Synthesize and Characterization of Rare Earth

Doped Ferrites

By

Ahad Ali Khan

CIIT/FA17-RPH-018/LHR

MS Thesis

In

Physics

COMSATS University Islamabad,

Lahore Campus– Pakistan

Spring, 2019
 COMSATS University Islamabad

Synthesize and Characterization of Rare Earth Doped

Ferrites
A Thesis Presented to

COMSATS University Islamabad, Lahore Campus

In partial fulfillment

Of the requirement for the degree of

MS

(Physics)
By

Ahad Ali Khan

CIIT/FA17-RPH-018/LHR

Spring, 2019

ii
Synthesize and Characterization of Rare Earth Doped
Ferrites
A Post Graduate Thesis submitted to Department of Physics as partial fulfillment
of the requirement for the requirement for the award of Degree of M.S Physics

Name Registration Number

Ahad Ali Khan CIIT/FA17-RPH-018/LHR

Supervisor Co-Supervisor

Dr. Salman Naeem Khan Dr. Amna Mir

Associate Professor Assistant Professor

Department of Physics Department of Physics

CUI, Lahore CUI, Lahore

COMSATS University Islamabad, Lahore Campus

July, 2019

iii
 Final Approval
This thesis titled

Synthesize and Characterization of Rare Earth Doped

Ferrites
By
Ahad Ali Khan
CIIT/FA17-RPH-018/LHR
Has been approved

For the COMSATS University Islamabad, Lahore Campus-Pakistan

External Examiner:

Dr. Majid Niaz Akhter

Assistant Professor, MNSUET, Multan Pakistan

Supervisor:

Dr. Salman Naeem Khan

Associate Professor, Department of Physics, CUI, Lahore

Co-Supervisor:

Dr. Amna Mir

Assistant Professor, Department of Physics, CUI, Lahore

HoD:

Dr. Muhammad Ashfaq Ahmed

Hod (Department of Physics) CUI, Lahore

iv
 Declaration

I Ahad Ali Khan and Fa17-RPH-18 of the student hereby declare that I have produced the
work presented in this thesis, during the scheduled period of study. I also declare that I
have not taken any material from any source except referred to wherever due that
amount of plagiarism is within acceptable range. If a violation of HEC rules on research
has occurred in this thesis, I shall be liable to punishable action under the plagiarism rules
of the HEC.

Date: Signature of the Student:

Ahad Ali Khan

CIIT/FA17-RPH-018/LHR

v
 Certificate

It is certified that Ahad Ali Khan Fa17-RPH-018 has carried out all the work related to this
thesis under my supervision at the Department of Physics COMSATS University Islamabad
Lahore Campus and the work fulfills the requirement for award of MS degree.

Date: Supervisor:

Dr. Salman Naeem Khan

Associate Professor

Department of Physics

CUI, Lahore

Head of Department:

Dr. Muhammad Ashfaq Ahmed

Department of Physics

CUI, Lahore

vi
 Dedication

To my friends without whom this research work would have been completed two months
earlier.

vii
 Acknowledgements

First and foremost, I would like to thank God Almighty for giving me the strength,
knowledge, ability and opportunity to undertake this research study and to persevere and
complete it satisfactorily. Without his blessings, this achievement would not have been
possible.

In my journey towards the graduation, I have found a teacher, an inspiration, and a pillar
of support in my Guide, Dr. Salman Naeem Khan (supervisor), Associate Professor. He has
been there providing his profound support and direction at all times and has given me
invaluable guidance and suggestions in my quest for knowledge. Without him, this thesis
would not have been possible and I shall eternally be grateful to him for his assistance.
And I owe my deepest gratitude to my co-supervisor Dr. Amna Mir, Assistant Professor.
Without her encouragement, support and continuous optimism this research work would
hardly have been completed.

I have great pleasure in acknowledging my gratitude to my research colleague, Rafia

Raees. Who propelled me on the course of this work and assisted me in collation of data
for my research. And my friends, Mudassir Hassan, Zohaib-ur-Rehman and Sabir Khan in
ensuring that the fire keeps burning and being there at times when I required motivation.
Their support, encouragement and credible ideas have been great contributors in the
completion of the thesis.

Ahad Ali Khan

CIIT/FA17-RPH-018/LHR

viii
 Abstract

In this study, Yttrium doped Copper ferrite (𝐶𝑢𝐹𝑒2−𝑥 𝑌𝑥 𝑂4 ; 𝑥 = 0.1, 0.2, 0.3, 0.4, 0.5) were
synthesized through sol-gel auto combustion technique. X-ray diffraction and scanning electron
microscope is employed to carry out structural and morphological study of as prepared samples.
The XRD patterns confirms the formation copper spinel structure, with increasing concentration
of dopant induces an impurity phase of YFeO3. And SEM images display the spherical like particles
with decreasing tendency ~ 2.14-1.28 μm. Vibrational modes were examined through Raman and
FTIR Spectra. Observed 5 Raman modes of Γ = A1g + E1g + 3T2g affirm spinel structure with M-O
bonding in undoped sample while increasing Yttrium concentration shifts the modes and
increases the intensity of 3T2g mode at 512.5 nm. FTIR plot the site preference of metallic ions,
Cu-O vibration at 651.5 nm corresponds to tetrahedral site. Dielectric and magnetic properties
were investigated through Vector Network Analyzer, range from 1-6 GHz. The decrease in real
permittivity from ~ 5-3 (F/m) as well as in real permeability ~ 2.5-1.75 (H/m) by increasing Y3+
content. This trend directly correlate with degree of crystallinity. The magnetodielectric
properties are suitable for use in radar systems and shielding applications.

ix
 Table of Contents

Contents
Chapter Number 1 ............................................................................................................................ 1

1.1 Magnetism ....................................................................................................................... 2

1.1.1 Magnetic Flux ........................................................................................................... 2

1.1.2 Magnetic Moment ................................................................................................... 3

1.1.3 Magnetic induction and magnetization ................................................................... 3

1.1.4 Hysteresis loop ......................................................................................................... 4

1.1.5 Diamagnetism .......................................................................................................... 5

1.1.6 Paramagnetism ........................................................................................................ 6

1.1.7 Ferromagnetism ....................................................................................................... 6

1.1.8 Ferrimagnetism ........................................................................................................ 6

1.2 Introduction to Ferrites.................................................................................................... 6

1.2.1 Crystal Structure of ferrites...................................................................................... 7

1.2.2 Spinel Ferrites .......................................................................................................... 7

1.2.3 Copper ferrite........................................................................................................... 8

Chapter Number 2 ............................................................................................................................ 9

Chapter Number 3 .......................................................................................................................... 15

3.1 Sol-gel Method ............................................................................................................... 16

3.2 Yttrium as a Dopant ....................................................................................................... 17

3.2.1 Yttrium or Y (39) ..................................................................................................... 17

3.3 Precursors for Ferrites ................................................................................................... 18

3.3.1 Chemical equations and Stoichiometry ................................................................. 18

Chapter Number 4 .......................................................................................................................... 20

4.1 X-Ray Diffraction ............................................................................................................ 21

x
4.2 FTIR ................................................................................................................................ 23

4.3 Raman Spectroscopy...................................................................................................... 24

4.4 Scanning Electron Microscope ....................................................................................... 26

4.5 Vector Network Analyzer (VNA) .................................................................................... 28

xi
 List of Figures

Figure 1.1 Magnetic field lines around a bar magnet [1] ................................................................ 2
Figure 1.2 Moment exerted by a bar magnet in applied magnetic field [2] .................................... 3
Figure 1.3 Hysteresis loop ................................................................................................................ 4
Figure 1.4 Magnetically categorized Periodic table [3] ................................................................... 5
Figure 1.5: Spinel structure of ferrite .............................................................................................. 7
Figure 3.1 Flow chart of research methodology ............................................................................ 16
Figure 3.2 sol-gel flow chart........................................................................................................... 17
Figure 4.1 Schematic demonstration of the Bragg’s law [6] .......................................................... 21
Figure 4.2 XRD pattern of Yttrium doped CuFe2O4 (Cu Yx Fe2-x O4) ........................................... 22
Figure 4.4 FTIR plot, portray the transmittance of the samples .................................................... 24
Figure 4.5 Raman plot depicts the different modes of vibration .................................................. 25
Figure 4.6 Schematic diagram of SEM [40] .................................................................................... 26
Figure 4.7 SEM images of Y doped CuFe2O4 .................................................................................. 27
Figure 4.8: EDS pattern of undoped and doped CuFe2O4 (Y0, Y1, Y2, Y3, Y4) ............................... 28
Figure 4.9 Variation of (A) real, (B) imaginary permittivity and (C) real, (B) imaginary permeability
in doped CuFe2O4. .......................................................................................................................... 31

xii
 List of Tables

Table 3-1: Quantity of each precursor for different samples ........................................................ 19

Table 4-1: Particle size of doped copper ferrite calculated from ImageJ software ....................... 27

xiii
Chapter Number 1

Introduction

1
The motive of this chapter is to understand the origin of magnetism in materials. In atomic level,
the angular momentum of electrons in atoms gives rise to the magnetic dipole moment. In the
absence of applied field, the magnetic moment contribution came from the orbital angular
momentum of electrons which orbiting around the nucleus and secondly the spin of electrons
around its own axis, give rise to the magnetic moment.

1.1 Magnetism
There are two ways of defining magnetism, one is engineer's way in terms of magnetic poles and
other is physicist's way in terms of circulating current. Magnetic field in terms of magnetic poles
was discovered by Michel and Coulomb in 1785. They gave the theory that two magnetic poles is
proportional to the product of their pole strengths, p, and inversely proportional to the square of
the distance between them, having resemblance of Coulomb’s law,

p1 p 2
F=
4r 2

Here u is the permeability of free space which has the value of 4π×10⁻⁷ (Wb/Am). They also found
out that magnetic monopoles do not exist, experimentally proved by bar magnet.

Figure 1.1 Magnetic field lines around a bar magnet [1]

1.1.1 Magnetic Flux

Another abstract concept of magnetism is magnetic flux which means that the field of magnetic
pole conveyed to a distant place by something which we denote as a flux. Explicitly amount of flux
passing through unit area perpendicular to the field is equal to the magnetic flux (strength). So,
magnetic flux relation is field strength times the area,

 = HA

2
Magnetic flux plays a significant role to generate electric current because a changing flux initiate
an electric current in any circuit which it intersects.

1.1.2 Magnetic Moment

Magnetic moment is the measurement of the material’s alignment tendency in an applied field.
And its vector quantity which determines the nature of magnetism in the substance.

Figure 1.2 Moment exerted by a bar magnet in applied magnetic field [1]

Suppose a bar magnet at a specific angle in an applied field, H, as shown in figure. And the force
of each pole is F=pH and the torque acting on the bar magnet is just the force times the
perpendicular distance from the center, is

1
pH sin  + pH sin  = pHl sin  = mH sin  ,
2

Where m=pl, mathematically the product of the pole strength and the length of the magnet is
called as magnetic moment. For circulating current, the product of current loop area A and
circulating current I is also termed as magnetic moment and defined as

m = IA

Magnetic moment cgs (centimeter-gram-second) unit is emu (electromagnetic unit) and SI unit is
A m².

1.1.3 Magnetic induction and magnetization

Magnetic response of the material in an applied magnetic field is known magnetic induction, B.
Magnetic inductions B units are gauss, Weber/m², or Tesla; 1 gauss = 10⁻⁴. The relationship
between magnetic field H and magnetic induction B is a property of the material. B, H and M
relating equation is

3
 B = o ( H + M )

Here M is the magnetization of the medium, defined as magnetic moment per unit volume,

M= (m/V) ((emu)/(cm³))

And μo is free space permeability.

Magnetization M depends on magnetic moments of the constituent’s ions, atoms and their dipole
moment interaction with each other [1].

1.1.4 Hysteresis loop

Diamagnet and paramagnet exhibit magnetic behavior only in an applied field (diamagnets have
negative susceptibility) and no magnetization is retained when the applied field withdrawn. The
retention of magnetic field phenomena occurs in ferromagnets and ferrimagnets. In these
material much larger magnetization obtained in a smaller magnetic field but at above certain
point the magnetization saturates. And magnetization remain in these materials while
plummeting the applied field to zero. This occurrence known as hysteresis and is essential in
technological applications.

Figure 1.3 Hysteresis loop

The graph of magnetic induction B versus magnetic field H is known as hysteresis loop graph.
When the field increases from the positive direction, the occurrence of magnetic induction can

4
be observed until it reaches. However further increase of applied field, saturation of
magnetization Bs occurs at certain point. When reversing the applied field H to zero, the
magnetization Br retain in the material. To demagnetize the material, additional magnetic field
required in reverse direction called the coercivity, Hc. Coercivity value classifies the material either
hard or soft magnets. When further increase the magnetic field H in reverse direction, magnetic
saturation Bs achieved in the reverse direction. This completes the major hysteresis loop.
Hysteresis loop determines the applications of ferromagnetic and ferrimagnetic materials [2].
Classification of magnetism in the materials depending on their bulk magnetic susceptibility:

Figure 1.4. Magnetically categorized Periodic table [3]

1.1.5 Diamagnetism
When there are paired of electrons in the shell, their spin cancel each other and these electrons
called as diamagnetic electron. Diamagnetic effect noticed when there is a change in orbital
motion due to an applied field. And diamagnetic materials repelled when they are exposed to the

5
applied magnetic field. These materials have negative susceptibility (magnitude about 10⁻⁶ per
unit volume) and negligible dependence on temperature.

1.1.6 Paramagnetism
Paramagnets do have a net magnetic moment, their magnetic moments weakly coupled to each
other. Their internal thermal energy causes the random alignment of magnetic moments and
requires large field to align them. And slightly deflect in the path of the field when they exposed
to the applied magnetic field. Many transition salts elements are paramagnetic in nature. Each
transition metal cation has a magnetic moment due to partially filled d-shell electron and have a
spatial separation of cations due to anions. Hence the magnetic moment interactions on the
neighboring cations are weak. In rare earth case, the magnetic moment source is highly localized
f-shell electrons, which do not coincide with f electrons on nearby ions. Paramagnets are
temperature dependent because as the temperature raised the thermal agitation of the spin
reduces.

1.1.7 Ferromagnetism
The unpaired electron spin in the atom causes the magnetic moment alignment. Due to random
alignment of domain walls in the bulk material, the ferromagnets have no net magnetization. But
domain walls do align with respect to applied magnetic field. Ferromagnets have inverse relation
with the temperature.

1.1.8 Ferrimagnetism
Ferrimagnets have characteristics of both ferromagnetism and anti-ferromagnetism. Below
critical temperature ferrimagnet exhibits spontaneous magnetization whereas the exchange
coupling between neighboring magnetic ions leads to antiparallel alignment of magnetic
moments which depicts the physiognomies of the anti-ferromagnetism.

1.2 Introduction to Ferrites

Ferrites are ceramic magnetic materials consist with divalent metal oxides and iron oxides
(general formula of spinel ferrites: MFe2O4). They are electrical insulator (because of no net charge
in their structure) and magnetically they are conductor that’s why they are extensively used in
high frequency applications because they can resist ac field and avoid undesirable eddy currents.

6
1.2.1 Crystal Structure of ferrites
According to structural symmetries they are many types of ferrites but widely used are spinel,
hexagonal and garnet ferrites.

1.2.2 Spinel Ferrites

Spinel ferrites has a general formula of MFe2O4, M is the divalent metal ion (Co2+, Fe2+, Ni2+, Cu2+,
Mn2+, Zn2+) with face centered cubic structure. In cubic spinel structure there are 32 oxygen atoms
which led to create voids in the structure, 8 tetrahedral (surrounded by 4 oxygen atoms) and 16
octahedral (surrounded by 6 oxygen atoms) sites respectively [modern ferrite]. These voids are
filled by metal ions (M2+, Fe3+). Spinel ferrites further classify into two types; normal spinel ferrites
and inverse spinel ferrites and it depends on the distribution of cations in lattice sites. In normal
spinel structure, 8 divalent (M2+) ions will prefer tetrahedral sites (A) and 16 trivalent (Fe3+) will
prefer the octahedral sites [B] and general formula for normal spinel structure will be (M)A [Fe2]B
O4. In inverse spinel structure, tetrahedral sites will be preferred by trivalent ions, remaining 8
trivalent ions will move towards octahedral sites with 8 divalent ions so inverse spinel structure
formula will be (Fe)A [MFe]B O4 [4], [5]. This distribution of ions will make structure electrically
neutral, that’s why they have high resistivity and low dielectric losses in applied field. (32O2- +
8M2+ + 16Fe3+ = -64 + 16 + 48 = 0)

Figure 1.5: Spinel structure of ferrite

Desired properties of Spinel ferrites can be obtain via different approaches such as cation
distribution, changes in crystal shape, varying concentration of metallic ions and different
synthesis techniques. Spinel ferrites also known as soft ferrites due to low coercivity, high

7
magnetization and thin hysteresis loop, this makes them applicable in many technological devices
to reduce EMI problems [6].

1.2.3 Copper ferrite

Copper ferrites is one of the type of spinel ferrites which receives a lot of attention recently due
to high permeability, mechanical hardness, cost effectiveness and chemical stability [7]. Copper
ferrite manifest an anomalous feature of phase transition from cubic to tetragonal due to the Jahn
Teller distortion of Cu2+ ions in lattice sites [8]. The phase transformation is temperature
dependent as well as Cu2+ and Fe3+ ions concentration.

Presently copper ferrite electromagnetic properties at microwave frequency studied extensively

[9]. The dielectric permittivity and magnetic permeability depend on the interaction between
electromagnetic waves and medium (copper ferrite). It’s expected that dielectric and eddy current
losses can be reduced by substitution of RE3+ ions with Fe3+ ions at higher frequency. Because rare
earth ions are critical in the nucleation and growth of nanoferrites and alters the magnetic spin
orientation to gain desired magnetic properties. Rare earth ions enter into octahedral sites which
distorted the Fe-Fe interaction, induces 4f-3d interactions and lead to structural defects, lattice
strain which ultimately changes the magnetic properties [1], [5]. The Cerium doped nickel ferrite
notably decrease the crystallite size and considerably reduces the dielectric losses [10]. Increasing
yttrium concentration onto cobalt ferrite result into decrease of magnetic saturation as well
decrease of dielectric losses at higher frequency due to the decrease of Fe3+-Fe3+ interactions [11].
Gd3+ ions alters the cobalt ferrite structure which led to decreases the loss tangent and also
tailored the dielectric relaxation which lowers the resonant frequency of rare earth doped cobalt
ferrite [12].

To best of our knowledge there is no systematic information available in the literature of yttrium
substituted copper ferrite at microwave frequency. The purpose of the present work is to
scrutinize the influence of Y3+ ions on the structural, dielectric permittivity and magnetic
permeability through various characterization techniques to explore feasibility for high frequency
applications.

8
Chapter Number 2

Literature Review

9
Zhao et.al. Studied the effect on cobalt ferrite by doping the rare earth (Gadolinium) ion through
hydrothermal method. For morphological analysis, the characterization techniques were XRD,
TEM and Raman Spectroscopy. These techniques confirm the cubic spinel phase of ferrite. They
observe that the particle size reduces by increasing the concentration of rare earth ion. Magnetic
properties determine by the VSM technique which shows that increasing concentration of rare
earth ion decreases the magnetic saturation and coercivity of nano ferrite. UV-vis spectroscopy
calculates the adsorption properties of the material. Increasing concentration of rare earth ion
increases the removal ability for CR which is suitable for dyes [13].

Xu Zuo et.al. Spin-polarized band structure calculation method taken into account to study the
magnetic behavior and electronic structure of copper ferrites in both normal and inverse spinel
structures. Calculations shows that the exchange constants and Neel configuration for normal and
inverse spinel structure may be unstable. For magnetic moments calculation Mulliken population
method used which shows that normal spinel structure may achieve very high magnetization.
Copper ferrite can exist in both normal and inverse spinel structures and can be half metallic
shown by calculated density of states [14].

M.M Rashad et.al. Cubic spinel Copper ferrite was synthesized by using hydrothermal route.
Statistical approach (Box-Behnken Program) used to find the optimum conditions for preparation
of nano ferrites such as temperature, time and pH. Varying parameters are temperature, time
and pH to obtain different samples. At temperature 200 C for 24 hours and maintaining pH 8 gives
the maximum magnetic saturation (Ms 83.7 emu/g). And the maximum catalytic efficiency was at
pH 12 approximately 95.5% due to higher surface area [15].

H Perron et.at. Nickel ferrite density functional theory calculation was carried out by using the
plane-wave basis sets. To study the magnetic structure of nickel ferrite the LSDA (local spin density
approximation) and the GGA (generalized gradient approximation) method were employed. The
GGA formalism were able to calculate the reliable results which is good agreement with
experimental data such as the lattice parameters, electronic properties and the bulk modulus
whereas LSDA were unable to calculate the reliable magnetic structure of Nickel ferrite. And
electronic deformation structure was computed which shows that metallic ions localized around
oxygen atoms which is because of electronegativity scale. The computed inverse spinel and its
metallic vacancies are in good agreement with experimental inverse structure [16].

10
Xiaafei Wu et.al. Different rare earths (RE= Pr3+, Sm3+, Tb3+, Ho3+) used as a dopant on Cobalt
ferrite to study their effects. The rare earth dopant nano ferrites were synthesized through
hydrothermal method. Various characterization techniques were carried out to investigate the
properties of ferrites such as XRD, TEM, FTIR, Raman Spectroscopy and VSM. XRD confirms the
cubic spinel phase of nano ferrites as expected. Rare earth dopant ferrites have a slight decrease
in particle size as well as in magnetic saturation and coercivity of rare earth doped cobalt ferrite.
Raman spectra determine adsorption capability of the material which indicate that rare earth
doped cobalt ferrite have an enhance adsorption property for Congo red (CR) and applicable for
removal dyes [17].

Zaheer Abbas Gillani et.al. Synthesized the rare earth (Neodymium) doped Lithium Cobalt nano
ferrite through micro-emulsion route. Various characterizations carried out to investigate the
properties and its applications. Thermal analysis shows the weight loss of ferrites with increasing
temperature till 950 C. XRD data depicts the cubic spinel phase and crystallite size which is in
range between 52nm-106nm which is in good agreement with research articles of rare earth
doped ferrites. FTIR analysis shows the shifting of two major bands towards lower frequency due
to increasing of Neodymium concentration. In the range of 1MHz-3GHz frequency use to measure
the dielectric parameters and damping effect observed due to increasing of neodymium
concentration. Magnetometer analysis revealed the increase in magnetic saturation and as well
as in coercivity with the doping of Nd3+ ions. The dielectric properties of ferrites propose that they
can be applicable in high frequency devices [18].

A B Ustinov et.al. Yttrium base garnet ferrites were fabricated to make tunable band-pass
microwave filters for microwave applications like photonic generators. The characteristics of
garnet filters centered on excitation, propagation and spin waves reception. Yttrium based filters
were exploited in tuning range of up to 3-7 GHz and filters insertion losses was about 2-3 dB,
bandwidth of 25-35 MHz. The results indicate that it is suitable for microwave applications more
likely in microwave photonic devices and oscillators [19].

Tokeer Ahmad et.al. By using citrate precursor method yttrium ferrite nanoparticles were
synthesized. Various characterization techniques were involve to investigate the properties of
material. Yttrium ferrite have a monophasic orthorhombic structure and also have a uniform
spherical nano particles. UV-vis spectroscopy measures the band gap of ferrites which is
approximately 2.5 eV. Yttrium ferrites have a multiferroic nature which is describe by magnetic

11
and electric hysteresis appearance. The fabricated ferrites showed the better power conversion
efficiency as compared to traditional Titanium dioxide system [20].

Mehdi Rahimi-Nasrabadi et.al. Cerium-doped copper ferrite were prepared by auto-combustion

method. Various characterization techniques were employed to extensively study the cerium-
doped copper ferrite properties. In the existence of prepared nanocrystalline ferrite as
photocatalyst, the percentage of methyl orange degradation was approximately 66 % after 60 min
radiation of UV light. Furthermore, CuFe2-xCexO4 nano ferrites indicates ferromagnetic behavior
at ambient conditions [21].

Kallol Kumar Saikia et.al. By using hydrothermal route Yttrium-doped Cobalt ferrite was
prepared. XRD characterization reveals the single and imprity phase formation occurs at higher
yttrium concentration. Due to oxygen vacancies and Maxwell-Wagner effect dielectric relaxations
were observed. And magnetic saturation decreases due to increase of yttrium content on cobalt
ferrite and also due to the decrease of Fe3+–Fe3+ interactions [11].

Rimi Sharma et.al. Yttrium substituted cobalt ferrite prepared through sol-gel technique for
magnetic photo-catalyst applications. Then various techniques were employed to study the
influence of Y3+ on cobalt ferrite. XRD confirms the generation of crystalline cubic spinel phase
and results suggest that rare earth ion decreases the crystallite size. Vibrating sample
magnetometer (VSM) reveal that magnetic strength decrease with addition rare earth ions onto
cobalt ferrite. Likewise band gap and BET surface area values were also altered because of the
addition of Y3+ ions. The results verified the enrichment in catalytic activity with Y3+ doping in
comparison to unadulterated CoFe2O4 irrespective of inorganic oxidant used. In addition,
recyclability of synthesized photo-catalysts demonstrated stability of materials for long term use
in wastewater treatment [22].

Sadeq H.Lafta et.al Prepared and study nickel nano ferrite through hydrothermal route and pH as
a variable parameter. Sodium hydroxide used as an oxidant and solution basicity controller with
metal chlorides. When pH reaches at 4 there was a phase transition of hematite to spinel ferrite.
With increasing pH crystallite size and lattice constant also affected, the lowest crystallite size and
highest lattice constant observe at pH=4. And at pH=10 maximum crystallite size noticed. At
neutral pH maximum magnetization (48 emu/g) value achieved as well as the minimum coercivity.
The ferromagnetic resonance (FMR) cavity tests were carried out to study the effect of pH on

12
permeability, the results revealed that high imaginary permeability linked to low coercivity and
high magnetization and aggregation [23].

Chung Ming Leung et.al. To enhance the magneto-mechanical properties and power efficiency
of magneto-electric gyrators (ME) yttrium ions were doped in nickel-zinc ferrite. XRD results
indicate that due to replacement of Fe3+ ions with Y3+ ions the polycrystalline structure occurs and
their lattice constant increases. Yttrium doping has a significant effect on magneto-mechanical
coupling (k33,m) and as well as mechanical quality (Qm) factors. Due increase of Y3+ ions the
magneto-mechanical coupling (k33,m) increases whereas mechanical quality (Qm) decreases. It was
found that these factors remain stable with increase of input power density up to 47 W/in3. Y ions
in the ferrite show that a maximum power conversion efficiency observed near 77%. These
outcomes offer the potential for yttrium doped ferrites for ME gyrator applications in power
electronic conversion devices [24].

S. Chakrabarty et.al. They studied the effect of yttrium doped cobalt ferrite by using citrate auto-
ignition route. Synthesize nano particles were examined through various characterization
techniques like XRD, UV-vis, TEM and Impedance Spectroscopy. XRD results reveal the occurrence
of single phase nanocrystalline structure; in addition TEM results confirm the presence of grain
and grain boundaries of nanoparticles. UV-vis indicates the shifting of band gaps due to increase
of yttrium contents on cobalt ferrite. Impedance spectroscopy shows how grain and grain
boundaries affect the conduction band of material. Dielectric properties were measured by
Harviliak-Nigami model (H.N.) model based functions. Conspicuous defects in the crystal structure
played the significant part on the overall transport properties of the system [25].

Franco Jr. et.al. Yttrium-doped cobalt ferrite synthesized combustion reaction method to study
the dielectric effect of yttrium ions onto cobalt ferrite. The applied frequency is between 100-2
MHz to measure the relative dielectric permittivity. The results revealed that with increasing
concentration of yttrium ions the dielectric permittivity increases and decreases with frequency.
The relaxation time found out to be increases with yttrium ions concentration by using Cole-Cole
model. Due to large ionic size of yttrium creates cation vacancies in the spinel structure as per
XRD results. By addition of yttrium ions onto cobalt ferrite enhances dielectric properties which
suggest that it have a vast applications in microelectronic applications [26].

13
Silvia E. Jacobo et.al. Investigate the structural properties and magnetic effect of replaced
Yttrium ions onto Ni-Zn ferrites. The doped nano-ferrites were synthesized through famous sol-
gel method. The frequency range was between 1 MHz to 1.8 GHz was set to find out the
microwave absorption properties. The XRD and SEM results suggest that by addition of yttrium
ions the crystallite size and cell parameters decreases. Substitution of yttrium ions also alters the
magnetic saturation as well as the permittivity and permeability of ferrites when they explored to
different ranges of frequency. Addition of Yttrium content decreases the dielectric constant as
well as the magnetic losses and exhibit the constant behavior over a wide range of frequency. And
yttrium-based ferrite can be considered as a good attenuator in the explored microwave range
due to its properties [27].

E. Uyanga et.al. Copper doped mg-ferrites were synthesized through solid reaction method.
Phase analysis confirms the formation of spinel structure. High Resolution Fourier Diffractometer
(HRFD) determines the investigated the crystal and magnetic structure. Neutron diffraction study
suggest that by addition of copper content the phase transition occurs from cubic to tetragonal
structure. With increasing copper content the magnetic moments increases at tetrahedral side.
The distribution of iron in tetrahedral and octahedral sites was acquired from the neutron
diffraction. Results call attention to a transformation of a mixed spinel to a fully inverse spinel
structures with copper substitution escalate while all Copper ions are engaged in B-sites. Attained
experimental results demonstrate that the copper is one of the suitable dopant for the
magnesium ferrite due to no major crystal and magnetic structures defect and also enriching the
heat generation capability [28].

14
Chapter Number 3

Research Methodology

15
This chapter emphasize on the research methodology. For synthesis of Yttrium doped copper
ferrites sol-gel method was employed. Then balanced chemical equations were construct to
calculate the quantity of precursors and then proceed towards different characterization
techniques for measuring the properties of the prepared samples. The flow chart of research
methodology shown in the Figure 3.1.

Spinel ferrites Synthesis

No

Spinel phase
by XRD

Yes

Structural properties measurement through XRD, FTIR, Raman and

SEM

Electric and Magnetic properties measurement at Microwave

frequency via VNA
Figure 3.1 Flow chart of research methodology

There are various synthesis techniques to synthesize such as Co-precipitation, Salt-melt method,
Ion exchange, Sol–gel, Citrate, Hydrothermal, combustion method and self-propagating high
temperature synthesis etc.

3.1 Sol-gel Method

In this current work, sol-gel method was employed for synthesis of Yttrium doped spinel ferrites
due to its stoichiometric control with narrow particle size distribution and works at lower

16
temperature with relatively short processing time [9]. The Figure 3.2 sol-gel flow chart of the
followed experimental scheme is presented below.

Figure 3.2 sol-gel flow chart

3.2 Yttrium as a Dopant

To best of our knowledge there is no systematic information available in the literature of yttrium
substituted copper ferrite at microwave frequency. Yttrium is relatively cheap rare earth element
and easily available in markets. The objective of the present work is to examine the impact of Y3+
ions on the structural, dielectric permittivity and magnetic permeability through various
characterization techniques to explore feasibility for high frequency applications.

3.2.1 Yttrium or Y (39)

Yttrium is a non-lanthanide rare earth element used in many vital applications. Yttrium is always
found in amalgamation with rare-earth minerals. 89Y is the only stable isotope found in the earth
crust. Yttrium has a silver-metallic appearance. Few of the important usages are

• It is extensively used in the making europium YVO4, and Y2O3 europium phosphors
provides the red color in color television tubes[29].

17
 • Yttrium based ferrites have fascinating electromagnetic properties. Y3Fe5O12 are efficient
transceivers of acoustic energy [20].
• Laser systems utilize Y as catalyst for ethylene polymerization [30].
• It is widely considered in Medical Physics applications such as cancer treatment drugs,
rheumatoid arthritis medicines, and surgical supplies [27].

3.3 Precursors for Ferrites

The precursors used for the synthesis of yttrium doped CuFe2O4 are Cupric nitrate tri hydrate
(Cu(NO3)2*3H2O, 99%), Ferric nitrate Nona hydrate (Fe(NO3)3*9H2O, 99%), Yttrium nitrate
hexahydrate (Y(NO3)3*6H2O, 99%) and citric acid monohydrate(C6H8O7.H2O). The metal nitrates
were mixed in deionized water for aqueous solution and citric acid was used as chelating agent
for ligand formation between ions. Ammonia was used to maintain pH=7 (as pH affects the crystal
growth and phases).

3.3.1 Chemical equations and Stoichiometry

Composition: Cu Yx Fe2-x O4 (x = 0, 0.1, 0.2, 0.3,.0.4). Five samples were be prepared by substituting
yttrium onto iron by varying concentration of Fe and Y at x = 0.1. For each sample mass of
reactants calculated by using balanced equation.

9Cu ( NO3 )2 * 3H 2 0 + 18Fe( NO3 )3 * 9 H 2O + 20C6 H 8O7 → 9CuFe 2 O 4 +36 N 2+269H 2O + 120CO 2

9Y ( NO 3 ) 3 *6 H 2O + 90Cu ( NO3 ) 2 * 3H 2 0 + 171Fe( NO3 ) 3 * 9 H 2O + 200C6 H 8O7 →

9YCu 10 Fe19 O 40 +360 N 2+2663H 2O + 1200CO 2

18Y ( NO 3 ) 3 *6 H 2O + 90Cu ( NO3 ) 2 * 3H 2 0 + 162Fe( NO3 ) 3 * 9 H 2 O + 200C6 H 8O7 →

9Y 2Cu 10 Fe18 O 40 +360 N 2+2636H 2O + 1200CO 2

27Y ( NO 3 ) 3 *6 H 2O + 90Cu ( NO3 ) 2 * 3H 2 0 + 153Fe( NO3 ) 3 * 9 H 2 O + 200C6 H 8O7 →

9Y 3Cu 10 Fe17 O 40 +360 N 2+2609H 2O + 1200CO 2

36Y ( NO 3 ) 3 *6 H 2O + 90Cu ( NO3 ) 2 * 3H 2 0 + 144Fe( NO3 ) 3 * 9 H 2 O + 200C6 H 8O7 →

9Y 4Cu 10 Fe16 O 40 +360 N 2+2582H 2O + 1200CO 2

18
Table 3-1: Quantity of each precursor for different samples

Reactants and Y0 Y1 Y2 Y3 Y4
Products Weight (gm) Weight (gm) Weight Weight Weight (gm)
(gm) (gm)
Copper Nitrate 2.41 2.41 2.41 2.41 2.41
Iron Nitrate 8.08 7.67 7.27 6.87 6.46
Yttrium Nitrate 0 0.383 0.766 1.15 1.532
Citric Acid 4.27 4.27 4.27 4.27 4.27
Ferrite 2.4 2.45 2.46 2.49 2.52

Hereafter, prepared samples characterize through various approaches in likes of XRD, SEM, FTIR,
Raman Spectroscopy and VNA to inspect the effect of yttrium onto copper ferrite.

19
Chapter Number 4

Results Discussion

20
After synthesis of yttrium doped CuFe2O4, the prepared samples were characterized through
various techniques to determine the properties of the spinel ferrite. Firstly XRD was done which
depicts the structure, crystallite size and impure phase in the material.

FTIR plot illustrates the transmission and absorbance properties of the ferrites. Raman
spectroscopy portrays the vibrational mode of the doped CuFe2O4. SEM and EDS renders the
morphological and grain size and elemental quantity of the doped CuFe2O4. And VNA measures
the complex electromagnetic properties of spinel ferrite at microwave frequencies.

4.1 X-Ray Diffraction

X-ray Diffraction is a tool to study the structural properties of the substance such as shape of the
crystal cell dimensions, phase identification, etc. In XRD, intense beam of x-rays interact with the
powder sample and then these constructive x-rays diffract according to the structure orientation
of the material. Then these diffracted X-rays collected at detector. The diffraction pattern
comprise of reflections at different intensities which can be used to determine the crystal
structure. The diffraction occurs when Bragg’s condition satisfies

𝟏 𝛌
𝒅 = 𝟐 (𝐬𝐢𝐧 𝛉)

Figure 4.1 Schematic demonstration of the Bragg’s law [6]

21
 ^ : YFeO3
Y4 Y3 Y2 Y1 Y0 JCPDS : 48-0529
^ * : CuO
^

*
*
Y4 JCPDS : 48-1548

*
Y3 ^ ^

*
Intesity (a.u)

*
Y2

*
^ ^

Y1

*
*
^

Y0 t-CuFe2O4
*
*
211 JCPDS : 340425
103

224
400
321
220
112

312
20 30 40 50 60 70 80
 / Degree

Figure 4.2 XRD pattern of Yttrium doped CuFe2O4 (Cu Yx Fe2-x O4)
The incident X-ray beam scattered from powdered samples (Cu Yx Fe2-x O4) range 0 to 80 degrees
and then diffraction angle occurred which correspond the d-spacing of the mineral as shown in
Figure 4.1. Conversion of these d-spacing allows us to identify the nature of mineral because each
mineral has distinctive d-spacing. An intense peak observed when powder has the lattice planes
with d-spacing suitable to diffract X-rays with specific value of theta (θ). And maximum reflection
intensity explains the maximum electron density variation at that lattice plane. The structural
properties of the prepared samples were determined with the X-Ray Diffraction, presented in
Figure 4.2. XRD source operating with Cu-Kα at 40 kV and 30 mA as source with step size of 0.026.
The peaks at 2θ are 30o, 34.87, 36.1o, 44o, 54.25o, 58o, 62.2, 63.83o in Y0 corresponds respectively
to [1 1 2], [1 0 3], [2 1 1], [2 2 0], [3 1 2], [3 2 1], [2 2 4], [4 0 0] indices of tetragonal phase with
space group I41/amd (JCPDS: 340425) [7]. There is also evidence of a minor impurity phase of CuO
at angle 35.54o and 38.7o (JCPDS: 48-1548). This is because of higher reactivity of Cu2+ ions
compared to Fe+3 and therefore copper and oxygen make a bond. For the very reason, there are
no traces of hematite [32]. Secondly, copper ferrite also has a property of structural transition
from cubic to tetragonal and this led to exchange of several Cu2+ ions into (A) from (B) sites
depending on temperature and concentration. Therefore, free Cu2+ ions react with O2- ions in
atmosphere to form an extra phase of CuO [33]. The doping of Y3+ ions into copper ferrite

22
confirms the change in crystal structure and their respective diffraction peaks has slight peak shift.
As Y3+ ions concentration increases it led to the formation of Yttrium-Orthoferrite phase (YFeO3)
is confirmed by XRD for Y1 to Y4 and CuO phase remain consistent. The major peaks of
Orthoferrite at 33.20o and at 52.04o are in consistent with the previous results [27]. This is due to
the higher reactivity of Fe3+ with Y3+ ions which led to the increase of oxygen vacancies indicates
the limited tolerance of rare earth ions into spinel structure due to bigger ionic radii of Fe3+(0.69
Å) compared to Y3+ (1.04 Å) [22]. This larger ionic radii induces strain in the crystal structure that
lead to the formation of Orthoferrite phase (JCPDS: 48-0529).

As the doping concentration increases, the significant broadening of peaks can be observed at
mentioned angles. These peaks correspond to the phase of copper and yttrium ferrites
superimpose and broaden the peak widths. Because the peak broadening is due to the multiple
phase in the samples, therefore the Scherrer’s formula is not used for the calculation of particle
size using these broaden peak. The sample Y1 from XRD suggest the crystal structure and with the
increase of RE doping introducing addition phase which resets in the formation of nano composite
that are visible in Y4 and Y5.

4.2 FTIR
FTIR (Fourier-Transform Infrared Spectroscopy) is dispersive instrument which calculates the
absorbance and emission of the material. FTIR works over a high spectral range which enables it
to collect all wavelengths simultaneously, this feature known as Multiplex or Felgett Advantage.
Initially FTIR obtain the interferogram (pattern formed by wave interference) of material by
striking of rays between 400-4000 nm and then mathematical process Fourier Transform applies
to obtain the spectrum. In short FTIR spectrometer collects and digitizes the interferogram then
performs the theoretical Fourier Transform function and display the spectrum [34].

For study the interaction between the cation and oxygen atom in tetrahedral and octahedral sites
we use Fourier Transform Infrared Spectroscopy. The Infra-Red transmission peaks of spinel
ferrite exist in range between 400-700 nm. In our case FTIR range starts from 600 nm onwards,
do due to limitation of device one peak is missing. The major peak observed at 651.5 nm as shown
in Figure 4.3, which indicates the interaction of Cu-O at tetrahedral site and also ascribes the
stretching vibration at this peak [35]. Gradual increase in transmission peak intensity can be
observed as the Y3+ ions replace the Fe3+ ions in the structure.

23
Figure 4.3 FTIR plot, portray the transmittance of the samples

4.3 Raman Spectroscopy

Raman spectroscopy operates at monochromatic light by laser beam and to detect the materials
inelastic scattering. Monochromatic photons were absorbed by the material and then re-eject
from the material which causes the inelastic scattering. Frequency of the ejected photons can
switched up or down compare to original monochromatic frequency, which is known as the
Raman Shift. This effect gives us the fingerprint of the compound through vibrational, rotational
and transitions of molecules in low frequencies.

In Raman spectroscopy, molecules deformed in applied electric field E and deformation measures
by polarizability α. When laser beam (electromagnetic wave) interact with sample it prompts the

electric dipole moment p = E which causes deformation in molecules [36].

The samples (Y0, Y1, Y2, Y3, and Y4) were further scrutinized by the Raman spectroscopy in
frequency range of 100-800 cm-1 shown in Figure 4.4. In spinel structure there are five major

24
Raman active modes based on the quasi-molecular description of normal mode motions of FeO4
tetrahedron, represented by Γ = A1g + E1g + 3T2g. In which A1g mode describes the symmetric stretch
of oxygen atoms along Fe-O bonds, Eg mode is due to the asymmetric and symmetric bending of
oxygen with respect to Fe, whereas 3T2g modes elucidates the symmetric and asymmetric
bending, stretching and translational movement of Fe and O in the unit cell [1]. In the present
study the undoped samples, Raman active mode observe with corresponding to their bands at
212.5, 402.6 and 525.7 can be attributed to T2g mode, 324 to E1g mode whereas 727.5 imputes to
A1g mode and these modes are consistent with the previous tetragonal structure [2], [3].

The peaks of doped samples are different from undoped sample due to the occurrence of YFeO3
phase in the samples (as reported in XRD results). The relative intensity of Raman peak at 512.53
increases with the doping of Y3+ ions in copper ferrite. This explicates the substitution of large Y3+
ions for Fe3+ ions and Cu2+ ions at octahedral, the difference of Y-O, Cu-O and Fe-O band length
may upsurge the presence of ion vacancies, lattice defect or the loss of symmetry at these sites[4].
To our best information there is no report of the Raman spectra of YFeO3 hexagonal, that’s why
we are unable to determine the influence of each modes.

Figure 4.4 Raman plot depicts the different modes of vibration

25
4.5 Scanning Electron Microscope
In SEM (Figure 4.5), the electrons in the beam interact with the sample, producing various signals
such as secondary electrons, backscattered electrons and characteristic X-rays which can be used
to attain information about the composition and surface topography of the material.
Backscattered electrons reflected back after elastic collision between the sample and beam
whereas secondary electrons produce from the sample atoms. SE are a result of inelastic
interaction between the beam and sample atoms and provides the surface information of the
sample. And characteristic X-rays conduct the elemental analysis of the sample. This means that
SEM also equipped with an energy dispersive X-ray detector (EDX). So within a few seconds SEM
device can also provide the chemical composition of the analyzed sample.

Figure 4.5 Schematic diagram of SEM [40]

26
The morphological images of the samples were obtained from SEM (scanning electron
microscope) to study the effect of doping on grain size and grain boundaries as shown in

Figure 4.6. The powder samples of Y0, Y1, Y2, Y3, and Y4 exhibits cubic/spherical like shape with
agglomeration to some elongate. The average particles size of samples were calculated by using
ImageJ software which lies at 2.14-1.28 (±0.2) μm. SEM images further confirms the coarseness
and porosity in some samples due to escape of gases in combustion process. The doping of Y 3+
ions causes the plummeting in grain size as shown in SEM images.

This trend may be attributed to the lattice strain and structural disorder due to conspicuous
dissimilarity in the ionic radii of the Y3+ and Fe3+ [38]. The prepared samples were indistinguishable
in the images because strong Fe-Fe magnetic interaction in the lattice which causes the
agglomeration of the particles and also because of surface energy in the grain boundaries of
crystallites [20]. Fig (EDX) shows the EDX patterns of the samples which depicts the
proportionality of chemicals with energy peaks of Cu, Fe, Y, O. And EDX patterns confirms the
incorporation of Y3+ ions into the copper ferrite with no impurities as shown in Figure 4.7. At lower
energy with higher intensity peaks corresponds the k-alpha radiation conversely at higher energy
with lower frequency corresponds to the k-beta radiation. Furthermore, the amount of these

27
elements for each powder, was found agree with the calculated amount during the synthesis,
representing the stoichiometry of these compounds.

Figure 4.6 SEM images of Y doped CuFe2O4

28
Table 4-1: Particle size of doped copper ferrite calculated from ImageJ software

Sample Average Grain (μm)

Y0 2.14

Y1 1.56

Y2 1.42

Y3 1.51

Y4 1.28

Figure 4.7: EDS pattern of undoped and doped CuFe2O4 (Y0, Y1, Y2, Y3, Y4)

4.6 Vector Network Analyzer (VNA)

Vector Network Analyzer measures the two port complex scattering parameters
(Transmission/Reflection) of the sample, by placing the sample in coaxial aircell. The permittivity
and permeability of the material can be measured through scattering equations. The material
interaction with the electromagnetic radiation is characterize by the permittivity, permeability
and conductivity. These properties are complex in nature because they varies with the frequency.

29
The ε’ real part of the complex permittivity (ε’-jε’’) determines the ability of the material to polarize
in response to the applied field where as the ε’’ imaginary part accounts for the losses (due to flow
of charges) mechanisms at the microscopies level. Similarly complex permeability (μ’-jμ’’) μ’ real
part refer to the formation of magnetic alignment within the material and μ’’ imaginary part
denotes the magnetic losses (due to damping of magnetic moments) in form of energy dissipation.
The ratio of imaginary part to real part is termed as the loss tangent δ of the material.

Electromagnetic assessment at microwave frequencies was made through the complex

permittivity and permeability measurements, using a coaxial line with Transmission/Reflection
(T/R) method. The samples measurement were carried out in the frequency range of 1GHz to 6
GHz by means of ROHDE & SCHWARZ Vector Network Analyzer by using coaxial transmission line
with sample holder to evaluate the scattering parameters of reflection (S11 and S22) and
transmission (S21 and S12) at two ports. The advantage of having coaxial line over other methods;
is that it measures in a wider frequency range with accurate results. Before starting the
measurements full two-port calibration was performed in order to remove errors due to source
match, load match, isolation, directivity and frequency response in forward and reverse direction
[41]. Then the S-parameter measurements were imported to Epsimu software in order to evaluate
and plot the complex permittivity and permeability of samples.

The variations in complex permittivity as a function of frequency in yttrium doped copper ferrite
studied at ambient conditions. The Figure 4.8 depicts the dispersion of real and imaginary part of
permittivity/permeability with frequency as a function. At low frequency both ε and μ have higher
value of samples, as frequency increases the reduction in 𝜀, 𝜇 noticed which is general behavior
of ferrites. This trend delineate the Maxwell-Wagner interfacial type polarization and in
agreement with Koop’s phenomenological model (dielectric structure is formed within the grain
boundaries when field applied) [42]. The properties of 𝜀, 𝜇 depends on the electron exchange
between Fe3+ and Fe2+ ions, when field applied local displacement of charges occurs in direction
of field, which subsequently illustrates the polarization of the samples. In ferrites there is a well-
known fact that the conducting grains split by poorly conducting grains (as grains shown in SEM
images). At low frequency, electrons move towards the grain boundary via hopping, electrons will
heap at the grain boundaries because of resistivity at grain boundaries and eventually polarization
occurs. As applied frequency increases, electron reverse their direction of motion and probability
at grain boundaries reduces owing to fact that beyond a particular frequency, the electron

30
exchange between Fe3+ and Fe2+ ions cannot trail the alternating field which result into decrease
in polarization and so as dielectric constant from ~ 4.8 − 3.2 (F/m) [43]. Reduction in dielectric
constant termed as relaxation which means the polarization no longer follows the applied field.
Complex permeability composed of two mechanisms domain wall motion and spin rotational
magnetization. Due to these type of magnetization (motion) there is a relevant resonance, spin
rotational resonance observed at higher frequency (GHz) range whereas domain wall resonance
noticed at lower frequency range [44]. At microwave frequency region, permeability of spinel
ferrite described by Snoek’s theory, in which variation in permeability depends on the
microstructure of the material [4]. Usually magnetic losses inversely depend on the resistivity of
the ferrite exhibits high losses at low frequency and vice versa.

At GHz region, peaks of permittivity occurred at 2.5 GHz, 4.3 GHz in all samples which get smaller
by increasing Y3+ ions (which cause increase in yttrium Orthoferrite formation). These peaks also
corresponding to imaginary permittivity suggesting that there may be a resonance occurring at
these frequencies which are characteristic of complex permittivity and permeability as shown in
Figure 4.8 [45]. And possible reasoning is the Clusterization of the crystalline grain and presence
of oxides which can increase the number of maxima in the imaginary part. The reduction in
permittivity can be interpret as presence of YFeO3 and CuO phase which could have increase the
electrical conductivity of the material as previously reported (in Nb-doped CoFe2O4) [46]. The
similar trend observed in complex permeability, with increasing yttrium concentration the values
of real and imaginary permeability decreases from ~ 3.8 − 2.2 (H/m) this might be due to rise of
3d-4f interaction which lowers the magnetic moment. Similar to permittivity plot, permeability
also has several peaks but at different frequencies, with peaks in 𝜇′ around at 2.2 GHz, 3.8 GHz.
The variations in the results also because of permeability and permittivity directly depend on the
high degree of crystallinity, as XRD results illustrate the variation in degree of crystallinity. Because
EM wave dispersion rate is higher in crystalline materials due to periodicity of crystals which
enable many energy levels.

These permittivity and permeability measurements at microwave frequencies of ferrites, make

them suitable for high temperature radar systems. While apparent peaks due to resonance at GHz
frequency suggest that Yttrium doped copper ferrite are suitable material for electromagnetic
shielding at specific microwave frequencies.

31
Figure 4.8. Variation of (A) real, (B) imaginary permittivity and (C) real, (B) imaginary permeability
in doped CuFe2O4.

32
Conclusion and Future Work
Yttrium doped copper ferrite successfully synthesized through sol-gel route. Various
characterization techniques elucidates the phenomenal properties of our material. XRD describes
the structural properties and occurring of other phases, importantly yttrium Orthoferrite (YFeO3)
which suggest the limited tolerance of Y3+ ions onto spinel structure. Because of greater difference
in ionic radii between Fe3+ and Y3+ ions. FTIR results indicate the vibrations at octahedral site
whereas Raman results confirms the spinel ferrite modes. VNA plot demonstrates the reduction
of complex permittivity and permeability due to decrease in crystallinity, due to decrease in
intensity counts as demonstrated in XRD results. And VNA measurements at microwave
frequencies suggests that this compound suitable for high temperature radar systems and
electromagnetic shielding. In future the prepared samples further characterize in waveguide
setup for high frequency applications, range from 18 to 50 GHz.

33
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