perfectly matching to
each other and all the experimental peaks are allowed Bragg 2 positions for Fd m space group.
In the refinement, the oxygen positions (x=y=z) have been taken as free parameters. However all

37
Table 3.1: Fractional atomic coordinates and isothermal parameter of different atoms obtained
from the Rietveld analysis of XRD patterns for the sample NiFe2O4.

Parameter→ x y Z Biso
Atom↓
Fe(Tet) 0.12500 0.12500 0.12500 0.31249
Ni(Tet) 0.12500 0.12500 0.12500 0.31249
Fe(Oct) 0.50000 0.50000 0.50000 0.67974
Ni (Oct) 0.50000 0.50000 0.50000 0.67974
O 0.25330 0.25330 0.25330 0.96997

Table 3.2: Reliability factors (Rp, Rwp, Rexp, RBragg, RF and χ2), lattice constant, bond lengths,
bond angles and crystallite size for the sample NiFe2O4. Errors of the lattice parameters have
been shown in bracket. For example, 8.36785 (94) means 8.3678±0.00094.

Parameters Value
Rp(%) 12.6
Rwp(%) 11.5
Rexp 8.96
RB(%) 4.43
RF(%) 5.70
χ2 2.12
a=b=c (Å) 8.34165 (56)
Volume (Å3) 580.438 (88)
O-Ni (bond length)(Å) 2.0501
O-Fe (bond length)(Å) 1.8429
Fe(B)-O-Fe(B)(bond angle)(degree) 91.5227
Fe(A)-O-Ni(B)(bond angle)(degree) 124.1310
O-Ni-O(bond angle)(degree) 88.4168
O-Fe-O (bond angle)(degree) 109.4715
Crystallite size (nm)
Scherrer method 23
W-H plot 18
Cation distribution (Ni0.121Fe0.879)A[Ni0.879Fe1.121] B

other atomic fractional positions have been taken as fixed. Other parameters, such as lattice
constants, isothermal parameters, occupancies, scale factors and shape parameters have been
taken as free parameters during fitting. Background has been fitted with sixth order polynomial
while the peak shapes have been described by pseudo-voigt profiles. The input file for Rietveld

38
refinement (known as PCR file) for the present sample is given in appendix A. The fractional
positions and isothermal parameters of the atoms obtained from Rietveld refinement for the
present sample is tabulated in Table 3.1. The Reliability factors (R-factors) obtained from
refinement such as Rp, Rwp, RBragg, RF and χ2 for the sample NiFe2O4 are listed in Table 3.2. One
can see from the Table 3.2 that the values of R - factors such as Rp and Rwp are slightly high.
Similar high values of R - factors for polycrystalline materials have been observed by other
groups. However, the value of goodness of fit (χ2) is satisfactory which justify the goodness of
refinement of the given XRD pattern. The distribution of cations among the tetrahedral and
octahedral interstitial sites was estimated by the Rietveld refinement of the occupancy values of
the Ni and Fe cations. The proposed occupancies of cations in the two interstitial sites were
calculated by considering a double population on the B sites as compared to the A sites with the
relative content of cations representing the formula NiFe2O4. The estimated cation distribution
from Rietveld analysis for the sample has been tabulated in Table 3.2.
The analysis of the crystallite size of the present sample has been carried out by using the
peak broadening of the XRD patterns. The broadening βhkl (FWHM) and 2θ (position of peak
centre in degree) have been estimated by fitting the diffraction peak profile to Gaussian function.
Typical fitting of Gaussian to highest intense peak (311) for the present sample is shown in Fig
3.3. The size of the crystallite has been calculated by employing the Scherer’s method and
Williamson-Hall method as discussed in chapter 2 under section 2.3.2. The Williamson Hall plot
for the present sample is shown in Fig 3.4. In the plot 3% error bar has been added. The average
crystallite size is found to be around nm using Scherer’s method whereas using Williamson-
Hall method it is around 18nm. The crystallite size obtained by Williamson Hall method is less
than those obtained by Scherer’s formulae within the same error bar. It is because, the strain
correction factor has been taken into account in case of Williamson Hall method whereas, it has
not been taken into account in Scherer’s method. It can be seen from the W-H plot (Fig 3.5) that
the sample shows a positive slope which indicates the presence of tensile strain in the sample
[59].
The spinel ferrite unit cell has a volume a3 (where a=lattice constant) with eight formula
units ([AB2O4]8), each with a mass of M/NA in grams. The X-ray density ( ) has
beencalculated using following standard relations shown in eq.
(3.1)

39
where is Avogadro’s number (6.0  1023 mol-1), M is the molecular weight of the NiFe2O4
ferrite sample (NiFe2O4 = 234.381 g.mol-1), Z is the number of formula unit present in a unit cell
(Z = 8) and a is the lattice constant.
Experimental Point 0.010 Experimental Point
Fiting to Gaussian
0.009 Fit to Linear

0.008
Intensity(A.U)

0.007

Cos
0.006
0.005
0.004
0.003
0.002
0.001
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
34.5 35.0 35.5 36.0 36.5
2(Degree) 4Sin

Fig 3.3: Fit to Gaussian to intense peak Fig 3.4: Willianson-Hall plot for the sample
(311) for the sample NiFe2O4. NiFe2O4.

The X – ray density is found to be 5.41365 g/cm3. Dislocation density was calculated with the
help of Crystallite size is given by = . The value is around 0.001891016/m2. A measure of

the how will the ions fit into a spinel structure unit cell is defined by the Goldschmid tolerance
factor (t) in AB2O4 structure where A is the divalent cations (i.e. tetrahedral site) and B is the
trivalent cations (i.e. octahedral site). It’s defined the following an equation in which rA is the
average radius of tetrahedral site (A- site) and rB is the average radius of octahedral site (B- site).
Ro is the ionic radius of oxygen (Ro is 1.35 Å). The tolerance factor can be expressed as [60]

(3.2)

The value of tolerance factor is close to unity (i.e. t = 1) for an ideal spinel structure. In the
present case the calculated tolerance factor for NiFe2O4 ferrite values is 0.89876 which is slightly
deviated from the standard value (close to unity). It suggests that the formation of spinel
structure with minimum number of defects.

40
3.2. Raman analysis
The Raman spectra recorded at room temperature in the frequency range of 200 – 1100 cm-1 of
NiFe2O4 is shown in Fig 3.5.
A1g

T2g(2)
Intensity(A.U)

T2g(3)

Eg

T2g(1)

200 300 400 500 600 700 800 900 1000 1100
Raman Shift(Cm-1)
Fig 3.5: Raman spectra of NiFe2O4
The full unit cell of Ni-ferrite (cubic symmetry) contains 56 atoms (eight molecules per unit cell)
but the smallest Bravis cell contains only 14 atoms so there are 42 vibrational modes are
possible. According to group theory there are 42 vibrational modes is possible in spinel structure
compounds. There are 39 normal modes among which 5th are Raman active for spinel structure
as per the group theory. The phonon of spinel structure are given by [59]
(3.3)
where (R) is the Raman, (IR) is the Infrared – active vibrations and (in) is the Inactive modes
respectively. Here the notation A is the 1-Dimensional, E is the 2-Dimensional and T is the
3-Dimensional representation. The symbol (g) is a symmetry w.r.t the center of inversion and (u)
is an anti-symmetry w.r.t the center of inversion. The Group theory has the five Raman active
modes, i.e. A1g + Eg + 3T2g and four infrared active modes (4T1u) for nickel ferrite. All five
Raman modes are observed at ambient conditions and it is composed of the motion of oxygen
anions and both the A-and B-site cations. The A1g mode occurs is due to symmetric stretching of
oxygen anion along Fe–O (Ni-O) tetrahedral site, Eg mode occurs due to symmetric bending of

41
oxygen anion w.r.t Fe respectively, and T2g mode occurs due to asymmetric stretching of oxygen
anion with respect to A-site and B-site cations. The T2g (2) and T2g (3) modes correspond to the
vibrations of the octahedral group. The T2g (3) mode is due to the asymmetric bending of oxygen
and asymmetric stretching of Fe/Ni–O gives rise to T2g (2) mode. The T2g (1) mode is attributed
to the translational movement of the tetrahedron (metal ion at tetrahedral site together with four
oxygen atoms) and octahedron (metal ion at octahedral site together with six oxygen atoms). The
modes above 600 cm-1 (i.e. strongest modes) belong to the motion of the oxygen atoms in
tetrahedral (AO4) group A-site and modes below 600 cm-1 belong to the motion of the oxygen
atoms in octahedral (BO6) group B-sites. To determine the natural frequency of the Raman active
modes of Ni-ferrite sample a least required to done square fit with Lorentzian line shape which
was used to fit the Raman spectra. The thick smooth lines are fits to the Lorentzian functions.
The bands corresponding to these modes are observed at ambient conditions in Raman spectrum
of NiFe2O4 whose values are T2g (1) = 215 cm-1, Eg = 330 cm-1, T2g (2) = 486 cm-1,
T2g (3) = 565 cm-1 and A1g = 695 cm-1the Raman shifts. The observed Raman Peaks are in good
agreement with those reported in literature [34].
3.3. FE-SEM analysis
The surface morphology of NiFe2O4 is shown in Fig 3.6. It shows that shapes of the particles are
nearly spherical.

Fig 3.6: FE-SEM image for the sample NiFe2O4

42
The particles are non- uniform in size and in-homogeneously distributed. The particle size
estimated from FE-SEM micrograph is larger than the crystallite size calculated using XRD. It
reveals that particles have been agglomerated at large extent.
3.4. UV analysis
The energy band gap and UV-visible absorption of a material are a prominent technique to
explore the optical properties of the NiFe2O4. The absorbance of a material generally depends on
several parameters such as grain size, oxygen deficiency, impurity centers, band gap and
roughness of the surface. The UV– Visible absorbance spectra for the sample recorded at room
temperature in the range of 200 – 700 nm is shown in Fig 3.7.
Absorbance(%)

(h)(U)

2 3 4 5 6 7
200 300 400 500 600 700 Energy(eV)
Wavelength(nm)

Fig 3.7: UV-Vis spectrum of NiFe2O4 Fig 3.8: Estimation of band gap using plot of
(ahv)2 versus photon energy
The optical energy band gap of the sample can be calculated from Tauc’s relation given by,

ν, νλ and then (3.4)

λ λ

where, Eph is the photon energy, C is the speed of light, λ is wavelength ( λ

, h is the plank’s constant and ν is velocity.
ν (3.5)
where, hν is the photon energy of the incident photon in eV, A is a constant and S depends on the
transition probability( S = 2 or 1/2 for the indirect and direct band transition and 3 or 3/2 for the

43
forbidden indirect or direct transition probability), is the absorption co-efficient and Eg is the
band gap. ν and ν were plotted against photon energy ν . The straight line
interception to the curve on x – axis gives the value of the optical band gap as shown Fig 3.8.
The values of direct band gap as determined from graphs are 2.58 eV for the NiFe2O4 ferrite. Our
result is consistent with the result reported in literature [34].
3.5: Dielectric properties of NiFe2O4
In order to investigate the dielectric response, the dielectric properties such as dielectric
constant (K ), dielectric loss tangent (tan δ), and AC conductivity (σac) were studied as a function
of applied frequency at room temperature
3.5.1. Dielectric constant
A dielectric material is electrically insulating (nonmetallic) material which exhibits an electrical
dipole structure i.e. there are separation of positive (+ve) and negative (-ve) electrically charged
entities on a molecular level (i.e. atomic level). The dielectric materials utilized as a capacitors.
The strength of dielectric material is known by its dielectric constant. The dielectric constant is
the real part of the complex permittivity (K), and is a measure of how electromagnetic signals
are affected by the material. A material having high dielectric constant concentrates more
electrostatic lines of flux and vice-versa. It is a number relating the ability of a material to carry
alternating current, relative to that in a vacuum. In the present study, the dielectric constant K 
for all the samples was calculated using the relation:

ε
(3.6)

(3.7)
ε

whereO is the dielectric constant of free space, K the dielectric constant of the material, A is
surface area of the sample, d is the thickness of the sample and C is the observed capacitance of
the sample. The variation of the dielectric constant (K ) with frequency at room temperature for
NiFe2O4 is shown Fig 3.9. It can be seen clearly that the dielectric constant decreases
continuously with an increase in frequency. The decrease in the dielectric constant with
frequency is a general behavior in spinel type materials [61, 62]. The dielectric constant
decreases rapidly at the low frequency region and the rate of decrease is slow at the high

44
 frequency region (where the behavior which is almost approaches to the frequency independent
behavior).

5000

Dielectric Constant(K') 4000

3000

2000

1000

0 1 2 3 4 5 6 7
10 10 10 10 10 10 10 10
Fequency(Hz)

Fig 3.9: Variation of dielectric constant with frequency

This behavior of the dielectric constant (K ) as a function of frequency can be explained by the
Maxwell – Wagner type of interfacial or space charge polarization in accordance with the Koops
phenomenological theory. The Koops suggested a theory in which the samples having
heterogeneous structure contain well conducting grains separated by the highly resistive thin grain
boundaries. The conductivity of grain boundaries that contribute more to the dielectric value at the
lower frequencies are mainly due to the presence of all type of polarization that is given by below:
= Pe + Pi + Pd + Psc (3.8)
where e represent as electronic polarization, i is an ionic polarization, d represent as a dipolar
polarization, and sc is space charge contributions respectively. In this model, the exchange of
electron (electronic exchange) between ferrous (Fe2+) and ferric (Fe3+) ions are responsible for the
electronic conduction and dielectric polarization in this ferrite sample such as Fe2+ Fe3+ and
Ni3+ Ni2+. This two charge carrier at the higher frequencies the electron/ hole exchange
frequency will not be able to follow the applied electric field due to this polarization decrease and
then reaches the constant value that is beyond a certain frequency limit. The exchange electron
between Fe2+ and Fe3+ ion in an n-type charge carrier as well as the hole exchange between Ni3+

45
and Ni2+ in the p-type charge carrier due to the local displacement of electron or hole in the
direction of the electric field which is causes due to polarization. The variation of the electrical
conductivity which is run as a parallel to the variation of the ferrous(Fe2+) ions on the B-site (i.e.
octahedral site) that is plays a important role in the processes of conduction as well as dielectric
polarization. The exchange electron between Fe2+ and Fe3+ in an n-type ferrite and hole exchange
between Ni2+ and Ni3+in the p-type ferrite which cannot follow the changes in the applied ac field.
Therefore, the dielectric constant value decreases with increasing of the frequency. Above
discussion can be summarized as, the present sample is in the form of powder which can be
imagined to consist of well conducting grains having perfect crystalline characteristics and it is
separated by poorly conducting grains boundaries. Hence it creates in-homogeneities which give
rise to a frequency dependent polarization. On the application of external electric field, the charge
carriers accumulate at the less conducting grains boundaries thereby creating space charge
polarization. At lower frequencies these charge carriers can follow the external applied field
alternations thereby contributing to the space charge polarization, whereas at higher frequencies
the electron exchange between charge carriers can not follow the external alternating field. Due to
which there is decrease in contribution towards space charge or interfacial polarization resulting in
low dielectric constant (K ) at higher frequencies. The dielectric constants with the frequency are
analyzed through employing the modified Debye equation which is expressed as [63]
(3.9)

5000
Experimental data point
Fitting to modified Debye Equation
Dielectric Constant(K')

4000

3000

2000

1000

0 1 2 3 4 5 6 7
10 10 10 10 10 10 10 10
Fequency(Hz)

Fig 3.11: Modified Debye equation fitting to dielectric constant versus frequency curve.

46
Here, is the high-frequency permittivity, is the low-frequency permittivity, is the
dielectric relaxation time and is the angular frequency respectively. Experimental data point
fitted to modified Debye equation is shown in fig 3.14. Using fitting, the value of spreading
factor ( ) and dielectric dipole relaxation times ( ) has been extracted. The value of spreading
factor is 0.600235. In general, the value of the spreading factor ( ) is varied from 0 to 1 [63].
The value of dielectric dipole relaxation times ( ) is 2.71×10-3s. Similar observation has been
reported in literature [63].
3.5.2: Dielectric Loss (tanδ)
Loss tangent or loss factor (tanδ) is represented as dissipated energy in a dielectric system. This
is caused by domain wall resonance.

4.0
3.5
3.0
2.5
2.0
tan

1.5
1.0

0.5
0.0
0 1 2 3 4 5 6
10 10 10 10 10 10 10
Frequency(Hz)

Fig 3.12: Variation of dielectric loss (tanδ) of NiFe2O4 with frequency.

The variation of tanδ as function of frequency at room temperature is shown in Fig 3.12. The
variation of dielectric loss tangent (tan δ) decreases with an increase in frequency for the
NiFe2O4 ferrite samples. This type of behavior can be explained on the basis of Koop’s model.
At lower frequencies, the principal effect is of low conducting grain boundaries so that more
energy is required for polarization in the grain boundaries due to which energy loss is high. On
the other hand at high frequency polarization between grain boundaries is inhibited and well
conducting grains are more effective in electrical conduction. Hence a small amount of energy is

47
required for polarization due to which the value of dielectric loss tangent (tanδ) is found to be
low at higher frequencies. Similar observation has been reported in the literature [62].
3.5.3: AC Conductivity (σac)
In the order to understanding the conduction mechanism the ac conductivity which can be
evaluated from the tanδ and dielectric which is expressed as

3.10

Where, is angular frequency is dielectric constant and tanδ is the dielectric loss tangent.
The variation of AC conductivity (σac) as a function of frequency for the NiFe2O4 ferrite system
at room temperature is shown in Fig 3.13. Generally the total conductivity is the summation of
the band and the hopping parts:

σac= σ0(T)+σ(ω,T) (3.11)

The first term is frequency independent or dc conductivity which is related to the drifting of
charge carriers and the second term is frequency dependent function and is related to the
dielectric relaxation caused by the localized electric charge carriers which obeys the empirical
power law [61]

σ ω ω (3.12)

0.0020
Ac conductivity(ac)

0.0015

0.0010

0.0005

0.0000

100 101 102

Frequency(Hz)
Fig 3.13: Variation of AC conductivity with applied frequency.

48
It can be clearly seen that the conductivity shows an increasing trend with an increase in
frequency for the NiFe2O4 sample. The conductivity mechanism in the NiFe2O4 is due to the
electron hopping, which can be involves of exchange of electrons between ions of the same
element in different valence states. When an electric field is applied the poorly conducting grain
boundaries are more active at lower frequencies and hence long range inter-wall hopping of
electrons between Fe3+ and Fe2+ ion is less at lower frequencies. As frequency of the applied
increases, the conductive grains become more active thereby promoting the intra-well hopping of
electrons between Fe3+ and Fe2+ ion in octahedral site ( i.e. B –site ). Above discussion can be
summarized as: the conduction mechanism in ferrites can be explained on the basis of exchange
of charge carriers between Fe2+and Fe3+ ions on octahedral sites [61]. At lower frequencies, the
grain boundaries are more active; hence the hopping frequency of electrons between Fe 3+ and
Fe2+ ions is less. At higher frequencies, the conductive grains become more active by promoting
the hopping of electrons between Fe2+ and Fe3+cations; therefore increases the hopping
frequency. So the conductivity is observed to increase with increasing frequency. Our result is
consistent with the result reported in literature [62].
3.6. Impedance Analysis
Impedance spectroscopy is a powerful technique to analyze the electrical properties of
materials. It may be used to investigate the dynamics of bound or mobile charge in the bulk or
interfacial regions of any kind of solid or liquid materials such as ionic, semiconducting, mixed
electronic–ionic materials and even insulators (dielectrics) and also on solid electrolyte materials
such as amorphous, polycrystalline and single crystal form & on solid metallic electrodes.
Impedance Spectroscopy data is commonly analyzed by fitting it to an equivalent electrical
circuit model. Most of the circuit elements in the model are common electrical elements such as
resistors, capacitors, and inductors. The usefulness of impedance spectroscopy lies in the ability
to distinguish the dielectric and electric properties of individual contributions of components
under investigations. The impedance due to grain interiors, grain boundaries and different
electrode properties can be measured independently. This technique also divides the resistive and
reactive part of the electrical component that gives the exact fig of electrical properties. The
frequency dependent real part of impedance ( ) and an imaginary part of the impedance is
correlated as can be expressed as [64]
(3.13)

49
Here is the complex impedance, which is represented as the stored energy ( ) and dissipated
energy ( ).The dissipated energy is directly proportional to the dielectric loss. The frequency
dependent real part of impedance ( ) and an imaginary part of the impedancecan be expressed
by equation
(3.14)

(3.15)

where, ω is the angular frequency, Rp is the parallel resistance, Cp is the parallel capacitance, is
the relaxation time (  is RpCp) and j is the complex quantity ( j = √-1 ).

According to Koops theory, the ferrite material can be regarded as in-homogeneous dielectric
structures consisting of fine conducting grains separated by poor conducting grain boundaries.
Hence, the conductivity at low frequency is due to grain boundary and dispersion at higher
frequencies is due to conducting grains. The frequency dispersion of the real part of the
impedance ( ) of NiFe2O4 at room temperature is depicted Fig 3.14. The logarithmic scale of
frequency is taken for clarity. It is observed that the magnitude of the real part of the impedance
( ) decreases with the frequency which is the normal behavior of the ferrites. There is a sharp
decrease in the real part of the impedance ( ) at lower frequency. Eventually it decreases
towards high frequency and remain constant at very high frequencies. The dispersion behavior of
Z’ at low frequency is the sign of the dielectric behavior because of contributions from various
active sources of polarization such as space charge polarization, ionic polarization, atomic
polarization and electronic polarization). The plot shows (Fig 3.14) the behavior of impedance is
non – dispersive at higher frequency. This can be happens because of the dipolar polarization and
surface charge polarization is failed to flip with respect to fast changing applied alternating
electric field which occurs at high frequency. Similar trend have been reported in literature [64].
In summary, the impedance at very low frequency is due to contribution from interfacial charge,
dipolar, atomic and electronic polarization. As the frequency increase, the polarization due to
dipolar and space charge or interfacial charge abruptly decreases and reaches to zero at high
frequency. Therefore, the non-dispersion impedance is observed at high frequency too. The
electronic dipole polarization in the NiFe2O4 ferrite may be understood by the considering the
electronic interaction or charge hopping between cations (Fe2+ and Fe3+ which reveals the dipole

50
(between Fe3+/2+ - O2-) relaxation). The charge hopping between Fe2+ and Fe3+ cations via oxygen
causes the confirmed that the displacement of electrons along the direction of electric field,
which can be determines the polarization and relative impedance behavior.

250

Real Part of Impedance(Z') 200

150

100

50

0
0 1 2 3 4 5 6 7
10 10 10 10 10 10 10 10
Frequency(Hz)

Fig 3.14: Frequency variation of the real part (Z’) of impedance spectrum of NiFe2O4 at room
temperature.

As the resistance of grain boundary is very high then electrons which can pile up at the interface
which is the cause of the surface charge polarization. Hence, the applied voltage drop in the
specimen could be arises across the grain and grain boundary which is causing space charge or
interfacial charge accumulation under the influence of electric field.
The variation of the imaginary part of the impedance ( ) with frequency at room
temperature of NiFe2O4 ferrites is shown in Fig 3.15. The logarithmic scale is taken in order to
have clarity. The plot shows the appearance of the peak maxima at particular frequency which is
termed as resonant frequency ( ). Thus, resonant frequency corresponds to maximum peak
which is determined from the frequency response of imaginary part of the impedance ( ).A
peak of maxima is observed when the frequency of the flipping dipole equals to frequency of
applied electric field, called as resonant frequency. The condition for the resonance is ωτ = 1,
where time constant τ = RC. The amplitude of the oscillations will be small for any frequency
other than the resonant frequency. Similar trend have been reported in the literature [64].

51
 Any practical system could not be represented by a pure resistor or capacitor, rather a
combination of two could make a real life system. If the real part of the impedance ( ) is plotted
on the X axis and the imaginary part of the impedance is plotted on the Y axis, it is known as
“Nyquist” plot or Cole-Cole plot.

Img Part of Impedance(Z'')

100

80

60

40

20

0
0 1 2 3 4 5 6 7
10 10 10 10 10 10 10 10
Frequency(Hz)

Fig 3.15: Frequency variation of the imaginary part (Z’’) of impedance spectrum of NiFe2O4 at
room temperature.

From the micro-structural point of view, a sample is assumed as a microstructure which is made
up of parallel conducting plates (grains) which is separated by the resistive plates (grain
boundaries). Cole-Cole plot has been extended to understand the grain and grain boundary effect
of a NiFe2O4 dielectric material, where the main contribution of resistance and capacitance which
is come from grain and grain boundary resistance and capacitance. The schematic diagram of ac
impedance measurement-setup in parallel plate capacitor geometry is shown in Fig. 3.16 (a). The
sample can be assumed as the electrical oscillator (parallel RC oscillator). The electrical charge
transport through grains, grain boundaries, and electrode interface has been modeled through
consecutive parallel RC circuits. The individual contributions of grain, GB and electrode interface
can be obtained by modeling of the Cole–Cole plot with the electrical equivalent RC circuits. It
gives an exact contribution of grain and grain boundaries effect on electrical transport properties
of dielectric materials [64]. Fig 3.17 shows the Cole–Cole plot with applied frequency (100 Hz–5
MHz) at room temperature (300 K) of NiFe2O4. It is noting that we have obtained single

52
semicircle. These semicircles are plotted through using Zsimp-win with different contribution of
series resistance (Rs), grain resistance (Rg), grain boundary resistance (Rgb), grain capacitance
(Cg) and grain boundary capacitance (Cgb).

Fig. 3.16: (a) Impedance measurement geometry and (b) electrical equivalent RC circuit of
grain and grain boundary models

350
Measured
300 Calculated

250
Z'' (K)

200

150

100

50

0 200 400 600 800

Z' (K)
Fig. 3.17 The Cole–Cole plots or complex impedance spectra for the samples NiFe2O4 selected
at room temperature. Equivalent circuits are shown as insets in respective figure.

53
Table 3.3: Grain resistance (Rg), grain capacitance (Cg), grain boundary resistance (Rgb) and
grain boundary capacitance (Cgb) obtained at room temperature from complex impedance
analysis

Sample T (K) Rs (Ω) Cg (F) Rg (Ω) Cgb (F) Rgb (Ω)

NiFe2O4 300K 4.372 2.1×10-9 2.37×104 1.5×10-9 1.9×105

The equation has given below for grains and grain boundary,

g = 1 / ωg= RgCg => Cg = 1/Rgωg (3.16)

g = 1 / ωgb= RgbCgb =>Cgb = 1/Rgbωgb (3.17)

where, g is the relaxation times which is corresponding to the grain and gb are the grain
boundary respectively. The equivalent electrical RC circuits based on impedance data are shown
in the Fig. 3.16 (b). The parameter Rs, Rg, Cg, Rgb and Cgb, correspond to series resistance,
grain resistance, grain capacitance, GB resistance, GB capacitance respectively. All the
parameters are obtained by modeling Cole–Cole plot to an appropriate electrical RC oscillator
circuit [64]. The electrical circuit (two parallel RC circuits) models were analyzed using the
ZSimpWin software in which frequency is implicit in every curve. The obtained electrical
elements values are enlisted in the Table 3.3. From the Cole – Cole plot, it is found that the Rg
contribution is dominant over Rgb in NiFe2O4 ferrite sample as indicated by the existence of
single semicircular arc.

54
 Conclusions and Future Scope
The present thesis work deals with the structural, optical and electrical characterization of the
NiFe2O4. The main results are summarized as follows.
1. Single phase samples have been successfully synthesized by citrate precursor method.
2. Rietveld analysis confirms the spinel structure of NiFe2O4 with cubic symmetry.
3. Cation distribution obtained through Rietveld analysis for NiFe2O4 shows the mixed
spinel structure.
4. The crystallite size of the sample calculated by Williamson hall method is less than
scherrer’s method.
5. The FE-SEM image reveals that particles are agglomerated at large extent.
6. The Raman analysis confirms the spinel structure of the sample and well supports the
XRD analysis.
7. The band gap of the material is 2.58 eV.
8. Dielectric constant decreases continuously with an increase in frequency.
9. The variation of dielectric loss tangent (tan δ) decreases with an increase in frequency.
10. The AC conductivity shows an increasing trend with an increase in frequency.
11. The behavior of real part of impedance is non – dispersive at higher frequency and
dispersive at low frequency.
12. The variation of the imaginary part of the impedance ( ) with frequency shows the
appearance of resonant frequency ( ).
13. Cole – Cole plot shows that the Rg contribution is dominant over Rgb as indicated by the
existence of single semicircular arc.
The present work gives some directions to work in future. Some of them are mentioned
below:
1. One could fully explore the temperature dependent dielectric and impedance properties of
these materials.
2. It can be used to form composite with PVDF (ferroelectric polymer) to optimize the
dielectric properties.
3. One could tailor its chemical composition by substituting different types of cations to
optimize its electrical and magnetic properties.

55
 APPENDIX-A
PCR file (input file to program FULLprof-2009) of NiFe2O4
NiFe2O4
! Current global Chi2 (Bragg contrib.) = 8.357
NPATT 1 1 <- Flags for patterns (1: refined, 0: excluded)
W_PAT 1.000
! Nph Dum Ias Nre Cry Opt Aut
1 0 0 0 0 0 0
! Job Npr Nba Nex Nsc Nor Iwg Ilo Res Ste Uni Cor Anm Int
0 5 0 0 0 0 0 0 0 0 0 0 0 0 ! -> Patt #: 1
!
! File names of data (patterns) files
NFO.dat
!
! Mat Pcr NLI Rpa Sym Sho
0 2 0 0 0 0
! Ipr Ppl Ioc Ls1 Ls2 Ls3 Prf Ins Hkl Fou Ana
1 0 1 0 4 0 1 0 0 0 0 ! -> Patt #: 1
!
! Lambda1 Lambda2 Ratio Bkpos Wdt Cthmmu R Asy Lim R polarz 2nd-muR ->Patt# 1
1.542500 1.542500 1.00000 40.000 5.0000 0.8000 0.0000 40.00 0.0000 0.0000
!
! NCYEpsR_atR_anR_prR_gl
50 0.20 0.80 0.80 0.80 0.80
! Thmin Step Thmax PSD Sent0 ->Patt#: 1
10.0000 0.010000 100.0000 0.000 0.000
!
!
18 ! Number of refined parameters
!
! Zero Code Sy Cos Code Sy Sin Code Lambda Code MORE -> Patt # 1
-0.04682 21.0 0.00000 0.0 0.00000 0.0 0.000000 0.00 0
! Background coefficients/codes for Pattern# 1 (Polynomial of 6th degree)
20.528 1.039 0.021 -0.006 0.000 0.000
31.00 41.00 51.00 71.00 0.00 0.00
! -------------------------------------------------------------------------------
! Data for PHASE number: 1 ==> Current R_Bragg for Pattern# 1: 10.33
! -------------------------------------------------------------------------------
ferri
!
! Nat Dis Ang Jbt Isy Str Furth ATZ Nvk More
5 0 0 0 0 0 0 1901.672 0 0

56
! Contributions (0/1) of this phase to the 1 patterns
1
! Irf Npr Jtyp Nsp_Ref Ph_Shift for Pattern# 1
0 5 0 0 0
! Pr1 Pr2 Pr3 Brind. Rmua Rmub Rmuc for Pattern# 1
0.000 0.000 1.000 1.000 0.000 0.000 0.000
!
F D -3 M <--Space group symbol
! Atom Typ X Y Z Biso Occ In Fin N_tSpc /Codes
FE1 FE 0.12500 0.12500 0.12500 0.12609 0.16615 0 0 0 0
0.00 0.00 0.00 141.00 171.00
NI1 NI 0.12500 0.12500 0.12500 0.12609 0.00991 0 0 0 0
0.00 0.00 0.00 141.00 171.00
FE2 FE 0.50000 0.50000 0.50000 -0.13816 0.31599 0 0 0 0
0.00 0.00 0.00 151.00 181.00
NI2 NI 0.50000 0.50000 0.50000 -0.13816 0.03037 0 0 0 0
0.00 0.00 0.00 151.00 181.00
O1 O 0.25261 0.25261 0.25261 9.20403 1.00000 0 0 0 0
131.00 131.00 131.00 161.00 0.00
! -------> Profile Parameters for Pattern # 1
! Scale Shape1 Bov Str1 Str2 Str3 Strain-Model
0.10284E-05 0.43166 -0.61657 0.00000 0.00000 0.00000 0
11.00000 91.000 0.000 0.000 0.000 0.000
! U V W X Y Gau Siz Lor Siz Size-Model
0.840170 -0.103595 0.644655 0.000000 0.000000 -0.586795 0.000000 0
81.000 0.000 0.000 0.000 0.000 101.000 0.000
! a b c alpha beta gamma #Cell Info
8.386074 8.386074 8.386074 90.000000 90.000000 90.000000
61.00000 61.00000 61.00000 0.00000 0.00000 0.00000
! Pref1 Pref2 Asy1 Asy2 Asy3 Asy4
0.37653 0.80392 0.03799 0.01500 0.00000 0.00000
0.00 00.00 111.00 121.00 0.00 0.00
! 2Th1/TOF1 2Th2/TOF2 Pattern # 1
10.000 100.000 1

57
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