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THESIS
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Ferrites are an important class of technological materials that have been recognized to
have significant potential in applications ranging from millimeter wave integrated
circuitry to transformer cores and magnetic recording. The technological importance
of ferrites increased continuously as many discoveries required the use of magnetic
materials. The ferrofluid technology exploited the ability of the colloidal suspensions
of micron-sized ferrite particles to combine the physical proprieties of the liquids with
the magnetism of the crystalline bulk ferrite materials for various applications such as
sealing, position sensing as well as the design of actuators. As such a tremendous
technological progress in electronics was inevitably accompanied by the development
of computing, transportation and non-volatile data storage technologies.
Miniaturization of the electronic devices became critical, thereby leading to the
reduction of the size of the magnetic materials to dimensions comparable to those of
the atoms and molecules. At this point, nanoscale ferrites have found enormous
potential applications in medicine and life sciences. The synthesis of ferrite
nanoparticles with controllable dimensionality and tailorable magnetic properties
along with the understanding of the structure property correlations have become one
of the topics of fundamental scientific importance.
Ferrite thin films have the potential to replace bulky external magnets in current
microwave devices. They can provide unique circuit functions that cannot be
produced by other materials. At microwave frequencies ferrite materials have low
losses, high resistivity and strong magnetic coupling, making them irreplaceable
constituents in microwave device technology. Ferrite thin films have also attracted
much attention in recent years as one of the candidates for high density magnetic
recording and magneto-optical recording media because of their unique physical
properties such as high Curie temperature, large magnetic anisotropy, moderate
magnetization, high corrosion resistance, excellent chemical and mechanical stability
and large Kerr and Faraday rotations. Magnetic soft ferrite thin films with high
resistivity and ac permeability were advanced for applications to micro-inductors,
micro-transformers and magnetic recording. In addition to these applications, both
copper and zinc ferrites have been proved to be good gas sensors and catalysts.
Recently, ferrite applications are being extended to include components used to shield
the electromagnetic interference (EMI).
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size and microstructure of the sample. The resistivity of ferrites is at least six to
twelve orders (depending on composition) higher than that of ferromagnetic materials
such as permalloys and silicon iron. This has given ferrites a distinct advantage as
magnetic materials of choice in high frequency applications.
Ferrites refer to the entire family of iron oxides that includes spinels, garnets,
hexaferrites, and orthoferrites. Ferrites, like ferromagnetic materials, consist of self
saturated domains, exhibit spontaneous magnetization and show the characteristic
hysteresis behavior and the existence of magnetic ordering temperature. Spinel
structure materials are cubic and have the form AB2O4 (A: divalent cations and B:
trivalent cations of Fe). The oxygen atoms make up an fcc lattice with two kinds of
interstitial sites, the tetrahedral (A) sites and octahedral (B) sites that are surrounded
by four and six oxygen ions respectively. The exchange interaction between A and B
sites is negative and the strongest among the cations so that the net magnetization
comes from the difference in magnetic moment between A and B sites. The Fe cations
are the sole source of magnetic moment and can be found on any of two
crystallographically different sites: tetrahedral and octahedral sites.
Given the complexity of the crystal structures of cubic spinel ferrites, the structural
disorder, ranging from cation disorder to grain boundaries, has a significant effect on
the electronic and magnetic properties. Moreover, these ferrites have open crystal
structures so that diffusion of metal cations readily occurs. Both CuFe2O4 and
ZnFe2O4 and mixed Cu1-xZnxFe2O4 ferrites are interesting materials for research and
industrial applications and taken as ideal systems for spinel ferrites. The crystal
structure of these materials is sensitive to the preparation conditions and consequently
influences their typical electrical and magnetic properties.
In contrast to copper ferrite, the bulk zinc ferrite belongs to normal spinel structure
with paramagnetic properties at room temperature and antiferromagnetic below the
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Neel temperature of about 10 K. It has been widely used for a long time in various
electronic components as a common ingredient in technologically important M-Zn
mixed ferrites (M: Mn, Cu, Ni, Co). Nanocrystalline zinc ferrite is also of great
interest in both research and technological fields due to its unique magnetic properties
that differ substantially from their bulk counterparts. This is partly due to the
dominant role of the uncompensated surface magnetic ions.
Copper-zinc ferrite system exhibits several interesting properties which make them
suitable for switching and memory devices, transformer cores, inductors, high
frequency application, gas sensor, catalysts, ferrofluids, etc.
OBJECTIVES
The general objectives of the present research are to investigate the composition,
crystal structure and grain size dependence of the electronic, magnetic and optical
properties of Cu-Zn ferrites (Cu1-xZnxFe2O4, 0 ≤ x ≤ 1).
Scope of study
To attain the above mentioned objectives, the following tasks were carried out
(1) Synthesis of magnetic ferrites MFe2O4 (where M: Cu, Zn and their mixture)
using different physical and chemical methods as follows:
(a) Ceramic method (Solid state reaction) for bulk samples
(b) Chemical methods (coprecipitation) for nanoparticle samples, and
(c) Deposition methods (RF-magnetron sputtering) for nanocrystalline thin
film samples
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(2) Study the crystal structure of the synthesized samples using (XRD) to
ascertain the phase formation and for determining the particle size using peak
broadening analysis.
(3) Observe the morphology, particle size, chemical composition, and the
crystallinity of the prepared samples using different microscopic probes like
Atomic Force Microscopy (AFM), Scanning Electron Microscopy (SEM) and
Energy Dispersive X-Ray Analysis (EDAX).
(4) Study the static and dynamic magnetic properties of the samples using
Vibrating Sample Magnetometer (VSM) and Electron Spin Resonance (ESR).
(5) Study the dielectric properties of the synthesized samples using Impedance
Analyzer.
(6) Study the optical properties of CuFe2O4, ZnFe2O4 and Cu0.6Zn0.4Fe2O4 thin
films and determine the optical constants of the film films such as refractive
index (n), extinction coefficient (k) and energy band gap using transmission
spectra recorded on UV-VIS-IR spectrophotometer.
Chapter 1:Introduction
This chapter includes the literature survey and the theoretical background with a focus
on the fundamentals of magnetism, general information on the ferrite materials,
description of the spinel structure, magnetic anisotropy, ferromagnetic resonance
(FMR) theory and dielectric properties of ferrite materials. The objectives of the
present work are also listed in this chapter.
The details of the experimental techniques used in the present study are described in
this chapter. These include the preparation methods of the ferrite materials and their
characterization. The sample synthesis has been carried out using different physical
and chemical methods, which include solid state reaction for bulk samples,
coprecipitation for nanoparticle samples, and RF-magnetron sputtering for
nanocrystalline thin film samples.
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(a) Preparation methods
The bulk ferrite samples of Cu1-xZnxFe2O4 (0 ≤ X ≤ 1) were prepared by solid state
reaction method using high purity (99.9%) starting materials Zinc (II) Oxide (ZnO),
Copper (II) oxide (CuO) and Iron (III) oxide (Fe2O3). In coprecipitation, the
nucleation and growth rates are two important steps to be controlled. Copper nitrate
trihydrate (Cu(NO3)2.3H2O), Zinc nitrate hexahydrate (Zn(NO3)2.6H2O) and Iron (III)
nitrate nonahydrate (Fe(NO3)3.9H2O) were used as starting materials. Sodium
hydroxide (NaOH) was utilized to chemically precipitate M-ferrite (MFe2O4 where
M: Zn, Cu and Cu+Zn) from a mixture of M-nitrate and iron nitrate. Thin films of
Cu-Zn ferrites were deposited using an RF-magnetron sputtering system (TORR
Company, USA) from 2-inch diameter polycrystalline sintered MFe2O4 (M = Zn, Cu,
Cu0.6Zn0.4) targets prepared by solid-state reaction using high purity ZnO, CuO and
Fe2O3 starting materials.
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Chapter 3: Properties of bulk Cu-Zn ferrites
Fe3+ and Cu1+⇌ Cu2+. When an electric field is applied, it could induce a local
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displacement of charge carriers through hopping to accumulate at the separating
boundaries. The build up of charge carriers at the interfaces corresponds to a charge
polarization and dielectric constant. At high frequencies, the jumping frequency of
electric charge carriers cannot follow the alteration of applied AC-electric field
beyond a critical frequency and the probability of charge carriers reaching the grain
boundaries decreases resulting in decrease of the polarization and dielectric constant.
The dielectric loss (tan) arises due to lag of the polarization behind the applied
alternating electric field and is caused by the impurities and imperfections in the
crystal lattice.
The AC-resistivity (AC) decreases with increasing frequency. The conduction
process in copper ferrites can be explained in terms of the electron-hopping model of
Heiks and Johnson. The charge carriers exchange Fe2+⇌ Fe3+ and Cu1+⇌ Cu2+ occurs
by random transfer between adjacent octahedral (B) sites in the spinel lattice. The
magnitude of exchange, which controls the conduction in ferrites, depends on the
concentration of Fe2+/Fe3+ and Cu1+/Cu2+ ion pairs present on B-sites. The dielectric
constant and dielectric loss tangent decrease with increasing zinc content up to x =
0.6 followed by an increase in x-value. This could be ascribed by the existence of two
types of charge carriers created during the sintering process where the Cu1+/Cu2+ pair
decreases and Fe2+/Fe3+ increases.
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treatment of the samples at higher temperatures leads to grain growth and provides
sufficient energy to allow reordering of the metal cations into their preferable sites
resulting in typical properties of the bulk material. The homogeneity of the samples
has been conformed by EDAX and SEM. The EDAX results show that the
synthesized samples have stoichiometry close to the starting composition. The
morphology of the samples investigated by SEM shows that the average particle size
varies in the 50 - 70 nm range.
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the bulk samples. The analysis of the data has been done on the same lines as for the
bulk samples.
EPR spectroscopy has provided significant information concerning the
homogeneity of the ferrite samples and the dynamics of the ferromagnetic transition.
This chapter covers the detailed temperature dependent EPR study on the
nanoparticles of zinc ferrite and copper substituted zinc ferrites. For zinc ferrite and
copper substituted zinc (10, 20 and 30% Cu) ferrite samples, the temperature
dependence of FMR spectra shows substantial changes in the line shape of resonance
near the transition temperature due to the existence of multi-magnetic phases (para-,
ferro- and antiferromagnetic phases) over a wide range of temperature. For 40 and
60% substituted, the ferro-to-para transition is very sharp. The data is analyzed in
view of various theoretical models.
This chapter contains a detailed study of the structural, magnetic and optical
properties of ferrospinel Cu1-xZnxFe2O4 (x = 0, 0.4 and 1) thin films deposited by rf-
magnetron sputtering.
The highest saturation magnetization (Ms) of 264 emu /cc (in-plane) and 188 emu
/cc (out of-plane) were obtained for the as-deposited CuFe2O4 films in pure Ar at 12
mTorr. The high deposition rate in reducing atmosphere leads to the formation of Cu+
ions which prefer occupation of the A-site in the spinel structure displacing Fe3+
cations to occupy the B-sites giving rise to the change in cation distribution among A
and B-sites and consequently leading to high value of MS. The decrease in MS value
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with increase in oxygen content is ascribed to decrease in film growth rate and Cu+
concentration which allow the cations to take up their preferable sites. The observed
change in the film properties with environment are due the presence of multivalent
copper and iron ions with differing site preferences.
The optical constants of the films were extracted from the transmission spectra by
the envelope method. It is found that the refractive index (n) and the energy band gap
(Eg) increase with increase in Zn-content. The films deposited under Ar environment
having lower values of n and Eg. These values are enhanced by depositing the films in
higher O2 gas pressure. The estimated direct energy band gap values for the film
deposited at 8 mTorr of gas pressure in pure Ar is 2.43 eV. For the films deposited in
pure O2, the band gap increases from 2.48 to 2.61 eV as the O2 pressure is increased
from 8 to 31mTorr. The absorption is attributed to the 3d5→3d44s1 transition of Fe3+
ions, where the 4s orbital of Fe3+ is thought to contribute to the conduction band. The
dispersion of the refractive index (n) is discussed in terms of the single-oscillator
Wemple–DiDomenico model. This model is also used to estimate the dispersion
parameters and the static refractive index.
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5.3 Cu0.6Zn0.4Fe2O4 thin films
The detailed studies on bulk Cu1-XZnXFe2O4 ferrites show that the highest
magnetization of ~ 330 emu/cc is obtained for the composition Cu0.6Zn0.4Fe2O4. There
is no report in the literature on the properties of copper-zinc ferrite thin films. We
carried out a detailed study of crystal structure, magnetic and optical properties of
Cu0.6Zn0.4Fe2O4 ferrite thin films. The films were deposited by RF-magnetron
sputtering with RF power of 100 W in pure Ar, pure O2 and (Ar+O2) at various
working gas pressure. The XRD patterns show that the deposited films are single-
phase and belong to spinel Cu0.6Zn0.4Fe2O4 ferrite with cubic symmetry without any
secondary or impurity phases. XRD studies also confirm the change in the crystal
structure with gas content and the nanocrystalline nature of the as-deposited films.
The average crystallite size increases from 5 to 21 nm with increase in Ar pressure
from 5 to 15 mT. With increase in Ar content the relative intensity ratios of planes
I220/I400, I440/I400 and I422/I400 increases. It is known that for spinel–ferrite the increase
in intensity ratios of these planes is related to the increase in disorder parameter and
consequently to the increase in magnetization. This behavior is an indication of the
film orientation which can be assigned to the special conditions of the film
preparation and the change in distribution of Cu, Zn and Fe ions among tetrahedral A-
site and octahedral B-sites. The films deposited at lower pressure show higher cell
parameter (8.5Å) compared to the bulk due to strain introduced in the film during
deposition. The strain reduces with increase in Ar pressure and cell parameter
approaches the bulk value.
The saturation magnetization (Ms) increases and coercivity (HC) decreases with
increasing Ar pressure. Ms decreases from 283 emu/cc to 150 emu/cc as the O2
content increases from 0 to 100 % in the (Ar + O2) mixture. The variation of working
pressure does not show any significant effect on the MS value when the films are
deposited in O2 environment alone. The large magnetization of the films sputtered
under Ar environment can be due to the appropriate deposition parameters used in the
present study which lead to preferential orientation of ferrimagnetic clusters. . The
high deposition rate in pure Ar environment can lead to freezing of some Cu-ions on
tetrahedral A-sites and equivalent number of Fe ions on octahedral B-sites during the
deposition process. Furthermore, the deposition in reducing (argon) atmosphere may
lead to the formation of Cu+ ion, having larger ionic radius than the Cu2+ ion. The Cu+
ions prefer occupation of the smaller four-coordinated A- site in the spinel structure
and displace Fe3+ cations to occupy the B- sites. The formation of Fe2+ cannot be
ruled out in the spinel structure where a fraction of Fe3+ will be replaced by Fe2+ ions.
So the general cation distribution can be represented as ((Cu2+Cu+)d
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Zn2+Fe3+1−d)tetra[Cu2+1−d(Fe2+Fe3+)1+d]octaO42− where d is the inversion parameter. The
occupancy of the nonmagnetic Cu+ and Zn2+ ions on A-sites dilutes the magnetic
moment on A-sites leading to large difference between magnetization on B and A
sites causing a strong negative super-exchange interaction between Fe3+ ions on both
sites which in turn cause ferrimagnetic behavior with large magnetization. The value
of coercivity, HC decreases from 170 to 67 Oe with increase in Ar pressure from 5 –
15 mTorr. This can be correlated to the crystallite size and the presence of significant
inhomogeneities. The smaller crystallites in the case of thin films deposited under low
Ar pressure has larger volume of the boundaries and consequently more energy is
required to rotate the grains by the external field and thus leading to higher coercivity.
The FMR spectra for the deposited films were recorded at a frequency of 9.2 GHz
for parallel ( H || ) and perpendicular ( H ) orientations of the applied field with respect
to the film plane. The parallel FMR spectra show single symmetric Lorentzian line-
shape. The perpendicular FMR spectra show slightly asymmetric with a second minor
peak. The strong out-of-plane dependence of the FMR spectra reveals the presence of
induced growth anisotropy in the films. This anisotropy decreases with O2 content.
The FMR resonance line width (H) is also strongly influenced by working gas
pressure. The decrease in H with Ar pressure correlates with the hysteresis and
coercivity in the magnetization data which decrease with increasing Ar pressure. The
line shape in perpendicular FMR is more sensitive to microstructural inhomogeneity
than the in-plane case. These qualitative conclusions are also consistent with the
highly textured nature of the films. The FMR parameters such as g-value and
anisotropy field (Hu) were extracted using Kittel’s equations from parallel ( H || ) and
perpendicular ( H ) orientations of the applied field with respect to the film plane.
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Summary and Conclusions
1. The analysis of x-ray diffraction data shows the nanocrystalline nature of the
samples indicating the presence of octahedral zinc in ZnFe2O4 and tetrahedral
Cu in CuFe2O4 thin films and nanoparticles.
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6. An enhanced magnetization compared to bulk zinc ferrite was observed in
films prepared by RF-magnetron sputtering. The magnetization reaches value
of about 42 emu/g at RT.
7. High value of saturation magnetization (Ms) of 264 emu /cc (in-plane) and 188
emu /cc (out of-plane) were obtained for the as-deposited CuFe2O4 thin films
in pure Ar.
8. The optical transmission of ZnFe2O4 thin films is high in the visible (about
85-80% depending on thickness and gas type and pressure), with excellent UV
absorption properties. The transmission and optical band-gap decrease with
increase in copper content and thickness of the films.
9. The post-deposition annealing of the films has been found to alter the film’s
microstructure and properties. Annealing alters the distribution of oxygen
defects, reduces the stress of the thin film and causes grain coarsening and re-
crystallization. Annealing increases the porosity, the transparency and optical
band gap for the films deposited in Ar-atmosphere.
10. Annealing at lower temperatures (< 200°C) does not show a significant effect
on the crystal structure. But annealing in air at higher temperatures (> 300°C)
increases the oxygen content and the porosity of thin films, leading to
improvement in the film transparency and grain alignment.
11. The dielectric constant and dielectric loss are smaller in the case of
nanoparticle samples than those of bulk counterparts. This could be attributed
to improvement in the homogeneity and density of the samples prepared by
coprecipitation method.
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Publications related to this dissertation
(i) International Journals:
[1] Magnetic and optical properties of rf-sputtered zinc ferrite thin films
M. Sultan and R. Singh,
J. Appl. Phys. 105 (2009) 07A512
[2] Structural and optical properties of RF-sputtered ZnFe2O4 thin films
M. Sultan and R. Singh,
J. Phys. D. 42 (2009) 115306
[3] Magnetization and crystal structure of RF-sputtered nanocrystalline CuFe2O4 thin
films
M. Sultan and R. Singh,
Materials Letter 63 (2009) 1764
[4] FMR Studies on Nanocrystalline Zinc Ferrite Thin Films
M. Sultan and R. Singh,
J. Phys. Conference Series (accepted)
[5] Crystal structure and magnetic properties of rf-sputtered Cu-Zn ferrite thin films
M. Sultan and R. Singh,
J. Appl. Phys. (accepted)
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