Multiferroics: Crystals and Thin Films

Abstract
Multiferroic materials have generated increasing interest in the scientific community over the past
decade, because of the unique coexistence of ferroic properties and possible potential applications for
new types of next generation novel devices. In this report, I present the analysis of the structure,
properties, processing, characterization and potential applications of multiferroic crystals and thin
films, covering structured FE properties (Polarization, leakage, switching), Magnetic properties
(canted and excess magnetism), Domains in films (100/110/111 and switching), Probing
Antiferromagnetism (with SHG, THz and XMLD), Coupling between FE and AFM, Coupling
between FE, AFM and FM, Coupling in nanopillar heterostructures, research progresses, potential
applications of Multiferroics and concluding with my suggestions. To present the overall view for the
deeper understanding of multiferroics, I have covered right from the study of Materials, Electronic
materials, Metal Oxides, Transition Metal oxides (TMO), properties of TMO, Thin film processing
(PLD, CVD, Sputtering, MBE) and then I have proceeded with to the in depth analysis of Multiferroic
Crystals and thin films right from its crystal chemistry using BiFeO3 as a model system.
Pradeep D Iyer
UGR Advisor: Dr. Ramesh Ramamoorthy
Department of Materials Science & Engineering University of California, Berkeley, CA 94720, USA
E-mail:pradeepdiyer@berkeley.edu

1.0 Introduction development of the next generation novel

The continuous research, developments and devices.
discoveries in the field of Condensed-matter,
especially in the sub fields of Material Physics 2.0 Multiferroics
and Material Chemistry in the 20th century, has Multiferroicity is the coupling between
made possible the massive technological magnetic and (ferro) electric order, which
progress in the fields of Microelectronics, originated from the magnetoelectric effect,
optoelectronics, Bio-electronics, computing discovered by Pierre Curie in 1894 (Fig-1) [1].
and data storage. The vertical integration of
material science and engineering through thin
film technology; has developed and produced
more complex sensors, integrated circuits,
displays, bio-electronic devices, data storage
and recording devices. The quest for
producing miniaturized and more powerful
devices with less power consumption drives
materials science and engineering to new limits
and it has led to the increasing interest, of the
researchers towards multiferroic materials,
which are very promising candidates for the
Fig-1, Magnetoelectric Effect [1]

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It is the magnetization by an electric field or
the induction of electric polarization by a
magnetic field. The study of the magnetic and
ferroelectric materials has led to some of the
most important technological advances to date.
2.10 Magnetoelectric (ME) effects.
The coupling between magnetic and electric
properties of a material is termed as magneto-
electric effects. These effects can be expressed
as the expansion of the free energy of a
material as follows.
Where PS and MS denote the components of
the spontaneous polarization and
magnetization and εij and µij are the electric
and magnetic susceptibilities, respectively. The
tensor αij corresponds to the induction of
polarization by a magnetic field or of
magnetization by an electric field and is
designated as the linear ME effect [4]. The
linear magnetoelectric effect can be expressed
as follows
Pi = αij Hj
Mi = αji Ej
Where α is the magnetoelectric tensor, non-
zero only in the absence of space and time-
inversion [2].
The ME effects are limited by the following
relation.
From this expression it is clear that in order to
obtain the largest ME effects in single phase of
a material, large dielectric constants and
magnetic susceptibilities are important. The
materials possessing these two properties are
called multiferroics and are the best candidates
to show strong ME effects.
Magnetism and ferroelectricity are involved
with local spins and off-center structural
distortions, respectively. These two seemingly
unrelated phenomena can coexist in certain
unusual materials, termed "multiferroics"[1-6],
and sometimes called "magnetoelectric
multiferroics ", possess two or more switchable
states such as polarization, magnetization or
strain[3,4].
Fig-2 Ferroelectricity and Antiferromagnetism in BFO
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The term (magnetoelectric) multiferroics
comprises not only ferroelectromagnetism but
also Antiferromagnetism, Antiferroelectricity
and ferroelasticity, eg- BFO in Fig-2 [7, 8 & 9].
2.20 Requirements for Multiferroics
The requirements for multiferroics are detailed
in Fig-3.
Fig-3 – Requirements for Multiferroics [8, 9]
So, Multiferroics can be defined as materials
which combine at least two “ferroic” properties
in the same phase such as ferromagnetic
order (spontaneous magnetic polarization that
can be reversed by a magnetic field),
ferroelectricity (spontaneous electric
polarization that can be switched by an applied
electric field) or ferroelasticity (change in
electric polarization accompanied by a change in
shape). Some materials not having
ferromagnetic but antiferromagnetic(Parallel
Magnetic field but opposing spins which varies
with temperature), ferrimagnetic (Incomplete
cancellation of antiferromagnetic arranged spins
giving a net magnetic moment), ferrotoroidic
(spontaneous magnetic vortex), or helimagnetic
ordering (Magnetic spin moments arrange
themselves in a spiral or helical pattern due to
exchange interaction between Ferromagnetic and
Antiferromagnetic ordering) are also accepted as
multiferroics (Fig-3).
There are only a few materials that possess
both ferroelectricity and magnetism, but their
coupling effect is not large enough for
industrial applications. The non-trivial spin-
lattice coupling, in these multiferroics has been
manifested through various forms, such as
linear and bilinear magnetoelectric effects,
polarization change through field-induced
phase transition, magneto-dielectric effect, and
dielectric anomalies at magnetic transition
temperatures [4, 5, 6 & 7].
So, before going deep in to the investigation of
multiferroics, I would like to briefly review
about the Materials from its origin, engineering
materials, Electronics material, Transition
metal oxides- its structure and properties for
better and deeper understanding about
multiferroics from the fundamental view point.
3.0 Materials
In general, materials are substances of which
something is composed or made. Materials can
be classified as Natural and Man made or value
added. Man-made or Value added materials are
termed as engineering materials (Fig-4) [13-16].
3.10 Materials Science and Engineering
(MSE)
The understanding of the behavior of materials
and their properties is only possible, with
detailed understanding of materials from its
atomic and electronic structure level. Quantum
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mechanics pioneered in explaining the atoms
and then solids starting from 1930s. The
combination of physics, chemistry, and the
focus on the relationship between the properties
of a material and its microstructure is the
domain of Materials Science. The development
of this science allowed the designing of
materials and provided a strong knowledge base
for engineering applications termed as Materials
Engineering [13-16].
3.20 Importance of MSE
All engineering disciplines need to know about
materials, even the most material-less, like
software or system engineering depends on the
development of new high performance material
like Multiferroics, which in turn alter the
economics, like software-hardware trade-offs,
miniaturization and high performance. The
knowledge of MSE enables Engineers,
Chemists, Designers, Researchers, Scientists to
select a material for a given use based on
considerations of design to cost with high
performance; also to understand the limits of
materials and the change of their properties with
use; and to create a new material that will have
desirable properties.
3.30 Historical Perspective of Materials
Materials are vital in the development of
civilization and are used to name the period of
civilization like Stone Age, Metal Age (Bronze
Age, Iron Age and so on. From the origin of
human life on Earth, the Stone Age people
used only natural materials, like stone, clay,
skins, and wood. The discovery of copper and
its alloys was the cause for the birth of Bronze
Age about 3000 BC. The use of iron and steel,
a stronger material that gave advantage in wars
started at about 1200 BC. The next big step
was the discovery of a cheap process to make
steel in 1850, which enabled the railroads and
the building of the modern infrastructure of the
industrial world.
Structural materials
Used for construction purposes. Includes
construction materials (steel beams, concrete,
wood, bricks, glass etc.), materials for
machines, cars, aircraft, ships, railways, roads,
bridges, pipelines, containers etc.
Functional materials
Used for their special properties like electrical,
magnetic, optical, thermal, chemical
properties, that decides the performance of the
system. Functional materials are called
Electronic Materials [13-16].
3.40 Classification of Electronic Materials
The electronic materials are classified by
application (Structural and Functional
electronic materials) and by composition
(Inorganic and Organic electronic materials)
as detailed in Fig- 4 [13-16].
But Electrical / Computer Engineers like to
classify materials based on electrical behavior
(Insulating, Semi- insulating and Metals) and
the Materials Engineers / Scientists like to
classify materials based on bond types (Ionic,
Covalent and Metallic / Van der Waals) or
Structure (Crystalline, Polycrystalline and
Amorphous materials).
As far as multiferroics are concerned, the
crystal chemistry of solids plays a vital role in
understanding and investigating the Atomic
Bonds and Band Structures and provides the
strong knowledge base for designing and
synthesizing new fascinating classes of
multiferroics.
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Fig: 4 – Classification of Materials [10-16]

Page 5 of 154
4.0 Atomic Bonds
and Band Structures
The chemical bond arises from a redistribution
of electronic charge when atoms are brought in
close proximity. The bond in solids results
from the superposition of charge densities of
all atoms in the system.
When an infinite number of atoms come
together to form solids they would form
bonding, non-bonding and antibonding
molecular orbitals of different energies so
close together that they blur into one another
forming a band. These molecular orbitals are
described by wave functions. The most
important point to come out of the theory is
that for N atomic orbitals in a molecule, N
molecular orbitals are the outcome.
4.10 Atomic Structure and Bonding
Atoms are composed of electrons, protons, and
neutrons. Electrons and protons are negative
and positive charges of the same magnitude,
A mole is the amount of matter that has a mass
in grams equal to the atomic mass in amu of
the atoms. Thus, a mole of carbon has a mass
of 12 grams. The number of atoms in a mole is
called the Avogadro number, Nav = 6.023 ×
1023. Note that Nav = 1 gram/1 amu. Where, M
is the atomic mass in amu (grams per mol).
Most solids have atomic densities around 6 ×
1022 atoms/cm3. The cube root of that number
gives the number of atoms per cubic
centimeter is about 39 million. The mean
distance between atoms is the inverse of that,
or 0.25 nm. This is an important number that
gives the scale of atomic structures in solids
(Fig- 5) [12].

The mass of the electron is negligible with

respect to those of the proton and the neutron,
which form the nucleus of the atom.

The unit of mass is an atomic mass unit (amu)

= 1.66 × 10-27 kg, and equals 1/12 the mass of a
carbon atom. The Carbon nucleus has Z=6, and
A=6, where Z is the number of protons, and A
the number of neutron. Neutrons and protons
have very similar masses, roughly equal to 1 Fig – 5 Shell model of an atom with electrons revolving
amu. All neutral atoms have the same number within shells and sub shells [17].
of electrons and protons, Z.

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4.20 Electrons in Atoms
The forces in the atom are repulsions between
electrons and attraction between electrons and
protons. The neutrons play no significant role.
Protons (Z) is what characterizes the atom,
electrons form a cloud around the neutron, of
radius of 0.05 to 2 nm. Electrons move in
‘fuzzy’ orbits called shells (Fig-5) [12].
According to quantum mechanics, the orbits
are identified by a principal quantum number
n, which is related to the size, n = 0 is the
smallest; n = 1, 2 are larger. (They are
"quantized" or discrete, being specified by
integers). The angular momentum l is
quantized, and the projection in a specific
direction m. Two electrons can be placed in an
orbit with opposite spins in a given n, l, m
shell [12].
In 1925, Wolfgang Pauli explained the
arrangement of electrons in an atom by his
exclusion principle. His hypothesis was that
only one electron can occupy a given quantum
state. Each electron in an atom has a unique
set of quantum numbers (the principle
quantum number gives its energy level, the
magnetic quantum number gives the direction
of orbital angular momentum, and the spin
quantum number gives the direction of its
spin).
In fact, we now know that that the Pauli
Exclusion Principle holds for not just
electrons but for any fermions (half-integer
spin particles like electrons, protons, neutrons,
muons.)
4.30 The Periodic Table
Elements are categorized by placing them in
the periodic table. Elements in a column share
similar properties. The noble gases have
closed shells, and so they do not gain or lose
electrons near another atom. Alkalis can easily
lose an electron and become a closed shell;
halogens can easily gain one to form a
negative ion, again with a closed shell.
The propensity to form closed shells occurs in
molecules, when they share electrons to close
a molecular shell. Examples are H2, N2, and
NaCl. The ability to gain or lose electrons is
termed electronegativity or electropositivity,
an important factor in ionic bonds.
The vertical columns in the periodic table of
the chemical elements are referred to as groups
(Fig-6). There are 18 groups in the standard
periodic table. The modern explanation of the
pattern of the periodic table is that the elements
in a group have similar configurations of the
outermost electron shells of their atoms, as
most chemical properties are determined by the
orbital location of the outermost electron. The
international way of numbering the groups of
the periodic table is using Hindu-Arabic
numerals / Indian numerals.
The type of orbital in which the atom's
outermost electrons reside determines the
"block" to which it belongs and the number of
valence shell electrons determines the group.
The total number of electron shells an atom has
determines the period to which it belongs.
Each shell is divided into different subshells
and as atomic number increases, they are filled
in roughly in this order (the Aufbau principle)
as shown in Fig-6.
Progressing through a group from the lightest
element to heaviest element, the outer-shell
electrons (those most readily accessible for
participation in chemical reactions) are all in
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the same type of orbital, with a similar shape, Fig-6 shows the periodic table of elements with
but with increasingly higher energy and various labeling schemes.
average distance from the nucleus [13].

Fig-6 the Periodic table

Page 8 of 154
For example, the outer-shell (or "valence")
electrons of the first group, headed by
hydrogen, all have one electron in an s orbital.
In hydrogen, that s orbital is in the lowest
possible energy state of any atom, the first-
shell orbital (and represented by hydrogen's
position in the first period of the table). In
francium, the heaviest element of the group,
the outer-shell electron is in the seventh-shell
orbital, significantly further out on average
from the nucleus than those electrons filling all
the shells below it in energy. The increase in
Fig-7 the Periodic table based on electronic configuration
the atomic number (i.e. charge on the atomic
nucleus) leads to greater spin-orbit coupling
between the nucleus and the electrons. Because
of the importance of the outermost shell, the
different regions of the periodic table are
sometimes referred to as periodic table blocks,
named according to the sub-shell in which the
"last" electron resides, e.g. the s-block, the p-
block, the d-block, etc (Fig-7). The elements
Ununbium, ununtrium, ununquadium, etc.,
have been discovered, but so far have not been
named [13].
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4.40 Bonding Forces and Energies
The Coulomb forces are simple: attractive
between electrons and nuclei, repulsive
between electrons and between nuclei. The net
force between atoms is given by a sum of all
the individual forces, and the fact that the
electrons are located outside the atom and the
nucleus in the center (Fig- 8) [12].

Fig- 9 Forces Vs Separation distance [12].

from each other. The interaction energy is the

integral of the force over the separation
distance, so these two quantities are directly
related (Fig- 10) [12].

Fig- 8 Forces and distance between atoms [12].

When two atoms come very close, the

force between them is always repulsive,
because the electrons stay outside and the
nuclei repel each other. Unless both atoms are
ions of the same charge (e.g., both negative)
the forces between atoms is always attractive at
large internuclear distances r. Since the force is
repulsive at small r, and attractive at small r,
there is a distance at which the force is zero.
This is the equilibrium distance at which the
atoms prefer to stay (Fig- 9) [12].
The interaction energy is the potential energy
between the atoms. It is negative if the atoms
are bound and positive if they can move away
[12]
Fig- 10 Energy Vs Separation distance .
The interaction energy is the minimum at the
equilibrium position. This value of the energy
is called the bond energy, and is the energy
needed to separate completely to infinity (the
work that needs to be done to overcome the
attractive force.) The strongest the bond
energy, the hardest is to move the atoms, for
instance the hardest it is to melt the solid, or to
evaporate its atoms [12].

Page 10 of 154
4.50 Atomic Bonds
Atomic Bonds are classified as primary and
Secondary Atomic bonds. The primary atomic
bonds are further classified as Ionic Bonds,
Covalent Bonds, and Metallic Bonds.
where the electrons spend more time in
between the nuclei than outside, thus
producing bonding (Fig- 12).

Ionic Bonding
This is the bond when one of the atoms is
negative (has an extra electron) and another is
positive (has lost an electron). Then, there is a
strong, direct Coulomb attraction. An example
is NaCl. In the molecule, there are more
electrons around Cl, forming Cl- and less
around Na, forming Na+. Ionic bonds are the
Fig- 12 Covalent Bonding
strongest bonds. In real solids, ionic bonding
is usually combined with covalent bonding. In
Metallic Bonding
this case, the fractional ionic bonding is
In metals, the atoms are ionized, loosing some
defined as %ionic = 100 × [1 – exp (-0.25
electrons from the valence band. Those
(XA – XB) 2], where XA and XB are the
electrons form a electron sea, which binds the
electronegativities of the two atoms A and B,
charged nuclei in place, in a similar way that
forming the molecule (Fig-11) [17].
the electrons in between the H atoms in the H2
molecule bind the protons. In metals, the atoms
are ionized, loosing some electrons from the
valence band known as metallic bonding.
Those electrons form an electron sea, which
binds the charged nuclei in place, in a similar
way that the electrons in between the H atoms
in the H2 molecule bind the protons (Fig- 13)
[18]
.

Fig-11 Ionic Bonding

Covalent Bonding
In covalent bonding, electrons are shared
between the molecules, to saturate the valence.
Fig-13 Metallic Bonding
The simplest example is the H2 molecule,

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Secondary Atomic Bond (Van der Waals)
Secondary Atomic and Molecular Bonds are
classified as Permanent Dipole Bonds and
Fluctuating Dipole Bonds.
Fluctuating Induced Dipole Bonds
Since the electrons may be on one side of the
atom or the other, a dipole is formed: the +
nucleus at the center, and the electron outside.
Since the electron moves, the dipole fluctuates.
Fig - 14 Van der Waals Bonds
This fluctuation in atom A produces a
fluctuating electric field that is felt by the
electrons of an adjacent atom, B. Atom B then
polarizes so that its outer electrons are on the
side of the atom closest to the + side (or
opposite to the – side) of the dipole in A. This
bond is van der Waals bonding (Fig-14) [18].
Polar Molecule-Induced Dipole Bonds
A polar molecule like H2O (Hs are partially +,
O is partially –), will induce a dipole in a
nearby atom, leading to induced dipole
bonding.
Permanent Dipole Bonds
This is the case of the hydrogen bond in ice.
The H end of the molecule is positively
charged and can bond to the negative side of
another dipolar molecule, like the O side of the
H2O dipole (Fig-15) [18].
Fig - 15 Permanent Dipole Bond in Ice
4.60 Chemical bonding Models
Chemical bonding models are theoretical
models used to explain atomic bonding
structure, molecular geometry, properties, and
reactivity of physical matter. Modern bonding
theories such as VBT, LFT, and MO theory
assume that bonds are formed by atoms
sharing electrons in directional orbital [18].
The Major Models
Valence Bond Theory (VBT), an early bonding
theory that has developed into Modern valence
bond theory. VBT views bonds as weakly
coupled orbitals, with each atom sharing a
valence electron in a manner governed by the
octet or 18 electron rules. Lewis structures are
a representation of VBT's most basic bonding
while molecular geometry is derived from
orbital hybridization [18].
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VSEPR
Valence shell electron pair repulsion (VSEPR)
theory describes molecular geometry through
the repulsion of electron fields which include
bonds and lone pairs and does not require any
application of orbital shape [18].
Crystal Field Theory (CFT)
CFT is an approximation that begins with the
geometries of the d orbitals derived from
quantum mechanics. Ligands (an atom, ion, or
molecule) with their electron density are
assumed to destabilize the metal d- orbitals and
they interact with raising their energy while the
remaining d-orbitals drop in energy to balance
the overall change in energy [18].
Ligand Field Theory (LFT)
LFT is a hybrid of CFT and MO Theory. It is a
simple application of MO Theory to transition
metal compounds [18].
Molecular Orbital (MO)
Molecular Orbital (MO) theory is a current and
often applied model of molecular bonding. MO
Theory assumes that bonds are derived from a
linear combination of atomic orbitals and each
pair of atomic orbitals involved in bonding
results in a bonding and anti-bonding orbital.
The destabilized orbitals of CFT are now seen
as anti-bonding component of orbitals that
have overall been stabilized through bonding
interactions [18].
4.70 Electronic band structure
The band structure of a material determines a
number of characteristics such as electronic,
optical properties etc. The band structure of a
solid describes ranges of energy that an
electron is limited to have due to the
diffraction of the quantum mechanical electron
waves in the periodic crystal lattice [18].
When several atoms are brought together to
form a molecule, their atomic orbitals split, as
in a coupled oscillation. This produces a
number of molecular orbitals proportional to
the number of atoms. When a large number of
atoms (of order 1020 or more) are brought
together to form a solid, the number of orbitals
becomes exceedingly large, and the difference
in energy between them becomes very small,
so the levels may be considered to form
continuous bands of energy rather than the
discrete energy levels of the atoms in isolation.
However, some intervals of energy contain no
orbitals forming band gaps [18].
This band gap is one of the most useful aspects
of the band structure, as it strongly influences
the electrical and optical properties of the
material. Electrons can transfer from one band
to the other by means of carrier generation and
recombination process. The band gap and
defect states created in the band gap by doping
can be used to create semiconductor devices
such as solar cells, diodes, transistors, laser
diodes, and others [18].
Basic concepts
Theoretically, a solid has a large number of
bands but a few lie at energies so high that any
electron that reaches those energies escapes
from the solid. These bands are usually
disregarded. Bands have different widths,
based upon the properties of the atomic
orbitals from which they arise. Allowed bands
may overlap, producing a single large band.
Metals contain a band that is partly empty and
partly filled regardless of temperature;
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therefore, they have very high conductivity.
The lowermost, almost fully occupied band in
an insulator or semiconductor is called the
valence band by the valence electrons of
individual atoms. The uppermost, almost
unoccupied band is called the conduction band
because only when electrons are excited to the
conduction band current flows in these
materials. The difference between insulators
and semiconductors is only that the forbidden
band gap between the valence band and
conduction band is larger in an insulator, so
that fewer electrons are found there and the
electrical conductivity is lower. Because one of
the main mechanisms for electrons to be
excited to the conduction band is due to
thermal energy, the conductivity of
semiconductors is strongly dependent on the
temperature of the material.
Band theory
The electronic structure of solids can also be
described by MO theory. A solid can be
considered as a supermolecule. One mole of
atoms (NA), each with X orbitals in the
valence shell contributes X moles of atomic
orbitals producing X moles of MO’s.
(Consider qualitatively bonding between N
metal atoms of ns1 configuration (Li, Na etc)
arranged in a chain; N = 2, 4, NA. If X=1, then
N ~ NA and they do not form bonds but they
do form bands [18-26].
Fig- 16, ns1 chain configuration (Li, Na)
The band appearing in the bonding region is
called valence band. The antibonding region is
called conduction band. In the case of metals
the valence and conduction bands are
immediately adjacent (Fig-16).
If an electrostatic potential is applied to a
conductor, the energy levels will tend to
change the electrons and they will be able to
flow using empty adjacent conduction band
(Fig-17) [18-26].
Fig-17 Intrinsic conductivity in semiconductors and
insulators
In the case of insulators and semiconductors,
the energy gap between the valence and
conduction bands is more or less significant;
electrons cannot easily get into the conduction
band and thermal or photo-energy is needed to
bring some electrons to the conduction band
(Fig-18) [18-26].
Fig- 18, Electronic band structure of metals,
semiconductors, and insulators.
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 Crystal orbitals (Bloch functions)
If N hydrogen atoms with atomic wave
functions (m = 1 … N) related by
symmetry and spaced at distance a, we can get
N MO’s (n = - N/2, …, 0, …, N/2) which
are called Bloch functions. For the n-th crystal
orbital, , we will have:

Fig- 19, Elements with band gaps and conductivities.

When n changes from 0 to N/2, variable k =
2πn / (aN)) (wave vector) changes from 0 to
Some elements with their respective band gaps
π/a and the type of the MO changes from the
and conductivities are tabulated in Fig-19 [18-
26]. completely bonding to the completely
antibonding as shown below in Fig-21,
Crystal Orbital theory 22.
The band structure of a crystalline material of
virtually any complexity can be found through
the application of the Molecular Orbital (MO)
theory for solid state materials (Crystal Orbital
theory). One of the ways to model a real (finite
size) crystal is by using cyclic boundary
conditions by assuming that a chain of bound Fig-21 Bonding to antibonding
atoms forms a very large ring. It turns out that
the energy levels in a cyclic molecule
composed of N hydrogen atoms look as shown
below in Fig-20 [18-26].

Fig-22 Energy levels of set of Molecular orbitals

Energy levels of the resulting set of MO’s

Fig-20 Energy levels N Molecular orbitals (band structure) can be described with help of

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continuous functions E and density of states Basically cluster calculations are molecular
(DOS) dn/dE [18-26]. orbital calculations carried out on a cluster
shown in Fig-24.
Bonding in Crystalline Metals
Crystal orbital theory can be used to rationalize
the well known fact that the metals with
highest melting points are those belonging to
6th and 7th groups as shown in Fig-23.

Fig-23 Crystal Orbital overlaps

A common way to analyze bonding in solids is

by calculating and analyzing the crystal orbital
overlap population (COOP). COOP is defined
in the same way as the bond order is defined in
MO theory of molecules. For any two atoms i
and j
COOP (i-j) = S2cicjSij
(Sij is the overlap integral for two atomic wave
functions; summation is performed for all pairs
of overlapping orbitals of atoms i and j). A
negative value of COOP means antibonding
situation while a positive value is characteristic
for bonding [18-26].
Cluster model
Cluster Model takes into account the
interaction of a metal atom with surrounding
Ligand atoms (oxygen in the case of oxides).
Fig- 24, Molecular orbital diagram for a octahedral MO6
Unit.
The MO diagram of a transition metal ion
octahedrally surrounded by 6 oxygen (Oh point
group).The different orbitals arises from the
combination of metal d orbitals and oxygen p
orbitals [20].
5.0 Crystals
A Crystal is defined as a solid composed of
atoms arranged in a periodic pattern in three
dimensions (3D) [19]. However, not all solids
are crystalline; some solids do not possess a

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periodic arrangement and are called amorphous one lattice point per cell. The number of lattice
or “undercooled liquids”. points is given by the following equation,
where Ni is the number of interior points, Nf is
5.10 Crystal Lattice Structures the number of face centered points and Nc is
the number of corner points:
Unit Cell
Periodicity in crystals is generally represented
by replacing the repeating unit by a point, the
resulting array of such points in space is called
lattice. In a space lattice the translation vectors, The symbols ‘f’ and ‘i’ refers to face-centered
a, b, c in the crystallographic directions define and body-centered cells, respectively, while A,
a primitive cell. B, C base-centered cells, centered on one pair
of opposite faces A, B, C (the A face is the
When a primitive cell or some other suitable face defined by b and c axes, etc.) [19-21].
combination is chosen as the repeating unit of
the lattice, it is referred to as the unit cell (Fig- Seven Crystal Systems
6). A crystallographic unit cell is defined by The seven crystal systems are detailed in Fig -
three translation vectors a, b, and c; and three 26 below.
angles α, β and γ. The most common types of
unit cells are the faced-centered cubic (FCC),
the body-centered cubic (BCC) and the
hexagonal close-packed (HCP). Other types
exist, particularly among minerals.

Fig - 25 Three Dimensional Unit Cell

A simple, or primitive, unit cell (symbol P or R

in the Fig-25), has only one lattice point per Fig -26, Seven Crystal Systems and Bravais Lattices
[18-
cell; a non-primitive unit cell has more than 20].

Page 17 of 154
The Bravais Lattices
In 1848 the French crystallographer Bravais
demonstrated that there are fourteen possible
lattice points by arranging the points in 3D. It
was so arranged that each point has
[statistically] identical surroundings [20]. The
14 Bravais lattices are detailed in Fig-27
below.
Fig -27, Bravais Lattices
The 14 Bravais lattices are as follows: (1)
triclinic P, (2) monoclinic P, (3) monoclinic C,
(4) orthorhombic P, (5) orthorhombic C, (6)
orthorhombic 1, (7) orthorhombic F, (8)
tetragonal P, (9) tetragonal 1, (10) cubic P,
(11) cubic 1, (12) cubic F, (13) hexagonal P,
(14) trigonal R (Fig -28) [21].
There are only 14 Bravais lattices because of
the unit cell selection is made based on the
following criteria,
o Highest symmetry
o Consistency with past convention to
minimize unit cell volume
o Satisfaction of minimal symmetry
requirements
Which limits the maximum of 14 lattices and
several of these criteria are used to define the
cell structure of a crystal.
Fig – 28, Fourteen Bravais Lattices
[18-20]
A crystal's structure and symmetry play a role
in determining many of its properties, such as
cleavage, electronic band structure, and optical
properties [20].
5.20 Types of crystals based on bonding
Based on bonding considerations five types of
crystals can be defined, which are ionic,
Page 18 of 154
covalent, metallic, molecular and hydrogen
bonded.
Ionic Crystals
These types of crystals are usually formed
between highly electro-positive and highly
electro-negative elements which favor electron
transfer. The atoms themselves are ionized
because the elements with higher electro-
negativity obtain the valence electrons of the
element with the low electro-negativity.
The different types of atoms become
oppositely charged and, are held together by
electrostatic forces. Ionic crystals such as NaCl
have relatively high melting points and are
hard. The cohesive energy calculations can not
be used to predict the structure of an ionic
solid.
Covalent Crystals
These crystals have covalent bonding between
all the atoms present in the crystal. These
crystals generally have high melting points and
are non-conductors. Diamond and zinc sulfide
are examples of covalent crystals.
Metallic Crystals
In metallic crystals individual metal atoms sit
on lattice sites, while the valence electrons
from each atom flow freely around the lattice.
Metallic crystals have high densities along
with high melting points.
Molecular Crystals
In this type of crystal, molecules within the
crystal are held together by secondary bonds
such as van der Waals forces or hydrogen
bonding (Eg- Sugar). Molecular crystals are
generally soft and have low melting points.
Hydrogen Bonded Crystals
Crystals with hydrogen bonds are a special
type of dipole-dipole force that exists between
an electronegative atom and a hydrogen atom
bonded to another electronegative atom. This
type of force always involves a hydrogen atom
and the energy of this attraction is close to that
of weak covalent bonds (155 KJ/mol). These
attractions can occur between molecules
(intermolecular), or within different parts of a
single molecule (intramolecular).
The hydrogen bond is a very strong fixed
dipole-dipole van der Waals-Keesom force, but
weaker than covalent, ionic and metallic
bonds. In many Oxide Hydrates or Hydrogen
oxides, hydrogen bonding contributes to the
cohesive energy.
5.30 Defects in Crystals
A perfect crystal, with every atom of the same
type in the correct position, does not exist. All
crystals have some defects. Defects contribute
to the mechanical properties of metals. Defect
is intentionally used to manipulate the
mechanical properties of a material. Adding
alloying elements to a metal is one ways of
introducing a crystal defect.
The basic classes of crystal defects are as
follows:
Point defects are places where an atom is
missing or irregularly placed in the lattice
structure. Point defects include lattice
vacancies, self-interstitial atoms, substitution
impurity atoms, and interstitial impurity atoms.
Linear defects are groups of atoms in irregular
positions. Linear defects are commonly called
dislocations.
Page 19 of 154
Planar defects are interfaces between
homogeneous regions of the material. Planar
defects include grain boundaries, stacking
faults and external surfaces.
Plastic deformation in a material occurs due to
the movement of dislocations (linear
defects).Any defect in the regular lattice
structure disrupts the motion of dislocation,
which makes slip or plastic deformation more
difficult. The defects of Oxides are explained
in detail in the Transition Metal Oxide section
[20]
. insulating
6.0 Metal Oxides
Multiferroic materials are poly crystals, which
belong to the family of “Transition Metal
oxides”. Metal Oxides are formed when metals
are oxidized by oxygen. Metal oxides can be
classified into two classes Non Transition
Metal Oxides and Transition Metal Oxides.
metallic (e.g. TiO). Other properties, especially
the "high-temperature" superconductivity of
mixed oxides (cuprates) have been recently
discovered. The typical examples of these
complex oxides crystal structure for cubic and
layered perovskites are given in Fig-29.
In Transition Metals (TM) the valence
electrons may be present in more than one
shell, making most TM to have more than one
oxidation state. The oxides of TM show a rich
variety of electronic properties, ranging from
to metallic and even
superconducting behavior. The same applies to
their magnetic properties, where every- thing is
found from Pauli paramagnetism to local
moment behavior including the occurrence of
ferromagnetism and antiferromagnetism.

6.11 Non-Transition Metal oxides

Oxides of non-transition metals, (Na2O, MgO,
Al2O3, SiO2) consist of a filled valence band
(derived from oxygen 2p) and an empty
conduction band (derived from the outer shells
of the metal atoms), separated by a large gap.
Such oxides are therefore diamagnetic
insulators under ordinary conditions. Since the
intrinsic activation energy for electronic
conduction is higher than the energy required
for the creation and migration of point defects,
ionic conduction predominates over electronic
conduction in many of these oxides at
moderately high temperatures [20-22].

6.12 Transition metal oxides
Transition metal oxides (TMO) are a series of
compounds with a uniquely wide range of
electronic properties from insulating (e.g.
Cr2O3), semi-insulating (e.g.BaBiO3) and
Fig – 29, Crystal structure of functional oxides
Additionally, these materials can often be
tuned from one electronic or magnetic phase to

Page 20 of 154
another by varying the temperature, pressure, accommodate oxygen-deficient non-
or by doping. Therefore, the transition metal stoichiometry (e.g. WO3−x, TiO2−x) without
oxides (TMO) have been the subject of intense oxygen vacancies could all be traced to a soft
experimental and theoretical studies for a long M-O potential that is again a direct
time. consequence of the out-of-centre distortion of
MO6 octahedra in d0 metal oxides [26-27].
Especially d-band TMO are of interest because
of their catalytic properties. Transition metal
oxides are used in a wide variety of
technologically important catalytic processes.
For example, they are used in selective
oxidation, selective reduction and
[20-22]
dehydrogenation .

The transition metal oxides form a large, rich

and still not well understood class of
compounds. These materials can have unusual
and useful electronic and magnetic properties.
Many of these properties strongly depend on
material defects like vacancies, dislocations,
stacking faults and grain boundaries. Fig - 30, Structures of do Oxides

The oxides of the early transition-metals 6.2 Structures of Transition metal oxides
(periodic groups 4, 5, 6 and 7) containing d0 Transition metal oxides can be classified into
and d1 electronic configurations are a special four basic structures based on crystallization
subclass, distinctly different from the other which are Rock Salt, Rutile, Corundum and
transition-metal oxides, showing several Perovskites. The basic structures are of three
unique features. types AX- type, AmXp type and AmBnXp
type (Fig-31) [20-22].
For example, crystal structures of d0 metal
oxides consist of distorted metal oxygen (MO6)
octahedra where the cation is displaced from
the centre of the octahedron (Fig-30) [20-22].
Several of the interesting features of these
oxides can be directly traced to this distortion.
The occurrence of layered structures and
distinct oxide hydrates for V2O5, MoO3 and
Re2O7 is a direct consequence of the distortion.
The high static relative permittivity and the
consequent ferroelectric behavior, the presence
of soft phonon modes and the ability to Fig - 31, Types of TMO Structures

Page 21 of 154
6.21 Rock Salt
Rock salt crystal structure is highly ionically
bonded. Large anions are arranged in cubic
close packing and all the octahedral interstitial
positions are filled with cations in this
structure. This structure has an octahedral
coordination (CN = 6). This type of
coordination predicted from the radius ratio
calculation of cation to anion should be 0.732-
0.414.
Fig -32 Rock Salt Structure
Eg: The NaCl is anion ccp (fcc). Radius Na+ =
1.02Å, radius Cl- = 1.81Å; radius ratio = 0.563.
So in the Na octahedral, each octahedral has
one anion, thus 100% octahedral sites are
filled. The coordination # Na = 6; coordination
# Cl = 6. Therefore, there is an fcc
arrangement of the Na cations and Cl anions.
For an fcc lattice there are 4 lattice points per
cell, the motif in this case is a Na cation and a
Cl anion. Therefore the cell contents are 4 Na
cations + 4 Cl anions (Fig -32) [28].
6.22 Rutile
TiO2 (titanium dioxide) is a nominal rutile
structure. It can be thought of as infinite
columns of edge sharing TiO6 octahedra. In
addition, it has its each edge-shared oxygen,
corner-shared with an adjacent infinite chain.
Each Ti is coordinated to 6 oxygen atoms (by
definition for octahedral coordination) and
each oxygen atom is coordinated to 3 titanium
atoms, 2 within a column, and 1 within the
adjacent column [28].
Titanium dioxide occurs naturally as the
mineral Rutile. The ionic radius of the titanium
(IV) ion is 0.745 Å and that of the oxide ion is
1.26 Å. The ratio of radii for the cation and
anion is thus r+/r- = 0.745/1.26 = 0.591. With a
radius ratio of 0.591, the cubic holes are too
large (r hole/r = 0.732). The titanium ions will
prefer to occupy octahedral holes in a close-
packed structure. The oxide ions in rutile pack
in a hexagonal close-packed structure. The
images below depict the structure of Rutile.
The red spheres represent the oxide ions and
the blue spheres represent the titanium (IV)
ions (Fig-33) [28].
Fig -33, Rutile Structure of Ti O2
Page 22 of 154
Rutile Derivative: ABO4, ordered and
disordered
Two different metals can replace Ti in the
rutile structure giving a new formula of ABO4,
keeping the metal-oxygen ratio. If the metals
are disordered on the site, then the
crystallographic description remains the same,
with 50% of each metal on the Ti site. While
this is most often the case, the metals can also
be ordered. Fig-34 shows structure of CoReO4.
Fig-34, CoReO4 rutile structure
In a 1-2-6 ratio, the metal cations will have the
same basic skeleton as rutile, but the cations
will order is such a way as to triple the c-axis,
i.e. the axis pointing along the infinite edge-
sharing columns. FeTa2O6 is shown below as
an example (Fig-35) [28].
Fig-35, FeTa2O6 tri-rutile structure
Skew-edge sharing, alpha PbO2 / columbite
structures
In some situations, the MO6 octahedra will
share skew edges and the infinite edge-sharing
columns become zigzagged instead of straight.
However, the edge-shared oxygen atoms still
share 1 corner with an adjacent chain and in
that sense the structure is the same as rutile. In
the Fig-36 below, FeWO4 is used as an
example. In the upper left, only the FeO6
octahedra are shown. In the upper right, the
WO6 octahedra are added, but the structure
orientation is the same. Two simplified
versions from the side are shown in the lower
panels [28].
In the case of ABO4, the A and B cations are
ordered on the two different sites typified by
Fe and W. In the case of AO2, e.g. alpha-PbO2,
the Fe and W sites are equivalent, and
occupied by the same cation (Fig-36) [28].
Fig-36, FeTa2O6 tri-rutile structure
Page 23 of 154
6.23 Corundum
The corundum structure is a general structure
of a class of minerals consisting of hexagonal
close packed O atoms with cations filling up
2/3 of the central octahedral sites. The cations
occur two in a row and they skip a site. This
pattern is staggered for adjacent rows. An
example is given in Fig-37.
Fig- 37 Corundum Structure – Al2O3
Al2O3 has a space group of R-3c, Number: 167,
Pearson symbol: hR10, Unit cell dimensions: a
= 4.758 Å, c = 12.991 Å, 90° 90° 120°,
Atomic positions: Al at (0, 0, 0.355), O at
(0.303, 0, 1/4) [28].
6.24 Pervoskite Structures
Perovskites are a large family of crystalline
ceramics that derive their name from a specific
mineral known as perovskite. The parent
material, perovskite, was first described in the
1830's by the geologist Gustav Rose, who
named it after the famous Russian mineralogist
Count Lev Aleksevich von Perovski. Number
of isostructural ternary oxide families exhibit
pervoskite, spinel, garnet, pyrochlore, K2NiF4,
and other structures whose electrical and
magnetic properties have been extensively
studied.
Multiferroics are perovskites with general
formulas of ABO3 and A2BBO68 with units of
cubic cell type (eg-LaxTiO3), tetragonal type
(eg-BaTiO3) and orthorhombic type (eg-
GdFeO3) structures (Fig-38) [28].
Fig- 38 Perovskite Structure
Many different types of distortions can occur
from the ideal structure of perovskites. These
include tilting of the octahedra, displacements
of the cations out of the centers of their
coordination polyhedra, and distortions of the
octahedra driven by electronic factors (i.e.
Jahn-Teller distortions). Multiferroic materials
have a slightly deformed symmetry with the
3m point symmetry group instead of the ideal
cubic symmetry m3m [28].
Many of the physical properties of perovskites
depend crucially on the details of these
distortions, particularly the electronic,
magnetic and dielectric properties which are so
important for many of the applications of
Page 24 of 154
perovskite materials. Some examples of
Pervoskites are given and discussed below.
Cubic Perovskite
The principle perovskite structure found in
ferroelectric materials is a simple cubic
structure containing three different ions of the
form ABO3. The A and B atoms represent +2
and +4 ions, respectively, while the O atom is
the Oxygen-2 ion.
This ABO3 structure is a face centered cubic
(FCC) lattice with A-atoms at the corners and
O atoms on the faces. The B atom completes
the picture and is located at the center of the
lattice. This A-atom is the largest of the atoms
and consequently increases the overall size of
the ABO3 (fcc) structure. As a result, there are
minimum energy positions off centered from
the original octahedron that can be occupied by
the B atom. Shifting of this atom due to
applied electric fields causes the structure to be
altered, creating electric dipoles Eg SrTiO3
(Fig-39) [28].
Fig: - 39. SrTiO3 - Cubic Perovskites
This structure can be visualized in terms of the
BO6 octahedra which share corners infinitely
in all 3 dimensions, making a symmetric
structure. The A cations occupy every hole
which is created by 8BO6 octahedra, giving the
A cation a 12-fold oxygen coordination, and
the B-cation a 6-fold oxygen coordination.
In (SrTiO3) the Sr atoms sit in the 12
coordinate A-site, while the Ti atoms occupy
the 6 coordinate B site. There are many ABO3
compounds for which the ideal cubic structure
is distorted to a lower symmetry (e.g.
tetragonal, orthorhombic, etc.) [28].
Sr2FeMoO6 - Double Perovskites
The double perovskite structure is named
because the unit cell of it is twice that of the
perovskite. It has the same architecture of 12
coordinate A- sites and 6 coordinate B sites,
but two cations are ordered on the B site.
Fig: - 40, Sr2FeMoO6 - Double Perovskites
Page 25 of 154
The example shown here is Sr2FeMoO6. The
Fe and Mo atoms have ordered in a 3D
chessboard type fashion (Fig-40) [28].
Layered Perovskites
Layered Perovskites can be identified as
Ruddleson-Popper, Aurivillius and Dion-
Jacobson phases. Layered perovskites consist
of infinite 2D slabs of the ABO3 structure
which are separated by some motif. The
general formula for the layered perovskite is:
A(n-1)B(n)O(3n+1). The differentiating
characteristics for the layered perovskites are
o The motif which separates the layers, and
o The offsetting of the layers from each
other.
In this formula, "n" indicates the size of the 2D
slabs. n=1 means the slab is one BO6
octahedron thick. n=2 means two BO6
octahedra thick, etc. The clearest examples of
this are the n=1 and n=2 Ruddleson-Popper
phases Sr2RuO4 and Sr3Ru2O7 (Fig-41) [28].
Fig: - 41, Ruddleson-Popper phases Sr2RuO4 and
Sr3Ru2O7
For these phases, Sr is the A cation, and Ru is
the B cation. The separating motif is a layer of
Sr2, and the perovskite slabs are offset by a
(1/2, 1/2) translation. Ruddleson Popper phases
has the general formula as A(n+1)BnO(3n+1),
indicating that the outer A atoms are part of the
2D perovskite slabs.
Aurivillius phases
The n=2 phase Bi3TiNbO9 is representative of
the Aurivillius phases, for which the general
formula is {Bi2O2}-{A(n-1) B2O7}.
For this phase, Ti and Nb are statistically
dispersed on the B site. The formula can be re-
written as: {Bi2O2}-Bi (Ti, Nb)2 O7. The
separating motif for all Aurivillius phases is a
rock-salt Bi2O2 layer. Bi is also the A cation,
but that need not be the case. The displacement
of the perovskite slabs is a (1/2, 1/2)
translation (Fig-42) [28].
Fig: - 42. Aurivillius phases of Bi2O2
Page 26 of 154
Dion-Jacobson phases
The Dion-Jacobson phases have the general
formula M+1A(n-1)BnO(3n+1). They differ from
the other layered phases by having a layer of
alkali metal as the separating motif. Below is a
picture of KLaNb2O7 and CsLaNb2O7. The
displacement of the perovskite slabs is either
(1/2, 0) or nothing at all depending upon which
alkali metal is used as the separating motif.
The crystal structures of d0 metal oxides
consist of distorted metal–oxygen (MO6)
octahedra where the cation is displaced from
the centre of the octahedron, creating several
of the interesting features of these oxides (Fig-
43) [28].
Fig-43 Dion-Jacobson phases of KLaNb2O7 and
CsLaNb2O7
Spinel structure
Spinel structure oxides with the formula of
AB2O4, are well-known magnetic materials.
Ferrimagnetic CoCr2O4 has a conical spiral
configuration. Some of the spinels (e.g.,
FeCr2O4) exhibit Jahn-Teller effect. Other
oxides showing this effect are rare earth
zircons (e.g., TbVO4, DyVO4) and PrAlO3. In
vandate spinels, AV23+O4, the d electrons are
localized when 2.88A < Rv-v< 2.97Α. Fe3O4 is
an inverse spinel. The spinels Li1-xM2+xTi2O4
where (M=Mg, Mn) and Li1+xTi2O4 shows
superconductivity.
Some of these hydrogen bronzes, Di- and
monophosphate tungsten bronzes of the type
Ax(PO2)4(WO3)2m (A = Na, K, Rb, or Ba)
possess hexagonal tunnels. The tunnels may be
empty, as in the monophosphate bronze
P4W8O32 (m=4), or occupied, as in the
diphosphate tungsten bronzes. CsP8W9O40, has
a unique anisotropic structure [20-28].
6.241 Spinel (MgAl2O4)
Spinel, MgAl2O4, is a rare gemstone that was
used to imitate rubies. The structure has face-
centered cubic symmetry and the general
formula is AB2O4. The oxygen atoms form an
fcc lattice. The A cations occupy tetrahedral
holes, and the B cation occupy octahedral
holes. It then follows that 1/8 of the tetrahedral
holes, and 1/2 of the octahedral holes are
occupied. The array of Al atoms sit on the
corners of tetrahedra which share corners
infinitely in 3 dimensions, an array known as a
Kagome net.
Fig- 44 Spinel structure of MgAl2O4
Page 27 of 154
The image above shows Al atoms sitting on the
corners of tetrahedral and the Mg atoms sitting
in tetrahedral holes (Fig-44) [28].
6.3 Properties of Transition Metal Oxide
Physical properties of metal oxides arise as
responses to external stimuli like mechanical
stress, electrical field, magnetic field and
temperature. The important properties TMO
are Electronic, magnetic, dielectric, optical and
catalytic properties. Also the metal to Non
metal transition Phenomenon and Super
conductivity is of notable importance [28].
6.31 Electronic Properties of TM Oxides
Transition metal oxides can be classified into
two classes based on its electronic
configuration those in which the metal ion has
d0 electronic configuration (empty d shell) and
those in which d shell is partially filled (Fig-
45). The d0 class of oxides has a filled oxygen
2p valence band and an empty metal d
conduction band; the energy gap is around 3-
5eV. High purity oxides of this class exhibit
intrinsic electronic conduction only at high
temperatures.
With the d0 cations at octahedral sites, the
oxides exhibit spontaneous ferroelectric
distortions (e.g., WO3). Many lose oxygen at
high temperatures, becoming
nonstoichiometric. Oxygen loss or insertion of
electropositive metal atoms into these oxides
promotes electrons to the conduction band.
The nature of electronic conduction in these
materials depends on the strength of electron-
phonon coupling and the width of the
conduction band derived from metal d states.
When the coupling is large and the band is
narrow, small polarons are formed and such
materials (e.g., NaxV2O5) exhibit hopping
conduction. When the conduction band is
broad, the material (e.g., NaxWO3) exhibits
metallic properties.
Transition metal oxides with partially filled d
bands can be metallic or insulating. Some of
them exhibit temperature-induced non metal-
to-metal transitions. Magnetic properties vary
anywhere from Curie-Weiss paramagnetism to
Pauli paramagnetism (through spontaneous
magnetism). Rare earth metal oxides
containing localized 4fn electrons are generally
insulators or hopping semiconductors and
exhibit paramagnetism [28].
Transition metal oxides with the dn
configuration exhibit metallic properties when
the overlap between orbitals of the valence
shells of constituent atoms is large. Two kinds
of metallic behavior can be distinguished: one
due to strong cation-cation interaction arising
from a small cation-cation separation, and the
other due to strong cation-anion-cation
interaction arising from a large covalent
mixing of oxygen 2p orbitals with cation d
orbitals. Iso-structural series of transition metal
oxides, possessing rock salt, corundum, rutile,
and perovskite structures, exhibit systematic
changes in electronic properties, wherein at
least one member of the series shows
properties of itinerant electrons while others
exhibit properties due to localized electrons [20-
28]
.
0
d (Empty d shell)
The d0 class of oxides has a filled oxygen 2p
valence band and an empty metal d conduction
band; the energy gap is around 3-5eV. High
purity oxides of this class exhibit intrinsic
electronic conduction only at high
temperatures. With the d0 cations at octahedral
sites, the oxides exhibit spontaneous
Page 28 of 154
ferroelectric distortions (e.g., WO3). Many lose Iso-structural series of transition metal oxides,
oxygen at high temperatures, becoming possessing rock salt, corundum, rutile, and
nonstoichiometric. perovskite structures, exhibit systematic
changes in electronic properties, whereas at
Oxygen loss or insertion of electropositive least one member of the series shows
metal atoms into these oxides promotes properties of itinerant electrons while others
electrons to the conduction band. The nature of exhibit properties due to localized electrons [20-
22].
electronic conduction in these materials
depends on the strength of electron-phonon
coupling and the width of the conduction band
derived from metal d states. When the coupling
is large and the band is narrow, small polarons
are formed and such materials (e.g., NaxV2O5)
exhibit hopping conduction. When the
conduction band is broad, the material (e.g.,
NaxWO3) exhibits metallic properties [20-22].

dn (Partially Filled d shell)

Transition metal oxides with partially filled d
bands can be metallic or insulating. Some of
them exhibit temperature-induced non metal-
to-metal transitions. Magnetic properties vary
anywhere from Curie-Weiss paramagnetism to
Pauli paramagnetism (through spontaneous
magnetism). Rare earth metal oxides
containing localized 4fn electrons are generally
insulators or hopping semiconductors and
exhibit paramagnetism.

Transition metal oxides with the dn

configuration exhibit metallic properties when
the overlap between orbitals of the valence
shells of constituent atoms is large. Two kinds
of metallic behavior can be distinguished: one
due to strong cation-cation interaction arising
from a small cation-cation separation, and the
other due to strong cation-anion-cation
interaction arising from a large covalent
mixing of oxygen 2p orbitals with cation d
orbitals.
Fig-45, Electronic and magnetic properties of binary
transition metal oxides
6.32 Magnetic Properties
Oxides with positive magnetic susceptibility
are called Paramagnetic and those with
negative magnetic susceptibility are called
diamagnetic. Paramagnetic oxides generally
follow the Curie’s Law.

Page 29 of 154

Where M is the magnetization, H is the
magnetic field, XM the molar susceptibility and
C is the Curie constant. Because of the
interaction between atomic moments giving
rise to an internal field in the oxide, the
susceptibility is described by Curie- Weiss
Law
Where θ depends on the nature of magnetic
interaction (ordering) and can either be
positive, negative or zero. Clearly when θ = 0
then the Curie-Weiss law equates to the Curie
law. When θ is non-zero, there is an interaction
between neighboring magnetic moments and
the material is only paramagnetic above a
certain transition temperature.
If θ is positive, the material is ferromagnetic
below the transition temperature and the value
of θ corresponds to the transition temperature
(Curie temperature, TC). If θ is negative, the
material is antiferromagnetic below the
transition temperature (Néel temperature, TN)
and the value of θ does not relate to TN. This
equation is only valid when the material is in a
paramagnetic state.
It is not valid for many metals as the electrons
contributing to the magnetic moment are not
localized. However, the law does apply to
some metals, e.g. the rare-earths, where the 4f
electrons, that create the magnetic moment, are
closely bound. The Pauli model of
paramagnetism is true for materials, where the
electrons are free and interact to form a
conduction band, which is valid for most
paramagnetic metals. In this model the
conduction electrons are considered essentially
to be free and under an applied field an
imbalance between electrons with opposite
spin is set up, leading to a low magnetization
in the same direction as the applied field. The
susceptibility is independent of temperature,
although the electronic band structure may be
affected, which will then have an effect on the
susceptibility.
The paramagnetism of transition metal
compounds is different from that of rare earth
compounds, because of the involvement of d
electrons to varying degrees in crystal bonding.
Ferrimagnetism is only observed in
compounds, which have more complex crystal
structures than pure elements. Ferrimagnetism
is a phenomenon in which the magnetic
moments of the atoms on different sub lattices
are opposed and unequal; therefore, a
spontaneous magnetization remains.
This happens when two or more chemically
different magnetic species, occupy two kinds
of lattice sites producing two sub lattices A and
B. The moments of ions in each sublattice are
ferromagnetically coupled, but coupling
between the moments of A and B is
antiferromagnetic. Since the net moment of A
and B are different, there is a resultant
spontaneous magnetization.
The temperature dependence of ferrimagnetism
is similar to that of ferromagnetism except that
the spontaneous magnetization decreases more
rapidly with increase in temperature.
Ferrimagnetism can be observed in Fe3O4 and
Spinel ferrites [29-30].
Page 30 of 154
Fig- 46, Types of magnetism with details

Page 31 of 154
Types of Magnetism the spontaneous magnetization, although this
The magnetic behavior of a material can vary term is usually used to describe the
widely, depending on its structure, magnetic magnetization within a single magnetic
ordering, and electronic configuration. There domain. (Fig-47) gives some examples of the
are five major types of magnetism are saturation polarization (PS) and Curie
Diamagnetism, Paramagnetism, Ferro- temperature (TC) of materials commonly used
magnetism, Antiferromagnetism, and in magnetic applications [30-31].
Ferrimagnetism as detailed in Fig-46 [29-30].

The fundamental properties of a magnetic

material are characteristic of the material and
are unaffected by the microstructure. These
properties include the Curie temperature,
saturation magnetization and magneto
crystalline anisotropy.

Saturation Magnetization
The saturation magnetization (MS) is a
measure of the maximum amount of field that
can be generated by a material. It will depend
on the strength of the dipole moments on the
atoms that make up the material and how
densely they are packed together. The atomic
dipole moment will be affected by the nature
of the atom and the overall electronic structure
within the compound. The packing density of
the atomic moments will be determined by the
crystal structure (i.e. the spacing of the
moments) and the presence of any non-
magnetic elements within the structure.
For ferromagnetic materials, at finite
temperatures, MS will also depend on how well
these moments are aligned, as thermal
vibration of the atoms causes misalignment of
the moments and a reduction in MS. For
ferrimagnetic materials not all of the moments
align parallel, even at zero Kelvin and hence,
MS will depend on the relative alignment of the
moments as well as the temperature. The
saturation magnetization is also referred to as
Fig-47, Saturation polarization (PS) and Curie
temperature (TC) of a range of magnetic materials
Magnetic Anisotropy
Magnetic anisotropy is a phenomenon of
aligning the magnetic moment in an easy axis
in zero fields. Magnetic anisotropy is the
direction dependence of a material's magnetic
properties. A magnetically isotropic material
has no preferential direction for its magnetic
moment in zero fields, while a magnetically
anisotropic material will align its moment to an
easy axis.
In a crystalline magnetic material the magnetic
properties will vary depending on the
crystallographic direction in which the

Page 32 of 154
magnetic dipoles are aligned. (Fig-48)
demonstrates this effect for a single crystal of
cobalt. The hexagonal crystal structure of Co
can be magnetized easily in the [0001]
direction (i.e. along the center-axis), but has
hard directions of magnetization in the <1010>
type directions, which lie in the basal plane
(90° from the easy direction).
A measure of the magneto crystalline
anisotropy in the easy direction of
magnetization is the anisotropy field, Ha (Fig-
48), which is the field required to rotate all the
moments by 90° as one unit in a saturated
single crystal. The anisotropy is caused by a
coupling of the electron orbital to the lattice,
and in the easy direction of magnetization this
coupling is such that these orbital are in the
lowest energy state.
Fig-48, Magneto crystalline anisotropy of cobalt
The easy direction of magnetization for a
permanent magnet, based on ferrite or the rare
earth alloys, must be uniaxial, however, it is
also possible to have materials with multiple
easy axes or where the easy direction can lie
anywhere on a certain plane or on the surface
of a cone. The fact that a permanent magnet
has uniaxial anisotropy means that it is
difficult to demagnetize as it is resistant to
rotation of the direction of magnetization [29-31].
Magnetic Domains
A magnetic domain describes a region within a
material which has uniform magnetization.
This means that the individual moments of the
atoms are aligned with one another. The
regions separating magnetic domains are called
domain walls, where the magnetization rotates
coherently from the direction in one domain to
that in the next domain. The concept of
magnetic domains was proposed by Weiss to
explain that ferromagnetic materials with
spontaneous magnetization could exist in the
demagnetized state. The findings of his work
revealed that within a domain large numbers of
atomic moments are aligned typically 1012 to
1018, over a much larger volume than was
previously suspected. The magnetization
within the domain is saturated and will always
lie in the easy direction of magnetization when
there is no externally applied field. The
direction of the domain alignment across a
large volume of material is more or less
random and hence the magnetization of a
specimen can be zero.
Magnetic domains exist in order to reduce the
energy of the system. A uniformly magnetized
specimen has a large magnetostatic energy
associated with it (Fig- 49a). This is the result
of the presence of magnetic free poles at the
surface of the specimen generating a
demagnetizing field, Hd. From the convention
adopted for the definition of the magnetic
moment for a magnetic dipole the
magnetization within the specimen points from
the South Pole to the North Pole, while the
direction of the magnetic field points from
north to south. Therefore, the demagnetizing
Page 33 of 154
field is in opposition to the magnetization of In addition, the atomic dipoles within the wall
the specimen. The magnitude of Hd is are not at 180º to each other and so the
dependent on the geometry and magnetization exchange energy is also raised within the wall.
of the specimen. In general, if the sample has a
high length to diameter ratio and is magnetized
in the long axis, then the demagnetizing field
and the magnetostatic energy will be low.

The break up of the magnetization into two

domains reduces the magnetostatic energy by
half (Fig-49b). In fact, if the magnet breaks
down into N domains then the magnetostatic
energy is reduced by a factor of 1/N, hence
Fig- 49(c) has a quarter of the magnetostatic
energy of Fig-49(a). Fig- 49(d) shows a closure
domain structure where the magnetostatic
energy is zero, however, this is only possible
for materials that do not have a strong uniaxial
anisotropy, and the neighboring domains do
not have to be at 180º to each other.
Fig-50, Schematic representation of a 180º domain wall

Therefore, the domain wall energy is an

Fig-49, Schematic illustrations of the break up of
magnetization into domains (a) single domain, (b) two
domains, (c) four domains and (d) closure domains.
The energy associated with a domain wall is
proportional to its area. Within the domain
wall, the dipole moments of the atoms are not
pointing in the easy direction of magnetization
and hence are in a higher energy state (Fig-50).
intrinsic property of a material depending on
the degree of magneto crystalline anisotropy
and the strength of the exchange interaction
between neighboring atoms. The thickness of
the wall will also vary in relation to these
parameters, as strong magneto crystalline
anisotropy will favor a narrow wall, whereas a
strong exchange interaction will favor a wider
wall.
A minimum energy can be achieved with a
specific number of domains within a specimen.
This number of domains will depend on the
size and shape of the sample, which will affect
the magnetostatic energy and the intrinsic
magnetic properties of the material, which will
affect the magnetostatic energy and the domain
wall energy [29-31].

Page 34 of 154
Magnetic Hysteresis
Hysteresis is well known in ferromagnetic
materials. When an external magnetic field is
applied to a ferromagnet, the atomic dipoles
align themselves with the external field. Even
when the external field is removed, part of the
atomic dipole alignment will be retained and
the material will become magnetized. The
relationship between magnetic field strength
Fig-51, Hysteresis loop for a ferro or ferrimagnetic material.
(H) and magnetic flux density (B) is not linear
in such materials.
If the relationship between the two is plotted
for increasing levels of field strength, it will
follow a curve up to a point where further
increases in magnetic field strength will result
in no further change in flux density. This
condition is called magnetic saturation.
Page 35 of 154
If the magnetic field is now reduced linearly,
the plotted relationship will follow a different
curve back towards zero field strength at which
point it will be offset from the original curve
by an amount called the remnant flux density
or remanence.
If this relationship is plotted for all strengths of
applied magnetic field the result is a sort of S-
shaped loop. The 'thickness' of the middle bit
of S describes the amount of hysteresis, related
to the coercivity of the material.
Ferromagnetic and ferrimagnetic materials
have non-linear initial magnetization curves
(dotted lines in Fig-51), as the changing
magnetization with applied field is due to a
change in the magnetic domain structure.
These materials also show hysteresis and the
magnetization do not return to zero after the
application of a magnetic field. Fig- 51 shows
a typical hysteresis loop; the two loops
represent the same data, however, the red loop
is the polarization (P = µoM = B - µoH) and the
blue loop the induction, both plotted against
the applied field.
The first quadrant of the loop is the initial
magnetization curve (dotted line), showing the
increase in positive polarization (and
induction) on the application of a field to a
demagnetized sample, and are both in the same
direction. The polarization increases initially
by the growth of favorably oriented domains,
which will be magnetized in the easy direction
of the crystal. When the polarization can
increase no further by the growth of domains,
the direction of magnetization of the domains
then rotates away from the easy axis to align
with the field.
When all of the domains are fully aligned with
the applied field, the saturation is reached and
the polarization can increase no further. If the
field is removed the polarization returns along
the solid red line to the y-axis (i.e. H=0), and
the domains will return to their easy direction
of magnetization, resulting in a decrease in
polarization.
In Fig-51, the line from the saturation point to
the y-axis is horizontal, which is representative
of a well aligned material, where the domains
are magnetized in the easy direction of the
crystal at the saturation point.
When the direction of applied field is reversed
then the polarization will follow the red line
into the second quadrant. The hysteresis means
that the polarization lags behind the applied
field and will not immediately switch direction
into the third quadrant (negative polarization).
The polarization will only decrease after a
sufficiently high field is applied to nucleate
and grow domains favorably oriented with
respect to the applied field or rotate the
direction of magnetization of the domains
towards the applied field. After applying high
enough field saturation, polarization will be
achieved in the negative direction. If the
applied field is then decreased and again
applied in the positive direction then the full
hysteresis loop is plotted.
If the field is repeatedly switched from positive
to negative directions and is of sufficient
magnitude then the polarization and induction
will cycle around the hysteresis loop in a
counter-clockwise direction. The area
contained within the loop indicates the amount
of energy absorbed by the material during each
cycle of the hysteresis loop [29-31].
Page 36 of 154
Magnetic parameters
The hysteresis loop is used to measure the
various parameters to characterize magnetic
materials. The Saturation polarization, PS and
Saturation magnetization, MS can be measured
from the first quadrant. Most of the useful
information is derived from the second
quadrant of the loop [29-31].
Remanence
The field that is produced by the magnet after
the magnetizing field has been removed is
called the remanence, Br or Pr [29-31].
Inductive coercivity
The reverse field required to bring the
induction to zero is called the inductive
coercivity, bHc, whereas the reverse field
required to bring the magnetization to zero is
called the intrinsic coercivity, MHc. The
maximum value of the product of B and H is
called the maximum energy product, (BH)MAX
and is a measure of the maximum amount of
useful work that can be performed by the
magnet. (BH)MAX is used as a figure of merit
for permanent magnet materials.
In addition, the shape of the initial
magnetization curve and the hysteresis loop
can provide information about the magnetic
domain behavior within the material. The
squareness factor is a measure of how square
the loop is and is a dimensionless quantity
between 0 and 1, defined by the ratio of the
reverse field required to reduce P by 10% from
the remanence to Hcp. A squareness factor of
one therefore corresponds to a perfectly square
loop. There are several other methods to
quantify the squareness of the loop, such as the
ratio of Pr to Ps [29-31].
Coercivity-mechanisms
There are various methods of increasing or
decreasing the coercivity of magnetic
materials, all of which involve the controlling
of the magnetic domains within the material.
For a hard magnetic material it is desirable that
the domains cannot easily rotate on its
direction of magnetization and the domain
walls do not move easily and nucleation of
domains is difficult. However to prevent easy
rotation of domains the material could have a
strong uniaxial magneto crystalline anisotropy.
If the size of a magnetic particle / grain
decreases then there is a critical size below
which the decrease in magnetostatic energy by
splitting into two domains is less than the
increase in energy due to the introduction of
the domain wall. Particles that are below this
critical size are known as “single domain
particles”, and if they have sufficiently high
anisotropy to prevent the easy rotation of the
direction of magnetization then the particles
will be permanently magnetic and difficult to
demagnetize. This type of coercivity
mechanism can be observed in melt-spun
NdFeB magnets where the crystal size is
~50nm, compared to the critical size for single
domain particles of ~300nm [29-31].
Magnetoelasticity
Magnetoelasticity refers to the coupling of the
magnetic and elastic fields in a material.
Magnetostriction is the result of the
magnetoelastic coupling and refers to the
dimensional change undergone by a material in
the presence of a magnetic field. Most
ferromagnetic materials, such as iron and
nickel, show some measurable shape change
when subject to a magnetic field. The highest
room temperature magnetostriction of a pure
element is Co - 60 microstrains [29-31].
Page 37 of 154
However, alloying elements can produce much
larger magnetostriction even under a small
field; examples are: DyFe2, and TbFe2. There
are two processes that contribute to
magnetostriction on a macroscopic level. The
one is migration of domain walls in the
materials in response to the applied field and
second is the rotation of the domains. These
two mechanisms cause the dimensional change
in the material which in turn raises the strain
energy of the system (elastic properties of
materials are discussed later). When strain
energy increases the material tries to elongate
in both horizontal and vertical directions when
a field is applied, but this is not possible
because ferromagnetic material usually possess
triangular domains for closure and this
orientation does not enable the material to
elongate in both directions simultaneously
(Fig- 52b).
Fig-52, (a) Domain Structure after strain energy and
exchange energy compromise, (b) Triangular domain
structure for most ferromagnetics, (c) elongation due to
reorientation and rotation
However, the strain energy is reduced by
decreasing the volume of the domains, which
means additional domain walls will be needed.
This would in turn increase the exchange
energy; therefore, the final domain structure is
usually a compromise between the two, as
shown in Fig-52a. Furthermore, the
reorientation of the domains due to the two
mechanisms mentioned above is shown in Fig-
53c.
Ferroelasticity
Ferroelasticity is a phenomenon in which a
material may exhibit a spontaneous strain
when a stress is applied. The applied stress will
cause a phase change to occur in the material
from one phase to an equally stable phase
either of different crystal structure (e.g. cubic
to tetragonal) or of different orientation (a
'twin' phase). The shape memory effect and
super elasticity are manifestation of
ferroelasticity. Nitinol (nickel titanium), a
common ferroelastic alloy, can display either
superelasticity or the shape-memory effect at
room temperature, depending on the
nickel/titanium ratio.
Super elasticity
Pseudoelasticity / Superelasticity, is an elastic
(impermanent) response to relatively high
stress caused by a phase transformation
between the austenitic and martensitic phases
of a crystal. It is exhibited in Shape memory
alloys. Pseudoelasticity is from the reversible
motion of domain boundaries during the phase
transformation, rather than just bond stretching
or the introduction of defects in the crystal
lattice.
Even if the domain boundaries do become
pinned, they may be reversed through heating.
Thus, a pseudoelastic material may return to its
previous shape (hence, shape memory) after
the removal of even relatively high applied
strains. One special case of pseudoelasticity is
called the Bain Correspondence. This involves
the austenite/martensite phase transformation
Page 38 of 154
between a face centered crystal lattice and a
body centered tetragonal crystal structure [32-
33]
. can be manufactured to almost any shape and
Superelastic alloys belong to the larger family
of shape memory alloys. When mechanically
loaded, a superelastic alloy deforms reversibly
to very high strains - up to 10% - by the
creation of a stress-induced phase. When the
load is removed, the new phase becomes
unstable and the material regains its original
shape. Unlike shape-memory alloys, no change
in temperature is needed for the alloy to
recover its initial shape. Superelastic devices
take advantage of their large, reversible
deformation and include antennas, eyeglass
frames, and biomedical stents. Nickel Titanium
is an example of an alloy exhibiting
superelasticity [32-33].
Shape memory alloys
Shape memory alloy (SMA) / smart alloy is an
alloy that "remembers" its shape. After a
sample of SMA has been deformed from its
original crystallographic configuration, it
regains its original geometry by itself during
heating (one-way effect) or, at higher ambient
temperatures, simply during unloading
(pseudo-elasticity or superelasticity). These
extraordinary properties are due to a
temperature-dependent martensitic phase
transformation from a low-symmetry to a
highly symmetric crystallographic structure.
Those crystal structures are known as
martensite (at lower temperatures) and
austenite (at higher temperatures) [34].
The three main types of SMA are the copper-
zinc-aluminum-nickel, copper-aluminum-
nickel, and nickel-titanium (NiTi) alloys. The
Copper based and NiTi (Nickel and Titanium)
based shape memory alloys are considered to
be engineering materials. These compositions
size. The yield strength of shape memory
alloys is relatively low compared to
conventional steel, but some compositions
have a higher yield strength than plastic or
aluminum. The yield stress for NiTi can reach
500 [MPa]. The high cost of the metal and the
processing requirements make it difficult and
expensive to implement SMA's into design. As
a result, these materials are used in
applications where the superelastic properties
or the shape memory effect can be exploited.
The range of applications for SMAs, are
increasing in recent years in the fields of
consumer/commercial applications, industrial
applications, medical applications. Nitinol wire
is also used in robotics, Aerospace to reduce
aircraft Engine noise by Boeing, General
Electric Aircraft Engines, Goodrich
Corporation, NASA, and All Nippon Airways
[35]
.
6.33 Electrical Properties
Electrical conductivity or specific conductivity
is a measure of a material's ability to conduct
an electric current. The conductivity σ is
defined as the ratio of the current density to
the electric field strength :
On the basis of the electrical properties solid
materials can be classified into metals,
semiconductors and insulators, where the
charge carriers move in band states. In certain
semiconductors and insulators, charge carriers
are localized and their motion involves
diffusive process. The expression for electrical
conductivity σ of a metal is given by
Page 39 of 154

Where l is the mean free path and m is the
effective mass of the electrons, n is the density
of conduction electrons, e is the electron
charge [20-21].
Intrinsic Semiconductors
In intrinsic Semiconductors with both electrons
and holes as charge carriers,
σ = ni e (un + up)
ni = (NcNv)1/2exp (-Eg / 2kT)
Where Nc and Nv are the effective density of
states in the conduction and valence bands
respectively. un and up are electron and hole
mobility [20-21].
Extrinsic Semiconductors
In the presence of donors and acceptors, the
conduction is extrinsic at low temperatures.
kT<< Eg and σ exp( - Ed / 2kT)
If the donor concentration is higher than of the
acceptor the conduction becomes intrinsic at
high temperatures [20-21].
Thermoelectric effect
The thermoelectric effect is the direct
conversion of temperature differences to
electric voltage and vice versa. The term
thermoelectric effect or thermoelectricity
encompasses three separately identified effects,
the Seebeck effect, the Peltier effect, and the
Thomson effect.
The Seebeck Coefficient α, is the constant of
proportionality between the voltage and
temperature gradient that causes it when there
is no current flow. It is defined as ∆V/∆T as
∆T 0, where ∆V is the thermo – emf
caused by the temperature gradient ∆T; It is
related to the entropy transported per charge
carrier.
The expression for Seebeck Coefficient α for
metals is as follows.
Metals are characterized by a small | α| with
temperature [20-21].
Intrinsic Semiconductors
In intrinsic semiconductors α is given by
Where S* is the entropy by charge carriers
(S*/k < 10µ V/K in metal oxides and EF is the
Fermi energy relative to the appropriate band
edge. The sign of α is generally positive for
hole conduction and negative for electron
Page 40 of 154
conduction. So the above equation can be
expressed as follows.
Extrinsic semiconductors
In extrinsic semiconductors is α generally
large (0.1 – 1 mV/K) and decreases with
increasing temperature [20-21].
Hall Coefficient
The Hall Effect refers to the potential
difference (Hall voltage) on the opposite sides
of an electrical conductor through which an
electric current is flowing, created by a
magnetic field applied perpendicular to the
current. The ratio of the voltage created to the
power of the product of the amount of current
and the magnetic field (I*B), divided by the
element thickness, is known as the Hall
coefficient RH.
For a simple metal where there is only one
type of charge carrier (electrons) the Hall
voltage VH is given by
Where I is the current across the plate length,
B is the magnetic flux density, d is the depth of
the plate, e is the electron charge, and n is the
charge carrier density of the carrier electrons.
Where Cr ~ 1, e is the electron charge, and n is
the charge carrier density of the carrier
electrons.
Hall Effect in semiconductors
When a current carrying semiconductor is kept
in a magnetic field, the carriers of the
semiconductor experience a force in a direction
perpendicular to the magnetic field and current
field, this is called Hall Effect in
semiconductors.
Where Eh is the Hall field
The simple formula for the Hall coefficient
given above becomes more complex in
semiconductors where the carriers are
generally both electrons and holes which may
be present in different concentrations and have
different mobilities. For moderate magnetic
fields the Hall coefficient is
where is the electron concentration, the
hole concentration, the electron mobility ,
the hole mobility and the electronic
charge.
For large applied fields the simpler expression
analogous to that for a single carrier type holds
[20-21]
.
6.34 Superconductivity
Superconductivity is a transition phenomenon
occurring in certain materials at extremely low
temperatures, characterized by exactly zero
electrical resistance and the exclusion of the
interior magnetic field (the Meissner effect).
Page 41 of 154
The electrical resistivity of a metallic
conductor decreases gradually as the
temperature is lowered. However, in ordinary
conductors such as copper and silver,
impurities and other defects impose a lower
limit. Even near absolute zero a real sample of
copper shows a non-zero resistance. The
resistance of a superconductor, on the other
hand, drops abruptly to zero when the material
is cooled below its "critical temperature".
The Meissner effect is the expulsion of a
magnetic field from a superconductor and it is
a fundamental property of the superconducting
state. It is used as a means of detecting
superconducting transitions. There are two
kinds of superconductors depending on their
magnetic behavior [20-21].
Type - 1 Superconductors
Materials in which superconductivity is
destroyed abruptly at a critical field Hc
(function of temperature) called type-1
superconductors.
Type - 2 Superconductors
In type 2 superconductors the magnetic flux
starts to penetrate the material at a field of Hc1
lower than the thermodynamic critical field Hc.
The magnetization gradually decreases with
increasing field strength until H = Hc2, the
superconducting state is completely destroyed.
Between Hc1 and Hc2 the material is in vortex
state consisting of rod-shaped regions of
normal conductivity within the
superconducting bulk substance.
Oxides are some of the most important
superconducting materials showing the highest
Tc values [20, 21-30].
6.35 Dielectric Properties
Dielectric materials are substances that are
poor conductors of electricity, but efficient
supporters of electrostatic fields. If the flow of
current between opposite electric charge poles
is kept to a minimum while the electrostatic
lines of flux are not impeded, an electrostatic
field can store energy. This property is useful
in capacitors, especially at radio frequencies.
Dielectric materials are also used in the
construction of radio-frequency transmission
lines. Most dielectric materials are solids and
some examples are ceramic, mica, glass,
plastics, and the oxides of various metals.
Some liquids and gases can serve as good
dielectric materials. Dry air is an excellent
dielectric, and is used in variable capacitors
and some types of transmission lines. Distilled
water is a fair dielectric. A vacuum is an
exceptionally efficient dielectric.
An important property of a dielectric is its
ability to support an electrostatic field while
dissipating minimal energy in the form of heat.
The lower the dielectric loss (the proportion of
energy lost as heat), the more effective is a
dielectric material [20, 21, 26].
Capacitance
When two parallel plates of area A, separated
by a small distance l, are charged by +Q, –Q,
an electric field develops between the plates
can be expressed as follows
Where D = Q/A. e0 is called the vacuum
permittivity and e the relative permittivity, or
dielectric constant (e = 1 for vacuum). In terms
of the voltage between the plates, V = E l,
Page 42 of 154

The constant C= Aee0/l is called the
capacitance of the plates [20, 21].
Field Vectors and Polarization
The dipole moment of a pair of positive and
negative charges (+q and –q) separated at a
distance d is p = qd. If an electric field is
applied, the dipole tends to align the positive
charge points in the field direction.
Dipoles between the plates of a capacitor will
produce an electric field that opposes the
applied field. For a given applied voltage V,
there will be an increase in the charge in the
plates by an amount Q' so that the total charge
becomes
Where, Q0 is the charge of a vacuum capacitor.
With Q' = PA, the charge density becomes
Where the polarization is given as follows,
Types of Polarization
Three types of polarization can be caused by
an electric field are detailed below,
o Electronic polarization→ the electrons in
atoms are displaced relative to the nucleus.
o Ionic polarization→ cations and anions in
an ionic crystal are displaced with respect
to each other.
o Orientation polarization→ permanent
dipoles (like H2O) are aligned.
The molar polarization of a solid is given by
the Clausius – Mossotti equation
ε ε
Where r, v are the dielectric constant of the
materials (relative to vacuum) and of vacuum
respectively, M is the molecular weight, N0 is
the Avogadro number and is the
Polarizability.
Frequency Dependence of the Dielectric
Constant
Electrons have much smaller mass than ions,
so they respond more rapidly to a changing
electric field. For electric field that oscillates at
very high frequencies (such as light) only
electronic polarization can occur. At smaller
frequencies, the relative displacement of
positive and negative ions can occur.
Orientation of permanent dipoles, which
require the rotation of a molecule can occur
only if the oscillation is relatively slow (MHz
Page 43 of 154
range or slower). The time needed by the
specific polarization to occur is called the
relaxation time [20, 21 and 36].
Dielectric constant
Another consideration is the dielectric
constant, the extent to which a substance
concentrates the electrostatic lines of flux. In
Dielectric materials the randomizing effect of
temperature is balanced by orienting effect of
the internal field. The dielectric constant is
derived as follows.
Where εr, is the dielectric constant of the
material( relative to vacuum), is the
optical high frequency dielectric constant, C is
the Curie constant, Tc is Curie temperature and
T is Dissipation temperature of the Dielectric
material.
Substances with a low dielectric constant
include a perfect vacuum, dry air, and most
pure, dry gases such as helium and nitrogen.
Materials with moderate dielectric constants
include ceramics, distilled water, paper, mica,
polyethylene, and glass. Metal oxides, in
general, have high dielectric constants [20, 21].
The prime asset of high-dielectric-constant
substances, such as aluminum oxide, is that
they make possible the manufacture of high-
value capacitors with small physical volume.
But these materials are generally not able to
withstand electrostatic fields as intense as low-
dielectric-constant substances such as air. If the
voltage across a dielectric material becomes
too great -- that is, if the electrostatic field
becomes too intense -- the material will
suddenly begin to conduct current. This
phenomenon is called dielectric breakdown.
Dielectric Strength
Very high electric fields (>108 V/m) can free
electrons from atoms, and accelerate them to
such high energies that they can, in turn, free
other electrons, in an avalanche process (or
electrical discharge). This is called dielectric
breakdown, and the field necessary to start the
breakdown is called the dielectric strength or
breakdown strength.
In components that use gases or liquids as the
dielectric medium, this condition reverses itself
if the voltage decreases below the critical
point. But in components containing solid
dielectrics, dielectric breakdown usually
results in permanent damage [20, 21].
Dielectric Materials
Capacitors require dielectrics of high e that can
function at high frequencies (small relaxation
times). Many of the ceramics have these
properties, like mica, glass, and porcelain).
Polymers usually have lower ‘e’ [20, 21].
6.36 Optical Properties
Transitions between 3d-states are of great
influence on the optical properties and often
determine the color of the compounds. For
example, the d-d transitions of the Cr3+ ions in
Cr2O3 are responsible for the green color of
this compound, used in ceramic glazing.
The equivalent transitions at Cr3+, embedded in
the different crystal-field of Al2O3, provide the
beautiful red color of ruby and are used for the
generation of laser light in the ruby [36, 37]. In
Page 44 of 154
addition, the energetic shift of these transitions
due to the pressure dependence of the crystal-
field splitting is used in sensors for very high
pressures of up to more than 109 Pa.
Electromagnetic Radiation & Light Interaction
The optical behavior of a solid material is a
function of its interactions with
electromagnetic radiation [Fig-53] having
wavelengths within the visible region of the
spectrum. Possible interactive phenomena
include refraction, reflection, absorption, and
transmission of incident light [36, 37].
Fig-53 Nature of Light
Atomic and Electronic Interactions
The dielectric constant of a transparent oxide
varies as a function of the frequency of the
oscillating electric field in the non absorbing
region of the electromagnetic spectrum. The
refractive index similarly varies with the
frequency, generally increasing with ω. Such
dispersion behavior of materials is of
importance in the choice of materials for
prisms and other purposes. Oxides absorb
electromagnetic radiation by different modes
depending on the nature of bonding.
Tightly bound electrons and ions in oxides
give rise to narrow resonance absorption,
electrons in the ultraviolet region, and ions in
the infrared region (restrahlen absorption).
Absorption of radiation due to loosely bound
electrons is generally attributable to inter-band
transitions. Such absorption bands in
semiconductors are broad and featureless, but
with a sharp absorption edge. Transition metal
ions give absorption bands because of the
presence of d-d transitions which are Laporte-
forbidden. Both donor and acceptor impurities
in semiconducting materials give absorption
bands owing to photo-ionization at energies
lower than the gap energies. Excitons
(electron-hole pairs) in insulators give
characteristic bands with the energy depending
on how tightly bound the electron-hole pair is.
Electrons in metallic and semiconducting
materials give raise to free carrier absorption,
the absorption coefficient being proportional to
square of the incident wavelength (hence high
in the infrared region for most metals). The
reflectivity of metals (e.g., ReO3, TiO) which
is related to the plasma frequency is almost
total up to high frequencies.
Inelastic scattering in solids is typified by the
Raman Effect. If a single phonon is involved,
the scattering is referred to as first-order
Raman Effect. In second-order Raman Effect,
two phonons are involved. In Brillouin
scattering, a special case of Raman scattering,
the phonons involved are from the acoustic
branch [20, 36, and 37].
Page 45 of 154
Refraction
Light radiation experiences refraction in
transparent materials and its velocity is
retarded and the light beam is bent at the
interface. Index of refraction is the ratio of the
velocity of light in a vacuum to the velocity in
a particular medium. The phenomenon of
refraction is a consequence of electronic
polarization of the atoms or ions, which is
induced by the electric field component of the
light wave. The optical coefficient is the index
of refraction n. The index of refraction relates
to the ratio of the velocity of propagation of an
electromagnetic wave in vacuum c to the
velocity v in a medium
------------- (1)
The refractive index similarly varies with the
frequency, generally increasing with ω
(Frequency of incident light). Such dispersion
behavior of materials is of importance in the
choice of materials for prisms and other
purposes [20, 36 and 37].
Whenever the index depends on the frequency
of the incident light n = n (ω), the medium is
said to be dispersive. In addition to a decrease
in the propagation velocity, light in a medium
may undergo absorption. The intensity a
distance x in the medium from the boundary is
given by
--------------- (2)
Where I0 is the incident intensity and the
absorption coefficient α is the fraction of
power absorbed in the medium per unit length.
The absorption coefficient is given by
---------------------- (3)
Where κ is the extinction coefficient,
The index of refraction n and the extinction
coefficient κ represent the real and imaginary
parts, respectively, of a single complex
quantity, namely the complex index of
refraction
------- (4)
Knowledge of ˜n allows derivation of
additional optical coefficients more useful in
comparing with predictions from theoretical
models, e.g., the complex dielectric constant
or the complex optical conductivity . The
complex dielectric constant obtained from
Maxwell’s equations is related to by
----- (5)
The complex optical conductivity
relates to giving
-------- (6)
Here is defined by the relation of the
electric displacement to the electric field, D
= . Conventionally represents the
response of bound charges, though may in
principle be redefined providing that Eq. (6) is
maintained. Rearranging Eq. (6) gives the real
σ1 and imaginary σ2 parts of the complex
optical conductivity
----------- (7)
Page 46 of 154
 --- (8)
Equations (5), (7), and (8) provide relations
between the complex index of refraction,
optical conductivity and dielectric constant:
(absorption) and (screening)
[20, 36]
. varies with wavelength of the incident light.
Reflection
When light radiation passes from one medium
into another having a different index of
refraction, some of the light is scattered at the
interface between the two media even if both
are transparent. The reflectivity R represents
the fraction of the incident light that is
reflected at the interface, or where I0 and IR are
the intensities of the incident and reflected
beams, respectively.
If the light is normal (or perpendicular) to the
interface, then n1 and n2 are the indices of
refraction of the two media.
If the incident light is not normal to the
interface, R will depend on the angle of
incidence. When light is transmitted from a
vacuum or air into a solid s, then the index of
refraction of air is very nearly unity.
The higher the index of refraction of the solid,
the greater is the reflectivity. (Eg- Silicate
glasses, the reflectivity ~0.05). The reflectivity
Reflection losses for lenses and other optical
instruments are minimized by coating the
reflecting surface with very thin layers of
dielectric materials such as magnesium
fluoride (MgF2).
Absorption
Nonmetallic materials are either intrinsically
transparent or opaque. Opacity results in
relatively narrow-band gap materials as a result
of absorption whereby a photon’s energy is
sufficient to promote valence band-conduction
band electron transitions. Transparent
nonmetals have band gaps greater than about 3
eV. Some light absorption occurs in even
transparent materials as a consequence of
electronic polarization [20, 36].
Optical Properties of Metals
Metals appear opaque as a result of the
absorption and then reemission of light
radiation within a thin outer surface layer.
Absorption occurs via the excitation of
electrons from occupied energy states to
unoccupied ones above the Fermi energy level.
Reemission takes place by decay electron
transitions in the reverse direction. The
perceived color of a metal is determined by the
spectral composition of the reflected light [20,
36]
.
Page 47 of 154
Opacity and Translucency in Insulators
Normally transparent materials may be made
translucent or even opaque if the incident light
beam experiences interior reflection and/or
refraction. Translucency and opacity as a result
of internal scattering may occur, (1) in
polycrystalline materials that have an
anisotropic index of refraction, (2) in two-
phase materials, (3) in materials containing
small pores, and (4) in highly crystalline
polymers [20, 36 and 37].
Fig-54 the spectrum of electromagnetic radiation,
including wavelength ranges for the various colors in the
visible spectrum
Color
For wide-band gap insulators that contain
impurities, decay processes involving excited
electrons to states within the band gap are
possible with the emission of photons having
energies less than the band gap energy. These
materials appear colored, and the color
depends on the distribution of wavelength
ranges in the transmitted beam [20, 36 and 37] (Fig-
54).
Optical phenomena
Three other important optical phenomena are
luminescence, photoconductivity, and light
amplification by stimulated emission of
radiation (lasers).
Luminescence
With luminescence, energy is absorbed as a
consequence of electron excitations, which is
reemitted as visible light. The electron-hole
pair produced in photo-excitation processes
reverts to the original state by releasing energy
to the lattice through creation of phonons or
radiative recombination, giving rise to
luminescence.
Such a de-excitation can be induced at
impurity sites called activators. Absorption and
emission processes in photoluminescence need
not occur at the same impurity sites. For
example, in Ca3 (PO4)2 doped with Ce and Mn,
absorption occurs at Ce sites (sensitizer) and
recombination at Mn sites (activator).
This process involves energy transfer between
two centers, and the luminescence intensity
therefore depends on the average distance
between impurity centers. The cation Eu2+ in
barium magnesium aluminate gives blue
emission, while Eu3+ in Y2O3 gives red
emission [20, 36 and 37].
Photoconductivity
The electrical conductivity of some
semiconductors may be enhanced by photo-
induced electron transitions, whereby
additional free electrons and holes are
generated.
Page 48 of 154
Lasers
Coherent and high-intensity light beams are
produced in lasers by stimulated electron
transitions.
Laser (light amplification through stimulated
emission of radiation) action is seen in
materials such as ruby (0.01 atom%Cr3+ in
Al2O3). This occurs because of population
inversion, achieved by optical pumping to
higher energy levels (4F1 and 4F2) from which
de-excitation occurs through a non-radiative
process to an intermediate level (2E), from
which lasing occurs to the ground state (4A2),
giving 6943 Ȧ radiation.
the other due to localized electrons. Further
TMO based on oxygen bonding is discussed
below.
6.371 Monoxides
Monoxides of 3d transition metals, TiO to
NiO, possess the rock salt structure and exhibit
interesting properties (Fig-55). TiO and VO
exhibit properties characteristic of itinerant d
electrons. MnO, FeO, CoO, and NiO show
localized electron properties.

The simulated laser light has the special

property of coherence and it has the same
phase and direction of propagation as the
incident photon. When Nd3+ is doped in
CaWO4, there is laser emission at 1.06 µm (4F
4
3/2 to I11/2) [20, 36]. The commonly employed
Nd-YAG laser is Nd3+ in Y3Al5O12 (yttrium
aluminum garnet).

The polarization produced in a solid is

generally proportional to the electric field of
the radiation. Electric fields produced can be
very high laser beams and nonlinear effects.
Polarization would then contain multiples of
frequencies. The number of photons with
frequencies 2ω, 3ω …, will however be small.
Generation of second and higher harmonics is
accomplished by using non-centrosymmetric
crystals such as KH2PO4, LiNbO3, and
KTiOPO4 [20, 37]. Fig- 55, Transition metal mono-oxides with rock salt
structure
6.37 Electronic and Magnetic properties in
relation to structure The properties can be understood in terms of
As explained in previous section 6.31, TMO cation-cation and cation-anion-cation
exhibit electronic properties two ways one is interactions in the rock salt structure. Direct
due to the presence of itinerant electrons and cation-cation interaction can occur through the

Page 49 of 154
overlap of cationic t2g orbitals across the face
diagonal of the cubic structure. When such an
interaction is strong (R < Rc and b > bc),
cationic t2g orbitals are transformed into a
cation sublattice t*2g band; if this band is
partially occupied, the material becomes
metallic (e.g., TiO). VO is less metallic, and its
magnetic susceptibility becomes temperature
dependent at low temperatures because the
increased nuclear charge contracts the radial
extension of the 3d orbitals of vanadium,
thereby decreasing the overlap of the t2g
orbitals.

The increasing nuclear charge across the TiO-

NiO series has the effect of lowering the 3d
manifold energy relative to the top of the
anionic 20 states (fig-55) [20, 36 and 37].

6.372 Dioxides
Dioxides of many of the transition metals
crystallize in the rutile structure, and their
electronic properties are shown in (Fig-56).
The rutile structure provides the possibility of
135o cation-anion-cation interaction between
corner-shared octahedral and 90o cation-anion-
cation interaction between edge-shared
octahedral. A direct cation-cation interaction is
possible along the direction c.
The octahedral crystal field of the cation and
the tetragonal structure provide an axial field,
which splits the triply degenerate metal t2g
orbital into a non degenerate t|| orbital and a
doubly degenerate t﬩ orbital. While t﬩ can form
π∗ bands with anion pπ orbitals, t|| forms cation
sub lattice d bands of the cation-cation distance
along the c-axis is less than Rc.
Fig-56, Transition metal Di-oxides with Rutile structure
The rutile structure therefore enables the oxide
to become metallic through cation-cation
interaction and/or through cation-anion-cation
interaction [20].
6.373 Sesquioxides
The important sesquioxides of the first row
transition metals crystallizing in the corundum
structure are Ti2O3, V2O3, Cr2O3, and α-Fe2O3.
Cr2O3, and α-FeO3 are antiferromagnetic
insulators. Ti2O3 and V2O3 exhibit
semiconductor-metal transitions at 410K and
150K, respectively.
The transition in Ti2O3 is broad, occurring over
a large temperature interval. In V2O3, the
transition is accomplished by
antiferromagnetic ordering. These properties

Page 50 of 154
can be understood in terms of the cation-anion-
cation interactions (135o and 90o) and cation-
cation interactions (in the basal plane and
along the hexagonal c-axis).
The structure provides a trigonal component to
the octahedral crystal field, which splits the t2g
orbitals into a1g (directed along cH) and eg(π)
directed in the basal plane. In Ti2O3, with one
d electron per atom and a small hexagonal c/a
ratio, both the cation-cation distances are
smaller than the critical value (Rcc < Rbb < Rc).
The a1g band is therefore filled and separated
from the empty eg(π) band by a finite gap,
accounting for the semiconducting behavior at
low temperatures.
In V2O3, with large c/a ratio and with two d
electrons per vanadium, Rcc < Rbb < Rc; the eg
(π) band is more stable than the a1g band. The
metallic nature of rhombohedral V2O3
indicates that these bands overlap to some
extent. In Cr2O3 and Fe2O3, the a1g and eg(π)
orbitals are half-filled. In Cr2O3, the eg
electrons are localized, but the a1g electrons are
likely to be intermediate, since the interaction
distance in the c direction is less than Rc. In
Cr2O3, with no eg(σ) electrons. Accordingly,
TN in Fe2O3 is higher (953 K) than in Cr2O3
(307 K). Fe2O3 exhibits weak, parasitic
ferromagnetism in the range 253 < T < 953 K.
In this temperature range, the atomic moments
lie nearly in the basal plane.
Anti-symmetric spin coupling is parallel to the
c-axis, and the anisotropic super exchange
cants spins in the basal plane to produce a net
moment. Upon application of a strong
magnetic field in the c direction, a field-
induced first-order spin-flip transition (Morin
transition) is observed around 260 K [20].
6.374 Properties of Pervoskites and Spinels
The physical properties of perovskite include
superconductivity, colossal magnetoresistance,
ionic conductivity, and a multitude of
dielectric properties, which are of great
importance in microelectronics and
telecommunication. The great flexibility
inherent in the perovskite structure enables
many different types of distortions, which can
occur from the ideal structure.
These include tilting of the octahedra,
displacements of the cations out of the centers
of their coordination polyhedra, and distortions
of the octahedra driven by electronic factors
(i.e. Jahn-Teller distortions). Many of the
physical properties of perovskites depend
crucially on the details of these distortions,
particularly the electronic, magnetic and
dielectric properties which are so important for
many of the applications of perovskite
materials.
The perovskite structure is ideally suited for
the study of 180o cation-anion-cation
interaction of octahedral site cations. The
possibility of cation-cation interaction is
remote because of the large interaction
distance along the face diagonal. Various
properties of perovskites are shown with the
examples: BaTiO3 is ferroelectric, SrRuO3 is
ferromagnetic, LaFeO3 is weakly
ferromagnetic, and BaPb1-xBixO3 is super-
conducting, while LaCoO3 shows a nonmetal-
to-metal transition. Several perovskite oxides
exhibit metallic conductivity; some examples
are ReO3, AxWO3, LaTiO3, AMoO3 (A = Ca,
Sr, Ba), SrVO3, and LaNiO3. Metallic
conductivity in perovskites is due to the strong
cation-anion-cation interaction.
Page 51 of 154
6.375 Mixed Valence
Many transition metal oxides contain cations in
more than one oxidation state. Properties of
these oxides are generally determined by the
rate of electron transfer between the different
oxidation states. A classification of such
compounds has been made by Robin and Day
on the basis of the valence delocalization
coefficient (Fig-57).
Fig-57, Different classes of Mixed Valent Solids
This type of mixed valence is different from
that prevalent in rare earth and actinide
materials, in which valence fluctuations, heavy
fermion behavior, and superconductivity are
found. Depending on the relative energies of
the fn configuration and the Fermi level due to
non-f electrons, three electronic regimes are
distinguished: the magnetic regime, the Kondo
regime, and the fluctuating valence regime.
EuO and SmS exhibit valence fluctuations
under pressure as a result of the promotion of
an f electron to the conduction band [20].
6.376 Defects in Oxides
Most crystalline materials are not perfect and
their regular pattern of atomic arrangement is
interrupted by crystal defects.
Fig- 58, Schematic illustration of defects in a compound
solid, using GaAs as an example.
In Fig-58, the defect notation in upper-case
letters stand for atoms or vacancies (V) on a
lattice site, and the subscripts for the lattice site
in a perfect crystal. The subscript i→ stands
for an interstitial site and the subscript S for a
substitutional site. Thus e.g. Asi stands for a
As atom on an interstitial site, VGa for a
missing atom on the Ga sublattice, GaAs for a
Ga antisite atom on the As sublattice, and BS
for a B atom on a substitutional site. This
notation is a variety of Kroger-Vink Notation
for non-ionic solids
A nonstoichiometric oxide can be defined as a
crystalline oxide in equilibrium with its
Page 52 of 154
environment, behaving as a more. The intrinsic defect concentration in
thermodynamically bivariant system. In
stoichiometric oxides, vacancies order
themselves to give rise to super structures or
complexes [20].
o Roth clusters are complexes of the form
given by,
VM – M3+tet – VM
where M is a transition metal, VM is the
vacancy created by the absence of a metal
atom, and the M3+ ion is tetragonally
surrounded by oxygen atoms. The ratio of
vacancies to tetrahedral M3+ ions in the Roth
cluster is 2:1 = 2.
o Another similar type of complex is the
Koch-Cohen cluster, which as a ratio of 3:4
= 3.25 in oxides of the form MO2+x or
MO2-x, a defect cluster, known as the
Bevan cluster which are tightly bound
vacancies along a body diagonal, <III>.
o Another type of defect cluster, where two
vacancies, one interstitial of one kind and
two interstitials of another kind, is known
as the 2:1:2 Willis cluster.
In ionic solids, the common point defects are
Schottky pairs (pairs of cation and anion
vacancies) and Frenkel defects (cation or anion
interstitial pairs plus a vacancy). When there is
a large concentration of Schottky pairs, the
measured pyknometric density of the solid is
considerably lower than the density from the
X-ray unit cell dimensions (e.g., VO) [20].
Creation of defects is generally an endothermic
process. Thus, the formation energies of
vacancies in ionic solids are generally 2eV or
these solids is therefore extremely small even
at high temperatures. The intrinsic defect
concentration in binary solids around 0.8Tm is
~10-5 [20].
Types of defects
The various types of defects that occur in ionic
solids are point, linear, planar and volumetric.
Point defects
Point defects arise from the absence of the
constituent atoms on the lattice sites or their
presence in interstitial positions. The presence
of alien atoms constitutes another type of point
defects. Point defects cause polarization of the
surrounding region in the crystal and give rise
to small displacements on neighboring atoms
or ions.
Thus a cation vacancy in an ionic solid will
have an effective negative charge, causing
displacements of neighboring anions. The
energy of formation of point defect depends
mainly on the atomic arrangement in the
immediate neighborhood of the point defect.
Linear defects
Linear defects in crystals are dislocations,
corresponding to rows of atoms that do not
possess the right coordination.
Planar defects
Planner defects are boundaries between small
crystallites (grain boundaries), stacking faults,
crystallographic shear planes, twin boundaries
and anti phase boundaries.
Volumetric defects
Segregation of point defects gives rise to 3D
volumetric defects.
Page 53 of 154
Crystallographic shear
One way by which anion-deficient
nonstoichiometry is accommodated in some
transition metal oxides is by eliminating point
defects by crystallographic shear. This leads to
the formation of isolated shear plane or a
random array of shear planes, known as
Wadsley defect.
In close packed oxides, we also see stacking
faults such as: tilt boundary (array of
periodically spaced edge dislocations), twist
boundary (array of screw dislocations), twin
boundaries (a layer with mirror plane
symmetry), and coincidence boundary (one
part of a crystal rotated with respect to another)
and antiphase boundaries (across which the
sublattice occupation is interchanged) [20].
6.377 Phase Transitions
When temperature rises and pressure is held
constant, a typical substance changes from
solid to liquid and then to vapor. Transitions
from solid to liquid, from liquid to vapor, from
vapor to solid and vice versa are called phase
transformations or transitions. Since some
substances have several crystal forms, there
can also be solid to another solid phase
transformation.
Phase transitions involve changes in atomic
configuration, electronic or the spin
configuration. During a phase transition, the
free energy of the solid remains continuous,
but thermodynamic quantities such as entropy,
volume, and heat capacity exhibit
discontinuous changes. Depending on which
derivative of the Gibbs free energy, G, shows a
discontinuous change at the transition. Phase
transitions are generally classified as first order
or second order. In a first-order transition,
where the G (P, T) surfaces of the parent and
product phases intersect sharply, the entropy
and the volume show singular behavior. In
second-order transitions, on the other hand, the
heat capacity, compressibility, or thermal
expansivity shows singular behavior.
Many physical properties diverge near Tc; that
is, they show anomalously large values as Tc is
approached from either side. An important
aspect of phase transition in solids is the
presence of two modes. Operationally, a soft
mode is a collective excitation whose
frequency decreases anomalously as the
transition point is reached. In second-order
transitions, the soft-mode frequency goes to
zero at Tc, but in first-order transitions, the
phase change occurs before the mode
frequency goes to zero. It has been found
convenient to classify phase transition in solids
on the basis of the mechanism.
Three important kinds of transition are as
follows: nucleation and growth transitions, a
typical example being the anatase-rutile
transformation of TiO2; positional and
orientational order-disorder transitions; and
martensitic transitions. Orientational order-
disorder is exhibited by many solids such as
ammonium halides, plastic (orientationally
disordered) crystals. A martensitic transition is
a structural change caused by atomic
displacements (and not by diffusion)
corresponding to a homogenous deformation
where the parent and product phases are related
by a substitutional lattice correspondence, an
irrational habit plane, and a precise
orientational relationship [20, 21].
Structural phase transitions are also classified
in the following manner:
Page 54 of 154
o Displacive: ferrodistortive, anti- But, RMnO3 (with R = Gd, Tb, and Dy)
ferrodistortive, and ferreoelastic possesses comparable transition temperatures
transitions. for the magnetic and the ferroelectric ordering,
o Order-disorder: vacancy ordering indicating that there might be direct coupling
Electronic: spin-state transitions. between them. For instance, the switching of
the electric polarization could be achieved by
applying magnetic fields [20, 21].

7.0 Multiferroic Crystals

Multiferroics are Poly crystals belonging to the
family of Transition Metal Oxides that have
coupled electric, magnetic, and structural order
parameters that result in simultaneous
ferroelectricity, ferromagnetism, and
ferroelasticity.

7.10 Origin and History of Multiferroics

The origin of multiferroics dates back to the
discovery of magnetoelectric effect. Pierre
Curie first postulated this effect in 1894.
Fig- 59 Magnetic phase diagram of RMnO3

The above Magnetic Mn Phase diagram (Fig-

59) shows hexagonal and orthorhombically-
distorted perovskite structures. Both differ on
the FE and AF ordering temperatures. Open
and closed triangles denote the Ne´el and lock-
in transition temperatures respectively. Rare-
earth manganites RMnO3 may be classified
into those with hexagonal structure (where R =
Ho to Lu) and those with orthorhombically
distorted perovskite structures (where R= La,
Gd and Dy). Fig-59 shows the magnetic phase
diagram for RMnO3.

The hexagonal RMnO3 (such as YMnO3 or

LuMnO3) show both, ferroelectric and
antiferromagnetic order, but the TFE ≈1000 K
Fig- 60 Magnetoelectric Effects: Historical Survey
and TN ≈100 K differ by an order of
magnitude which would not produce a feasible
Following the theoretical prediction by
coupling between the two order parameters. [38]
Dzyaloshinskii in 1959 and the first

Page 55 of 154
experimental observation by Astrov [39] in 1960
and Folen in 1961 (Fig-60), the magneto
electric effect was studied intensively in the
1960s and 1970s [40] attracted continuing
interest for more than four decades. The
history of multiferroics research dates back to
1958 from the work by Smolenskii and
coworkers (Fig-60) [40].
Numerous multiferroics have been identified to
date. Examples are some boracites (Ni3B7O13I,
Co3B7O13I, etc.), some fluorides [BaMF4 (M =
Mn, Fe, Co, and Ni)], magnetite Fe3O4,
hexagonal manganites (YMnO3, HoMnO3,
etc.), perovskites ABO3 having a Bi or Pb ion
on the A site and transition metal(s) on the B
site [e.g., PbFe 1−X NbxO3, BiFeO3 and
BiMnO3], CdCr2S4, and hexagonal ferrites
(e.g., LuFe2O4).
Scientific communities around the world have
made lot of contributions in publishing several
reviews in the past years which led to the
understanding of magnetoelectric effect,
characterization of magnetoelectric
multiferroics, according to the origin of their
multiferroic nature [40].
Fig- 61 Multiferroic research progress and trend
7.20 Progress of researches in Multiferroics
The field gained interest in the past decade
(Fig-61) after the observation of gigantic
ferroelectric polarization in one of the
conventional multiferroics, BiFeO3 (Bismuth
ferric Oxide) at room temperature [40], and the
discovery of a new class of multiferroics
showing a large magnetoelectric effect.
In 2003, ferroelectric activity was found in
rare-earth manganites with orthorhombically
distorted perovskite structure, TbMnO3, which
shows antiferromagnetic orders with long
wavelength modulation as compared to their
chemical unit cell, [44] owing to competing
magnetic interactions. In this new multiferroic
compound, a large magnetoelectric effect has
been observed at the onset field of a
metamagnetic transition. More recently,
theoretical and experimental studies of the
rare-earth manganites revealed that the
ferroelectricity originates from a cycloidal
spiral spin structure. These results indicate the
emergence of a new class of ferroelectrics in
which the origin of ferroelectricity is related to
magnetic order and is different from known
ferroelectrics. Magnetoelectric effects in
materials provide a great opportunity to use an
electric field to control ferromagnetism.
Magnetoelectric coupling between electric and
magnetic order parameters has been
theoretically predicted, and there is intense
interest in its implementation in device
architectures to take advantage of these
properties for applications in many fields, such
as agile electromagnetics, optoelectronics or
Spintronics [40].
7.30 Constraints in most multiferroics
The major constraint in most multiferroics is
that, the temperature scale for ferroelectric
Page 56 of 154
order is much larger than for magnetic order,
and the origins of these orders have no relation
to each other, which leads to only weak
coupling between magnetism and
ferroelectricity. Single-phase multiferroics
show spontaneous magnetization and
polarization simultaneously at ambient
conditions, remains elusive as most systems
(Eg: manganites) exhibit multiferroicity only at
low temperatures [40].
Fig-62 - RE MnO3 Vs Other Multiferroics
The case of ferromagnetic and ferroelectric
couplings within one phase is very difficult to
be found in reality because ferromagnets tend
to be metals and ferroelectrics need to be
insulators.
However one multiferroic material namely
BiFeO3 (BFO), has played a key role in
rejuvenating the field after a report of large
ferroelectric polarization combined with
interesting magnetic properties at room
temperature in bulk BFO [41].
But numerous reports of Professor Ramesh
Ramamoorthy and associate researchers on the
properties of BFO thin films, Nano structures
and Nanopillar forms are quite promising and
encouraging for further research to use the
BFO thin films in industrial applications,
especially in the new and novel device
applications.
7.40 Structures of Multiferroics
Multiferroics are perovskites with general
formulas of ABO3 and A2BBO68 with units of
cubic cell type (eg-LaxTiO3), tetragonal type
(eg-BaTiO3) and orthorhombic type (eg-
GdFeO3) structures. Many different types of
distortions can occur from the ideal structure
of perovskites. These include tilting of the
octahedra, displacements of the cations out of
the centers of their coordination polyhedra, and
distortions of the octahedra driven by
electronic factors (i.e. Jahn-Teller
distortions). Multiferroic materials have a
slightly deformed symmetry with the 3m point
symmetry group instead of the ideal cubic
symmetry m3m.
7.50 Mechanism of Multiferroics
Normally, ferromagnetism and ferroelectricity
exclude each other, but in multiferroic
materials, researchers have reported
magnetoelectric coupling in the same phase in
materials like TbMnO3, DyMnO3, GdMnO3,
and BFO. Several theories about mechanisms
of multiferroics have been proposed to explain
the origin of multiferroicity in the different
materials that are discussed below [42-45].
7.51 Paramagnetic doping.
Coexistence of ferroelectric and ferromagnetic
order parameters can be established when a
transition metal ion is being replaced partially
by a paramagnetic ion. The solid solution
[PbFe2/3W1/3O3]1−x[PbMg0.5W0.5O3]x is the first
Page 57 of 154
system in which magnetic and electric ordering
have been found to coexist. The Mg and W
ions are diamagnetic and cause the
ferroelectricity, and the d5 orbitals of Fe3+ ion
are responsible for the magnetic ordering.
Because of the mutually diluting properties,
these systems possess low magnetic ordering
temperatures [20, 42-45].
7.52 Lone-pair asymmetry.
The chemical compounds of BiRO3 (where R =
Fe, Mn, Cr) exhibits multiferroicity when a
lone pair of s2 (Bismuth ion) hybridizes with an
empty p orbital of R-cation and causes a
structural distortion by exhibiting
ferroelectricity. Examples are: In Bi2FeCrO6 a
spontaneous magnetization of 2µB and a
spontaneous polarization of 80 µC cm−2 at
room temperature are reported [41]. BiMnO3
possesses saturated magnetic moment with the
magnitude of 3.6 µB at 10 K. For BiFeO3, bulk
magnetization measurement shows 6.1 µC
cm−2 [41].
7.53 Electrostatic and size effects.
The Electrostatic and size effects contributes a
good coupling effect, for example in YMnO3.
The hexagonal crystal structure consists of
non-connected layers of MnO5 trigonal
bipyramid corners linked by its in-plane
oxygen ion (Op). In addition, an apical oxygen
ion (OT) produces close-packed planes
separated by a layer of Y 3+ ions. The trigonal
bi-pyramids represent the MnO5 polyhedra and
the spheres represent Y ions. There are two
major atomic displacements in the crystal
structure from the centro symmetric P63/mmc
to the ferroelectric P63cm: Firstly, a buckling
of MnO5 polyhedral structure results in a
shorter c-axis and secondly the displacement is
a vertical shift of the Y ions away from the
high temperature mirror plane, while keeping
the distance to OT constant [45].
Fig- 63 Crystal structure of YMnO3 in the paraelectric
and ferroelectric phases
As a result of this buckling phenomenon, one
of the two Y-Op bond lengths is reduced, and
the other bond length is enlarged, leading to a
net electric polarization. This asymmetric
environment of the Y ions was recognized
under neutron-powder-diffraction and X-ray
diffraction studies. Since Y3+ or Mn3+ have no
lone pair of electrons and the Mn ions remains
close to the centre of their oxygen cages, the
driving force for ferroelectricity in YMnO3 is
entirely caused by the electrostatic and size
effects (Fig-64). This is derived from the long
range dipole-dipole interaction and the oxygen
rotated in such way to make huge Y-Op off-
centre displacements, which produces an
electrical polarization and a stable
ferroelectric state in YMnO3 structure.
7.54 Microscopy ME correlation
Efremov, et.al mentioned that besides the well-
known site-centered and bond centered charge
ordering in doped manganites of the type R1-
XCax MnO3 (where R=La or Pr), But there is
one intermediate situation among them which
Page 58 of 154
can produce multiferroics [46]. Charge ordering
in the sites leads to a checker board ordering
pattern as shown in Fig-64(a) and is known as
Site-Centered ordering (SCO). When the
charge ordering occurs in the bonds instead of
in the sites, as depicted in Fig-64(b), it is called
a Bond-Centered Ordering (BCO).
Fig- 64 Three types of charge ordering
For example, Pr1-XCaXMnO3 with x = 0.4. The
intermediate state can be found in the doped
Lanthanum-Calcium compounds at x ≥ 0.5 and
in the Pr-Ca system at x = 0.3 as in Fig-64(c).
The asymmetry on this intermediate phase
leads to an ordered dipole moment and
consequently produces ferroelectricity.
7.60 BFO Structure – as a model system
As of today, several composite materials,
consisting of separate piezoelectric and
magnetic phases, have been reported to show
magnetoelectric coupling at room temperature
[47, 48]
, a requirement for device applications.
However, the availability of room-temperature
single-phase multiferroics is very limited.
Among the few room temperature single-phase
magnetoelectric multiferroics reported so far,
BiFeO3 shows the highest ferroelectric
polarization, with a ferroelectric Curie
temperature (TC) of ~1,100 K and an
antiferromagnetic N´eel temperature (TN) of
~640 K. Both ferroelectricity and
antiferromagnetism have long been known in
BiFeO3 single crystals, and recent studies of
BiFeO3 thin films have confirmed the
existence of a large ferroelectric polarization,
as well as a small magnetization, both of which
are consistent with theoretical predictions.
Although the possibility of coupling between
the ferroelectric polarization and the weak
ferromagnetism has been investigated using
first-principles density functional theory [52, 53],
there have been no previous investigations of
the coupling between ferroelectricity and
antiferromagnetism in this material. In addition
to its fundamental interest, such a coupling
would offer the intriguing possibility of
electric field controllable ferromagnetism
through exchange bias to an electrically
controllable antiferromagnetic component [51-
53]
.
BFO structure can be characterized by two
distorted perovskite unit cells (ar = 3.96 Å, αr =
0.6°) connected along their body diagonal,
denoted by the pseudocubic <111>, to form a
rhombohedral unit cell (Fig-65) [56, 57]. The
large displacement of the Bi ions relative to the
octahedral FeO6 induces ferroelectricity
resulting in two important considerations.
Firstly, the ferroelectric polarization lies along
the pseudocubic <111> leading to the
formation of eight possible polarization
Page 59 of 154
variants, corresponding to four structural polarization direction with six equivalent easy
variants [54, 57 and 58]. axes within that plane (Fig-65) [58, 60].

Secondly, the antiferromagnetic ordering of Therefore, it is obvious that there is a coupling

BFO is G-type, in which the Fe magnetic between antiferromagnetism and ferroelectric
moments are aligned ferromagnetically within polarization. Recent studies of BFO thin films
(111) and antiferromagnetically between have shown that canting of the
adjacent (111). BFO is also known to exhibit a antiferromagnetic sub lattice is the reason for
spin cycloid structure in the bulk [54] and the the existence of a large ferroelectric
preferred orientation of the polarization, as well as a small net
antiferromagnetically aligned spins is in the magnetization of the Dzyaloshinskii–Moriya
(111), perpendicular to the ferroelectric type [55, 60].

Fig.65 Schematic of the crystal structure of BFO and the ferroelectric polarization (arrow) and antiferromagnetic plane
(shaded planes).

8.0 Thin films microelectronics, materials science and

Multiferroic thin films are thin films of engineering, electrical engineering, applied
materials consisting of two or more solid state physics and chemistry, bio-medical,
multiferroic properties. In general thin films is telecommunications and so on, for both
a field of the utmost importance in today's research and industrial applications.

Page 60 of 154
Advanced, high- performance computers, high-
definition TV, digital camcorders, sensitive
broadband imaging systems, flat-panel
displays, robotic systems, and medical
electronics and diagnostics are but a few
examples of miniaturized device technologies
that depend on the utilization of thin film
materials [20, 53].
8.10 History of Thin Films
The first studies of thin films (magnetic films)
of electronic material were conducted in 1884
by Professor August Kundt [61]. He fabricated
thin films of iron, cobalt, and nickel, and was
able to measure the rotation in the polarization
of light transmitted through these films in a
direction parallel to the film magnetization.
Fig-66 Material for Insulating Oxide Thin Films
8.20 Materials for Thin Films
Electronic materials are mainly used to
fabricate or grow thin films and they can be
classified in to insulating, semi-insulating and
metallic. Thin films can be classified in to
Ferro / Ferrimagnetic thin films, Ferro / Ferri
electric thin films and Magnetoelectric /
Multiferroic thin films.
Most of the magnetoelectrics and multiferroics
are insulating oxides, which are extensively
used as thin films in electronics,
microelectronics and research for advanced
materials and for potential novel device
applications as detailed in (Fig-66).
Page 61 of 154
8.30 Thin-film deposition / Processing and tailoring of the microstructure and
Thin-film deposition is a technique for properties of thin films.
depositing a thin film of material onto a
substrate or onto previously deposited layers.
Most deposition techniques allow layer
thickness to be controlled within a few tens of
nanometers and some allow single layers of
atoms to be deposited at a time.

General infrastructures for processing

o PLD, CVD, Sputtering, solgel facilities for
thin film processing.
o Laser MBE to process complex oxides like
crystalline oxides on Si
o Clean room environment for
characterization and device processing.
o Scanning force microscopy for
characterization like Piezoforce
microscopy of FERAMS
o Nanoscale domain dynamics using AFM, Fig-67 Classification of the most common deposition
processes
MFM, TUNA.
o Switching dynamics using AFM for high
speed measurements. General Characteristics of Thin Film
o Facilities for FE, transport, interface, Deposition

Deposition Rate
pyroelectric studies

Film Uniformity
o Advanced Light Source for Insitu studies
o Across wafer uniformity
using synchrotron.
o Run-to-run uniformity
o NCEM for TEM studies

Materials that can be deposited
o Metal
8.31 Classification of deposition processes
o Dielectric
Most of the thin film deposition processes and
o Polymer
technologies originate from purely physical or

Quality of Film – Physical and Chemical
purely chemical processes as detailed in Fig-
Properties
67. All the available thin film processing
o Stress
techniques are based on liquid phase chemical
o Adhesion
processes, gas phase chemical processes, glow
o Stoichiometry
discharge processes and evaporation methods
[62] o Film density, pinhole density
. From the past couple of decades numerous
o Grain size, boundaries and orientation
novel processes that utilize a combination of
o Breakdown voltage
different techniques have been developed and
o Impurity level
this combination allows a more defined control

Page 62 of 154

Deposition Directionality
o Directional: good for lift-off, trench
filling
o Non-directional: good for step coverage

Cost of ownership and operation
Uniform Coating
Uniform Coating for spherical surfaces with
source on its edge (Fig-69) is given by

Mass Deposition Rate per unit area of

source surface
Mass Deposition Rate (Rm) per unit area of
source surface is given by Langmuire –
Knudsen relation below [62, 63 and 64].

Fig-69 Uniform Coating for spherical surfaces

Angle independent and uniform coating used

Maximum deposition rate reaches at high
chamber vacuum (P ~ 0) (Fig-68).
to coat instruments with spherical surfaces.
Uniformity on Flat Surfaces
Uniform Coating for flat surfaces (Fig-70) is
given as follows

Fig-68 Mass Deposition rate

Page 63 of 154
 Fig-71 Graph showing Sample size Vs Source –Sample
distance in Uniform Coating requirements for flat
surface

Thickness Deposition Rate vs. Source Vapor

Pressure
Fig-70 Uniform Coating for flat surface
Rate of thickness deposition vs. Source Vapor
Pressure is illustrated in the Fig-72.
Uniformity requirement for Flat Surfaces
Uniform Coating for flat surfaces (Fig-71) is
given as follows

Fig-72 Thickness Deposition Rate Vs Source Vapor

Pressure

Page 64 of 154
Pe is function of source Temperature,
So, higher the vapor pressure, the higher is the
material’s deposition rate [62, 63 and 64].

Deposition Rate vs. Source Temperature Fig-73 Vapor Pressure Vs Temperature

Deposition Rate vs. Source Temperature is
illustrated in the Fig-73 [62, 63 and 64]. Classification of Processes
Basically there are two types of Vapor
depositions, which are Physical Vapor
Deposition (PVD) and Chemical Vapor
Deposition (CVD). Other thin film growth
techniques from liquid and solution phase are
also in practice.

Physical Vapor Deposition

Deposition happens because of a physical
reaction.

Fig-74 Physical Vapor Deposition

Page 65 of 154
These processes create the solid thin films
directly from the material without any
chemical reaction. The deposited material is
physically moved on to the substrate (Fig-74).
Types of PVD
o vacuum evaporation
o sputtering
o Molecular beam epitaxy (MBE)
Chemical Vapor Deposition
In CVD, the deposition happens because of a
chemical reaction. This process creates the
solid thin films directly from chemical
reactions in gas and/or liquid compositions or
with the substrate material. The solid material
is usually not the only product formed by the
reaction. By products can include gases,
liquids and even other solids.
Types of CVD
o Atmospheric pressure chemical vapor
deposition (APCVD)
o Low pressure chemical vapor deposition
(LPCVD)
o Plasma assisted (enhanced) chemical vapor
deposition (PACVD, PECVD)
o Photochemical vapor deposition (PCVD)
o Laser chemical vapor deposition (LCVD)
o Metal-organic chemical vapor deposition
(MOCVD)
o chemical beam epitaxy (CBE)
Other thin film growth techniques - from liquid
and solution phase are:
o spray coating
o spin coating
o electroplating
o liquid phase epitaxy
8.32 Vacuum Systems
Many prevalent deposition techniques used in
modern thin film technology requires the
creation of vacuum condition for the
deposition to occur. The quality and
consistency in quality of final products (thin
film) depends on these vacuum systems [62].
Basic Vacuum Concept
Vacuum is the absence of gases, moisture and
particles which normally fill our environment.
In a deposition system a container is provided
and the majority of these elements are removed
to create a vacuum. The vacuum condition is
an important factor to get suitable vacuum
environment to produce quality thin films.
Vacuum condition, accelerates the mean free
path for atoms by eliminating the presence of
gases that could react with the materials to be
deposited; It could reduce the vapor pressure
and lower the evaporation temperature of the
target material and provides the ultimate clean
vacuum environment.
Measure of vacuum
In vacuum measurements, pressures are mostly
measured in millimeters of mercury or torr.
One torr is the pressure necessary to support a
column of mercury with a height of one
millimeter.
1 atmosphere = 101 KPa = 760 torr.
Vacuum conditions are classified as low
vacuum of pressure range 105 to 103 Pa (760-
25 torr), Medium vacuum 103 to 10-1 Pa (25
torr to 0.75 milli torr), High vacuum 10-1 to10-4
Pa (~ 10-3 to 10-7 torr) and Very high vacuum
10-4 to 10-7 Pa ( ~ 10-7 to 10-12 torr). Most
practical deposition processes occur in the
medium to high vacuum ranges [62].
Page 66 of 154
There are two pressure regimes in vacuum
systems, and gases behave differently in each
regime.
o In the viscous flow regime, gas flows as a
fluid, where the mean free path of the gas
molecules is much smaller than the
dimensions of the apparatus.
o In the molecular flow regime, the mean
free path is much longer than the
characteristic dimensions of the apparatus.
In this regime, gas molecules interact
almost entirely with the walls of the
chamber, acting independent of each other.
Gas flow in either regime is measured in torr
liters per second, which is equivalent to mass
per second. The conductance of a tube
describes how much gas flows through the
tube for a given pressure differential between
the ends. The mass flow is given by
Where Q is the mass flow, P1 is the pressure at
the input of the tube, and P2 is the pressure at
the output and C is the conductance of the
tube.
Conductance in the viscous flow regime is
proportional to the average pressure in the tube
and is high, compared to the molecular-flow
regime, because the gas molecules push each
other along. In the molecular-flow regime,
conductance through a tube is independent of
pressure and is given by
Where D is the diameter of the tube in
centimeters, and L is its length, also in
centimeters.
Pumping speed is expressed in liters per
second. The amount of mass going through the
Pump is given by
Where P is the pressure at the inlet of the
pump, and Sp is the pump speed. The net speed
of a pump connected to a vacuum chamber by
a tube is
The time required to pump the system from an
initial pressure of P0 down to P is
Where, V is the volume of the chamber.
Vacuum Chambers
Generally vacuum chambers are made out of
stainless steel or glass chambers because they
do not corrode, are easily cleaned, non
magnetic and have good out-gassing
characteristics. Stainless is used for large
vacuum systems because of its relatively high
strength, ease of welding and machinability.
The vacuum system consists of a vacuum
chamber, pumping system, deposition sources
and monitoring equipment, as explained in
Fig-75. Two basic configurations are (i) a glass
or stainless steel enclosure sealed to a metal
base or door by a gasket and (ii) a stainless
steel chamber with several ports to connect
depositions sources and measurement sensors.
Page 67 of 154

Fig-75 Typical Vacuum System
The bell jar vacuum system is less expensive to
construct and maintain. The disadvantage is
that the gaskets used to seal the bell and the
base plate together create a large contact area
with relatively high leakage rates. As a result
bell jar systems normally cannot reach the low
vacuum pressures that other stainless steel
vessels can obtain [62,63].
8.33 Pumping systems
The valve-and-piston principle is still the most
widely used way of extracting air in the
viscous-flow regime. Modern mechanical
pumps feature multiple stages, specialized low-
vapor-pressure oil sealants, and electric
motors.
Mechanical pumps can attain base pressures of
a few milli torr or a few tens of milli torr,
though below about 100 milli torr the oil used
in them will leak back into the chamber being
pumped on. This is called back- streaming,
which is undesirable. Back-streaming can be
eliminated by placing a high-vacuum pump
between the mechanical pump and the chamber
[62, 63 and 64]
.
Mechanical pumps are seldom operated below
100 milli torr, and for this reason they are
called as roughing pumps. To achieve even a
moderate vacuum of 10−2 torr or better, a
different pump design must be employed. The
most common and reliable high-vacuum
pumps in use today are turbo-molecular
pumps, or turbo pumps for short.
These are basically just very high-speed fans,
whose blades are moving at speeds comparable
to the speeds of gas molecules. Turbo pumps
are capable of sustaining very high
compression ratios, the ratio of the gas
pressure at the output to that at the input.
Typical compression ratios are in the order of
107 for air, for an outlet pressure of 100mtorr.
This low outlet pressure is maintained by a
mechanical pump, which acts as both a
roughing pump for the system and a backing
pump for the turbo. One advantage of using a
turbo pump in conjunction with a mechanical
pump is that the turbo pump’s compression
ratio depends strongly on the molecular weight
of the gas being pumped.
The log of the compression ratio is
proportional to the square root of the molecular
weight of the gas. Because the oils used in
mechanical pumps typically have very high
molecular weights, the compression ratio
across the turbo pump for these oils is
considerably higher than 107 and the turbo
pump effectively blocks any back-streaming
from the roughing pump. Speeds for turbo
pumps are usually independent of the type of
gas being pumped and they are specified by
their speeds [62, 63 and 64].
Page 68 of 154
Contamination
Contamination in the vacuum system is the
result of leaks from the vacuum container and
evaporation of moisture and other materials
from the inside walls of the container known as
out-gassing. The rate of out-gassing from a
surface can be expressed as
Where Or is the rate of out-gassing, q is the
specific out-gassing rate for the material and A
is the surface area.
The specific out-gassing rate is unique for a
given material as in Fig-76. The types of
materials used in vacuum system, the quality
of seals (rubber seals, metallic seals etc) and
the general clean environment can limit the
maximum obtainable vacuum [62, 63].
Fig-76 Specific out-gassing rates for materials
Some of the widely used processes like Pulsed
Laser Deposition (PLD), Chemical Vapor
Deposition (CVD), Sputtering and Molecular
Beam Epitaxy (MBE) are discussed below.
8.34 Pulsed Laser Deposition (PLD)
Pulsed laser deposition (PLD) is an efficient
method to produce thin films by utilizing a
technique called laser ablation. PLD gained
tremendous interest after T.Venketesan in 1987
first applied this method to create high
temperature superconductive (HTSC) films.
PLD is applicable to almost any material, in
particular to compounds that are difficult to
produce in thin-film form by other techniques.
Examples of such materials include complex
ceramic materials such as high-temperature
superconductors and certain magnetic
materials (e.g., yttrium iron garnet (YIG) and
ferromagnetic shape-memory (FSM) alloy Ni-
Mn-Ga.
PLD is a very reliable technique and due to the
short interaction times and the strong non
equilibrium conditions, allows some unique
applications
o Synthesis of metastable materials that
cannot be produced by standard deposition
techniques, (e.g. NbN, or Fe-Ag
supersaturated solid solution).
o Formation of films from species that are
generated only during PLD.
o Fabrication of nanocrystalline films.
o Formation of composite films consisting of
different materials.
Pulsed laser deposition is one of the newer
techniques to deposit thin films, and uses the
interaction between photons (laser beam) with
material surfaces [67].
Page 69 of 154

Fig-77 PLD Process
The PLD process is shown in Fig-77 and the
complete PLD system is shown in Fig-78. The
pulses of a high power laser situated outside
the vacuum deposition chamber are focused by
optics onto the target surface, where they are
absorbed.
Fig-78 Principal components of the vacuum system
The absorbed energy is converted into
electronic excitations, followed by a transfer
into thermal, chemical, and mechanical energy,
which causes the ablation and exfoliation of
the surface, which results in the plume
formation. To produce the plume a minimum
power density is needed, which will depend
mainly on the target material, laser
wavelength, and pulse duration.
The plume consists of a mixture of energetic
neutral atoms, molecules, ions, electrons,
clusters, micron-sized particulates, and molten
droplets. Gases, (i.e. O2, N2) can be introduced
in the chamber to promote gas phase reactions,
surface reaction, or to maintain the film
stoichiometry. The plume expansion is
followed by the re-condensation of the material
on a substrate [62, 63 and 64].
The targets are mainly rods or cylinders. Rod-
shaped targets have the advantage that the laser
beam ablates always a new point suppressing
surface roughening, structure formation, and
surface enrichment in one element due to
preferential sputtering or due to elemental
enrichment in the molten phase (specially in
multi-component targets).
As a consequence, the density of particulates
and changes in the plasma direction are
minimized and when an additional gas pulse is
used, it can be mounted closer to the rod
geometry. The distance between target and
substrate is typically 3-8 cm, while the
thickness uniformity of the growing film is
improved by rotation of the substrate.
Excimer Lasers
The term “excimer” is an abbreviation of
“excited dimmer” which is a reminder of the
Page 70 of 154
excited Xe2 molecules used as laser gas in the upper laser level, which is unstable and decays
first systems [64]. Modern excimer lasers use via spontaneous emission within ≈ 2.5 ns.
excited rare gas halogen molecules (exciplex)
as active media due to the higher efficiency.
The most common laser mixtures are: ArF
(λ=193 nm), KrF (λ=248 nm), XeF (λ=351
The formation rate of the ionic and excited
nm), and XeCl (λ=308 nm) and recently a real
precursors must be high enough to produce
excimer, i.e. F2 (157 nm) [63, 64].
excimers at a rate of several 1023/cm3/s to
allow lasing to occur [63, 64].
KrF Excimer laser
The light from an excimer laser is the result
Mechanisms of PLD
from a molecular gain medium in which the
The principle of pulsed laser deposition is a
lasing takes place between a bound upper
very complex physical phenomenon. It
electronic state and a repulsive ground
involves the formation of plasma plume with
electronic state. Energy is pumped into the gas
high energetic species and even the transfer of
mixture by a fast avalanche electric discharge
the ablated material through the plasma plume
excitation (electric discharge strengths of 10-
onto the heated substrate surface [62, 63 and 64].
15 kV/cm). In contrast to most other laser
types, the excitation of the active media of an
The thin film formation process in PLD can be
excimer laser is performed by kinetic
divided into the following four stages.
processes, involving a third body collision
partner (i.e. buffer gas). This is necessary to
o Laser radiation interaction with the target.
absorb a part of the kinetic energy of the KrF
o Dynamics of the ablation materials.
collision. The most important reactions for a
o Deposition of the ablation materials with
KrF laser are:
the substrate.
o Nucleation and growth of a thin film on the
substrate surface

Each stage in PLD is critical to the formation

of quality epitaxial crystalline, stoichiometric,
uniform thin films with small surface
roughness.

The main advantages of PLD:

o Conceptually simple: a laser beam

vaporizes a target surface, producing a film
with the same composition as the target.
o Versatile: many materials can be deposited
The collision of the Kr* and F- ion and the
in a wide variety of gases over a broad
collision partner results in the formation of the
range of gas pressures.

Page 71 of 154
o Cost-effective: one laser can serve many
vacuum systems.
o Fast: high quality samples can be grown
reliably in 10 or 15 minutes.
o Scalable: as complex oxides move toward
volume production [62, 63 and 64].
8.35 Sputtering
Sputtering is a vacuum evaporation process
which physically removes portions of a coating
material called the target, and deposits a thin,
firmly bonded film onto an adjacent surface
called the substrate (Fig-79). The process
occurs by bombarding the surface of the
sputtering target with gaseous ions under high
voltage acceleration. As these ions collide with
the target, atoms or occasionally entire
molecules of the target material are ejected and
propelled against the substrate, where they
form a very tight bond. The resulting coating is
held firmly to the surface by mechanical
forces, although, in some cases, and alloy or
chemical bond may result [65, 66].
Fig- 79 Sputtering Vacuum Deposition Process
Sputtering has proven to be a successful
method of coating a variety of substrates with
thin films of electrically conductive or non-
conductive materials. One of the most striking
characteristics of sputtering is its universality.
Since the coating material is passed into the
vapor phase by a mechanical rather than a
chemical or thermal process, virtually any
material can be deposited. Direct current is
used to sputter conductive materials, while
radio frequency is used for non-conductive
materials.
The range of sputtering application is large.
Current applications of great importance
include thin films of:
o Magnetic materials for data storage tapes.
Typical materials are Co-Ni, Tb-Fe and
Co-Ni-Cr.
o Optical materials for lens characteristics.
Typical materials are CeO2, MgO and
MgF2.
o Lubricant materials for reducing friction.
Typical materials are MoS2, WS2, and
PTFE.
o Wear-resistant materials to lengthen cutting
tool life. Typical materials are TiN, TiC,
and ZrB2.
o Metallizing materials for microcircuits.
Typical materials are Al, W-Ti, Al-Si and
Al-Cu.
o Transparent conducting materials. The
most typical material is xLn2O3 -ySnO2.
o Thin-film resistors. Typical materials are
Ni-Cr, Cr-Si and Cr- SiO.
o Amorphous bubble memory devices.
Typical materials are Gd-Co. Lu3Fe5O12,
and Gd3Ga5O12.
o Microcircuit mask blanks. The most typical
material is Cr.
Page 72 of 154
Additional applications include oxide
microcircuit insulation layers, amorphous
optical films for integrated optics devices,
piezoelectric transducers, photoconductors,
luminescent films for display devices, optically
addressed memory devices, video discs, solid
electrolytes and thin film lasers [65, 66].
Types of Sputtering
The basic principle of sputtering is the same
for all sputtering technologies. The differences
typically relate to the manner in which the ion
bombardment of the target is realized.
Types of Sputtering are:
o DC sputtering
o DC Magnetron sputtering
o RF sputtering
DC Diode Sputtering Deposition
Target (source) and substrate are placed on two
parallel electrodes (diode) inside a chamber
filled with inert gas (Ar).When a DC voltage
(~ kV) is applied to the diode the free electrons
in the chamber are accelerated by the e-field
(Fig-80).
Fig- 80 Schematic of DC diode sputtering Vacuum
Deposition Process
These energetic free electrons in-elastically
collide with Ar atoms and excitation of Ar
occurs and the gas glows which induces the
ionization of Ar forming Ar+ + 2nd electron.
The 2nd electrons repeat the above process
causing the gas to breakdown and the
discharge to glow (plasma) (Fig-80) [65, 66].
Near the cathode, electrons move much faster
than ions because of smaller mass and positive
charge build up near the cathode, raising the
potential of plasma. Fewer electrons collide
with Ar and a few collisions with these high
energetic electrons results in mostly ionization,
rather than excitation forming a dark zone
(Crookes Dark Space) (Fig-81).
Fig- 81 Self sustained discharge in DC diode sputtering
Vacuum Deposition Process
Discharge causes voltage between the
electrodes reduced from ~103 V to ~102V,
mainly across the dark space and the electrical
field in other areas is significantly reduced by
the screening effect of the position charge in
front of cathode. Positive ions entering the
Page 73 of 154
dark space are accelerated toward the cathode
(target), bombarding (sputtering) the target.
The atoms knocked out from the target
transport to the substrate (momentum transfer,
not evaporation!) and generate 2nd electrons
that sustain the discharge (plasma) [65, 66].
Requirement for Self-Sustained Discharge
If the cathode-anode space (L) is less than the
dark space length, then the ionization occurs
with a few excitations and cannot sustain
discharges. On the other hand, if the Ar
pressure in the chamber is too low then a large
electron mean-free path is created and the 2nd
electrons reach anode before colliding with Ar
atoms and cannot sustain discharge either.
Condition for Sustaining Plasma:
Where L is the electrode spacing and P is the
chamber pressure For example: Typical target-
substrate spacing: L ~ 10cm and P > 50 mtorr.
Deposition Rate vs. Chamber Pressure
Mean-free path of an atom in a gas ambient:
Sputtering deposition rate R:
High chamber pressure results in low
deposition rate as shown in the example:
L = 10 cm, P = 50 mtorr
o λ~ 0.1 cm
o sputtered atoms have to go through
hundreds of collisions before reaching the
substrate
o significantly reduces deposition rate
o also causes source to deposit on chamber
wall and re-deposit back to the target
Large LP sustains plasma and small LP
maintains good deposition rate and reduces
random scattering.
DC Magnetron Sputtering
In DC Magnetron Sputtering low chamber
pressure is used to maintain high deposition
rate and a magnetic field is used to confine
electrons near the target to sustain plasma as
shown in Fig-82.
Fig- 82 Schematic of DC Magnetron sputtering
If a magnetic field parallel to the cathode
surface is applied the electrons will be hopping
(cycloid) near the surface (trapped).
Impact of Magnetic Field on Ions
The impact of Magnetic field on ions is
explained in Fig -83 below.
Page 74 of 154

Fig- 83 Schematic of DC Magnetron sputtering showing
the impact of Magnetic field on ions.
Hopping radius r:
Where, Vd is the voltage drop across the dark
space (~ 100 V), B is the magnetic field (~ 100
G) for electron r ~ 0.3 cm and Ar+ ion the r ~
81 cm.
Then the current density (proportional to
ionization rate) increases by 100 times and
required discharge pressure drops 100 times
and deposition rate increases 100 times~ as
shown in Fig-84 [65, 66].
Fig- 84 DC Magnetron sputtering – Deposition rate Vs
Chamber pressure
RF Sputtering
The use of radio frequency, RF to sputter
material was investigated in the 1960’s.
Davidse and Maiseel used RF sputtering to
produce dielectric films from a dielectric target
in 1966. In 1968 Hohenstein co-sputtered glass
using RF and metals (Al, Cu, Ni) with DC, to
form cermet resistor films. RF sputter
deposition is not used extensively for
commercial PVD for several reasons. The
major reasons are it is not economic to use
large RF power supplies due to their high cost
and the fact that you introduce high
temperatures, due to the high self-bias voltage
associated with RF power, into insulating
materials.
DC sputtering cannot be used for depositing
dielectrics because the insulating cathode will
cause charge build up during Ar+ bombarding,
which reduces the voltage between electrodes
and the discharge distinguishes. To eliminate
this problem AC power was used, that
developed the RF Sputtering technique.
Fig- 85 RF sputtering
Page 75 of 154
Using AC power at low frequency (<100 KHz)
both electrons and ions can follow the
switching of the voltage (Fig-85) [65, 66].
At high frequency (> 1 MHz) the heave ions
can no longer follow the switching and the ions
are accelerated by dark-space (sheath) voltage.
The electron neutralizes the positive charge
buildup on both electrodes however; there are
two dark spaces which sputter both target and
substrate at different cycles as shown in Fig-
86.
Fig- 86 RF sputtering with AC voltage bias
Where VT is the voltage across the target
sheath, Vs is the voltage across substrate
sheath, AT is the area of target electrode and As
is the area of substrate electrode. Larger dark-
space voltage develops at the electrode with
smaller area making the target electrode VT
small [65, 66].
Reactive sputtering
In this process, a small amount of some non-
noble gas such as oxygen or nitrogen is mixed
with the plasma-forming gas. After the
material is sputtered from the target, it reacts
with this gas, so that the deposited film is a
different material, i.e. an oxide or nitride of the
target material.
Reactive sputtering Process
Reactive gases like oxygen or nitrogen is
added to the chamber during deposition
(evaporation or sputtering). Chemical reactions
take place on substrate and target. The target
may get unwanted impurities if chemical
reactions are faster than sputter rate. This can
be avoided by adjusting the reactive gas flow
to get good stoichiometry without
incorporating excess gas into film [65, 66].
8.36 Molecular Beam Epitaxy (MBE)
MBE is a technique for epitaxial growth
through the interaction of one or several
molecular or atomic beams that occurs on a
surface of a heated substrate (Fig-87).
Fig. 87 Schematic diagram of a MBE system
Page 76 of 154
The solid source materials are placed in
evaporation cells to provide an angular
distribution of atoms or molecules in a beam.
The substrate is heated to the necessary
temperature and, when needed, continuously
rotated to improve the growth homogeneity [64,
66]
. 1400oC, molybdenum and tantalum are widely
MBE operating conditions
o The mean free path λ of the particles
should be larger than the geometrical size
of the chamber. It is easily fulfilled if the
total pressure does not exceed 10-5 Torr
(Fig-88).
o The condition for growing a sufficiently
clean epilayer must be satisfied. (Eg: For
the monolayer deposition times of the
beams tb and the background residual vapor
tres the relation is t res < 10-5 tb. This can be
fulfilled by (UHV) ultra high vacuum).
Fig. 88 Graph showing Mean Free path
UHV is the essential environment for MBE.
Therefore, the rate of gas evolution from the
materials in the chamber has to be as low as
possible. So pyrolytic boron nitride (PBN) is
chosen for the crucibles which give low rate of
gas evolution and chemical stability up to
used for the shutters, heaters and other
components, and only ultra pure materials are
used as source. To reach UHV, a bakeout of
the whole chamber at approximately 200oC for
24 hours is required any time after having
vented the system for maintenance. A
cryogenic screening around the substrate
minimizes spurious fluxes of atoms and
molecules from the walls of the chamber.
Despite this big technological problem, MBE
systems permit the control of composition and
doping of the growing structure at monolayer
level by changing the nature of the incoming
beam just by opening and closing the
mechanical shutters. The operation time of a
shutter of approximately 0.1s is normally much
shorter than the time needed to grow one
monolayer (typically 1-5s). Careful variation
of the temperatures of the cells by PID
controllers permits the control of the intensity
of the flux of every component or dopant of
better than 1 %.
Fig-89 RHEED Oscillations
The UHV environment of the system is also
ideal for many insitu characterization tools,
Page 77 of 154
like the RHEED (Reflection High Energy
Electron Diffraction). The oscillation of the
RHEED signal exactly corresponds to the time
needed to grow a monolayer and the diffraction
pattern on the RHEED window gives direct
indication over the state of the surface as can
be seen in Fig-89 [64, 66].
Effusion Cells
The effusion cells used in MBE systems
exploit the evaporation process of condensed
materials as molecular flux source in vacuum.
In a closed enclosure, for pure substances,
equilibrium is established between the gas and
the condensed phase. Such systems have only
one degree of freedom f, that means that the
pressure peq is a function of the temperature T
and can be approximately expressed by the
Clapeyron equation.
Where, ∆H is the evaporation enthalpy and k B
the Boltzmann constant. Under this
equilibrium condition, we observe that when
the peq is very low, it is possible to treat the
incoming and the outcoming flux
independently. A close look to the fluxes of
particles having a mass m on the condensed
phase surface shows that the maximum value
for the evaporated flux Γm is
This assumes that each molecule from the gas
phase is always trapped by the surface and an
equal opposite flux of material must leave the
condensed phase to maintain the equilibrium
pressure.
Considering now that the impinging beam is
partially reflected and only a fraction ‘a’ is
accommodated on the surface, the complete
expression for the flux leaving the surface can
be easily found as
The factor ‘a’ is dependent on the microscopic
status of the surface and is strongly
unpredictable.
The Knudsen evaporating method overcomes
this problem providing a molecular beam that
is independent of ‘a’. An ideal Knudsen cell is
composed of a large enclosure where the
condensed material is in thermodynamic
equilibrium with the gas phase and peq is not
perturbed.
The ideal Knudsen cell (as explained in in
Section: ) exhibits an angular distribution of
the evaporated particles that follows a cosine
law, where the angle θ is referred to the normal
to A.
The beam is usually bent through an angle of
270° in order to ensure that the gun filament is
not directly exposed to the evaporant flux.
Lower vapor pressure materials are deposited
through this process because of the non
uniformity in heating in this process. Typical
deposition rates for electron beam evaporation
ranges from 1 to 10 nanometers per second.
In this process, slow streams of an element can
be directed at the substrate, so that material
deposits one atomic layer at a time.
Page 78 of 154
Compounds such as gallium arsenide are
usually deposited by repeatedly applying a
layer of one element (Ga), then a layer of the
other (As), so that the process is chemical, as
well as physical.
The beam of material can be generated by
either physical means (that is, by a furnace) or
by a chemical reaction (chemical beam
epitaxy) [64, 66].
A typical MBE chamber is shown in Fig-90 to
visualize the actual equipment.
Fig. 90 MBE Growth chamber
Topotaxy
In Topotaxy (heterotopotaxy / homotopotaxy),
a specialized technique similar to epitaxy, thin
film crystal growth occurs in three dimensions
due to the crystal structure similarities between
the substrate crystal and the growing thin film
material [64-66].
Chemical deposition
In this process, a fluid precursor (one of the
compounds that participate in the chemical
reaction that produces another compound)
undergoes a chemical change at a solid surface,
leaving a solid layer on the surface with little
regard to direction. Thin films from chemical
deposition techniques tend to be conformal,
rather than directional. Chemical deposition is
further categorized by the phase of the
precursor like liquid phase, Gas Phase [65, 66].
8.37 Chemical vapor deposition (CVD)
generally uses a gas-phase precursor, often a
halide or hydride of the element to be
deposited. In the case of MOCVD, an
organometallic gas is used. Commercial
techniques often use very low pressures of
precursor gas.
CVD Process
Reactive precursor gases are introduced into
the chamber and heat is applied to activate the
decomposition of gases to form plasma. The
gas is absorbed by the substrate surface and
reactions takes place on substrate surface and
the thin film is formed. Transport of volatile
byproducts away form substrate takes place
through Exhaust waste (Fig-91, 92) [65, 66].
Fig. 91 Schematic diagram of CVD Process
Page 79 of 154
Types of CVD reactions
o Pyrolysis Compound Formation
o Reduction
o Oxidation
o Compound Formation
The types of reactions are explained in detail
below.

Pyrolysis (Thermal Decomposition)

CVD Deposition Condition

Mass-Transport Limited Deposition
o At high temperature such that the reaction
Reduction (Lower temperature than Pyrolysis) rate exceeds the gas delivering rate.
o Gas delivering controls the film deposition
rate.
o Film growth rate is insensitive to
temperature
o Film uniformity depends on whether
reactant can be uniformly delivered across
a wafer and wafer-to-wafer.

Reaction -Rate Limited Deposition

o At low temperature or high vacuum such
Oxidation that the reaction rate is below the gas
arriving rate.
o Temperature controls film deposition rate.
o Film uniformity depends on temperature
uniformity across a wafer and wafer-to-
wafer.

Types of CVD
o Low-Pressure CVD (LPCVD)
o Plasma-Enhanced CVD (PECVD)
o Atmosphere-Pressure CVD (APCVD)
o Metal-Organic CVD (MOCVD)

Page 80 of 154
Low-Pressure CVD (LPCVD)
Thermal energy for reaction activation
o System works at vacuum (~ 0.1 –1.0 torr),
resulting in high diffusivity of reactants
reaction-rate is limited.
o Wafer can stacked closely without lose
uniformity as long as they have the same
temperature
o Temperature is controlled around 600 -
900ºC by “flat” temperature zone through
using multiple heaters
o Low gas pressure reduce gas-phase
reaction which causes particle cluster that
contaminants the wafer and system

Fig. 92 Schematic diagram of PECVD

Plasma-Enhanced CVD (PECVD) materials that cannot sustain high
Plasma enhanced CVD uses an ionized vapor, temperature
or plasma, as a precursor. Commercial o Surface reaction limited deposition;
PECVD, relies on electromagnetic means substrate temperature control (typically
(electric current, microwave excitation), rather cooling) is important to ensure uniformity)
than a chemical reaction, to produce a plasma
[65- 70]
. Common CVD Reactants
Process stages of PECVD

o Use RF-induced plasma (as in sputtering

case) to transfer energy into the reactant
gases, forming radicals (decomposition)
o Low temperature process (< 300 ºC) For
depositing film on metals and other

Page 81 of 154
 Fig-93 Comparison chart for various thin film deposition technologies
Technological comparison
The comparison chart for typical thin film
deposition technology is given above (Fig-93).
Chemical Solution Deposition
In (CSD) a liquid precursor, usually a solution
of organometallic powders dissolved in an
organic solvent is used. This is a relatively
inexpensive, simple thin film process that is
able to produce stoichiometrically accurate
crystalline phases [65- 70].
Sol-Gel In the sol-gel process the precursor is
dissolved in a solvent (forming a sol or gel
depending on the reactor conditions) and
precipitates due to chemical reactions. The sol-
gel process consists of 4 basic steps:
Hydrolysis, Condensation, Polymerization of
particles, growth of particles, agglomeration
and formation of networks.
The outcome of the process depends on several
factors that influence the hydrolysis and
condensation rates. Among them, there are few
that are considered to have a greater impact:
pH, nature and concentration of catalysts,
H20/precursor molar ratio and temperature [65-
70]
.
Page 82 of 154
Doping Process
The pure semiconductor is basically neutral. It
contains no free electrons in its conduction
bands. Even with the application of thermal
energy, only a few covalent bonds are broken,
yielding a relatively small current flow. A
much more efficient method of increasing
current flow in semiconductors is by adding
very small amounts of selected additives to
them, generally no more than a few parts per
million. These additives are called impurities
and the process of adding them to crystals is
referred to as Doping (Fig-94).
Fig- 94 Doping a Semi conductor
The purpose of semiconductor doping is to
increase the number of free charges that can be
moved by an external applied voltage. When
an impurity increases the number of free
electrons, the doped semiconductor is
NEGATIVE or N TYPE, and the impurity that
is added is known as an N-type impurity.
However, an impurity that reduces the number
of free electrons, causing more holes, creates a
POSITIVE or P-TYPE semiconductor, and the
impurity that was added to it is known as a P-
type impurity. Semiconductors which are
doped in this manner with either ‘N’ or ‘P’
type impurities are referred to as EXTRINSIC
semiconductors.
N-Type Semiconductor
The N-type impurity loses its extra valence
electron easily when added to a semiconductor
material, and in doing so, increases the
conductivity of the material by contributing a
free electron. This type of impurity has 5
valence electrons and is called a
PENTAVALENT impurity. Arsenic,
antimony, bismuth, and phosphorous are
pentavalent impurities. Because these materials
give or donate one electron to the doped
material, they are also called DONOR
impurities.
Pure germanium may be converted into an N-
type semiconductor by "doping" it with any
donor impurity having 5 valence electrons in
its outer shell. Since this type of semiconductor
(N-type) has a surplus of electrons, the
electrons are considered MAJORITY carriers,
while the holes, being few in number, are the
MINORITY carriers.
P-Type Semiconductor
The second type of impurity, when added to a
semiconductor material, tends to compensate
for its deficiency of 1 valence electron by
acquiring an electron from its neighbor.
Impurities of this type have only 3 valence
electrons and are called TRIVALENT
impurities. Aluminum, indium, gallium, and
boron are trivalent impurities. Because these
materials accept 1 electron from the doped
material, they are also called ACCEPTOR
impurities.
Page 83 of 154
Methods of doping
The methods of doping are Diffusion, Ion
implantation and doping during growth which
are explained below.
Diffusion
In this method, the semiconducting material to
be doped is placed in a furnace wherein the
furnace contains an atmosphere of a carrier gas
and a dopant containing gas. The doping
containing gas is greater than about 0.1 volume
percent of the total volume in the furnace
chamber. The pressure of the composite gas is
greater than about 0.1 Torr. The composite gas
has an oxidizing agent concentration of less
than about 1 part per million (Fig-95) [68-70].
Fig- 95 Doping a Semi conductor by diffusion method
This method permits the direct doping of a
silicon surface to form a shallow n-doped
region having a high peak concentration by a
diffusion process thereby eliminating damage
to the silicon surface from ion implantation
which is the commonly used method to
achieve these high doping concentrations.
Since the method is non directional trench
sidewalls can be doped at high concentrations.
Ion implantation
The introduction of dopants in a semiconductor
is the most common application of ion
implantation. Dopant ions such as boron,
phosphorus or arsenic are generally created
from a gas source, so that the purity of the
source can be very high. These gases tend to be
very hazardous.
When implanted in a semiconductor, each
dopant atom creates a charge carrier in the
semiconductor (hole or electron, depending on
if it is a p-type or n-type dopant), thus
modifying the conductivity of the
semiconductor in its vicinity (Fig-96) [68-70].
Fig- 96 Doping a Semi conductor by Ion implantation
Doping during growth
In this method the dopant is injected into the
plasma and are based on the interactions of
plasma or neutral gas with the surfaces of
substrate at different temperatures and varying
electric potentials (co-sputtering, dc-sputtering,
thermally activated injection to the neutral gas,
plasma-assisted transport) (Fig-97) [68-70].
Page 84 of 154

Fig- 97 Doping a Semi conductor during growth
Procedure Sample preparation for Solid -
Solid Reaction Method
The samples can be prepared for standard solid
- solid reaction by using appropriate quantities
of precursors (Eg. ZnO of 99.99% purity) and
(Eg.MnO2 of 99.99% purity) can be mixed and
ground properly in order to obtain sub-micron
size precursors. The mixture should then be
calcined at 400oC for 8 hrs in air or appropriate
atmosphere of Oxygen, Nitrogen, or hydrogen.
The calcined powder obtained should be
pressed to form dense pellets and sintered at or
above transition temperature but below the
melting temperature according to the materials
to be calcined (eg 12 hrs at temperatures
ranging from 500oC to 900oC in suitable
atmospheres mentioned above for the Mixture
of ZnO and MnO2).
The pellets thus obtained have to be
characterized for physical as well as magnetic
properties and can be used as a source material
to make thin films using PLD [62- 64].
8.40 Characterization Techniques
The description of the structure of a solid
requires the determination of the crystal
system, space group, unit cell dimensions,
atomic coordinates and electron density
distribution around the atoms by means of
diffraction involving X-rays, electrons or
neutrons called characterization.
8.41 X-Ray diffraction
X-Ray diffraction (XRD) is used to identify
and characterize solids. Synchrotron X-
radiation of continuously variable wavelength
has made X-ray diffraction a powerful
structural tool for the study of solids. A
technique of great utility in determining the
structures of oxides is the Rietveld treatment of
powder X-ray diffraction.
X-diffraction can be utilized for phase
identification, quantitative analysis of mixtures
of phases, particle size analysis, and
characterization of physical imperfections and
in situ studies of reactions. Variable
temperature X-ray diffraction of crystalline
materials is used to study phase transitions,
thermal expansion, and thermal vibrational
amplitude of atoms on solids [20].
Advanced developments of XRD
Soft X-ray spectroscopies, X-ray absorption
(XAS), X-ray emission (XES), and Resonant
inelastic X-ray scattering (RIXS)
spectroscopies are advanced developments of
XRD [20].
8.42 Magnetic Dichroism Spectroscopy
The term dichroism is used more generally to
reflect the dependence of photon absorption of
a material on polarization. In fact, it is derived
from Optics which means changes in the
Page 85 of 154
absorption of polarized light on passing
through a material in two different directions
called dichroism.
The origin of the dichroism effect can be
anisotropies in the charge or the spin in the
material known as magnetic dichroism. The
principles and applications of magnetic
dichroism techniques in the x-ray region, the
X-Ray Magnetic Circular Dichroism (XMCD)
and X-Ray Magnetic Linear Dichroism
(XMLD) techniques are discussed below [71].
8.43 X-ray absorption spectroscopy (XAS)
X-ray absorption spectroscopy (XAS) utilizes
the energy dependent absorption of x-rays to
obtain information about the elemental
composition of the sample, as shown in Fig-98.
Fig- 98 X-ray absorption spectra of a wedge sample,
revealing the composition at various points along the
wedge
The Fe signal increases from bottom to top
because of the increasing Fe layer thickness
and the Ni signal decreases because of the
limited electron escape depth of the total
electron yield signal used to record the spectra.
The Cu signal is constant, reflecting its
constant 1nm thickness (Fig-99). It also gives
information on the chemical environment of
the atoms and their magnetic state. Core
electrons are excited in the absorption process
into empty states above the Fermi energy and
thereby probe the electronic and magnetic
properties of the empty valence levels. The
magnetic properties of 3d transition metal
elements Fe, Co and Ni are largely determined
by the 3d valence electrons. Since X-ray
absorption spectra are governed by dipole
selection rules the d-shell properties are best
probed by L-edge absorption studies (2p to 3d
transitions). The L-edge X-ray absorption
spectra of the transition metals and oxides are
dominated by two main peaks separated by
about 15 eV as shown in Fig-99 [71, 72].
Fig- 99 L - edge x-ray absorption spectra of Fe, Co and
Ni in the form of the elemental metals and as oxides.
The two main structures are called the L3 (lower energy)
and L2 absorption edges
The two main peaks in the spectra arise from
the spin orbit interaction of the 2p core shell
and the total intensity of the peaks is
proportional to the number of empty 3d
valence states. The metal spectra show two
broad peaks, reflecting the width of the empty
Page 86 of 154
d-bands. The oxide spectra exhibit
considerable fine structure, called multiple
structure. The empty oxide states are more
localized than metal states and their energies
are determined by crystal field and multiple
effects. Multiple effects arise from the spin and
orbital momentum coupling of different 3d
valence holes (or electrons) in the electronic
ground state, and from coupled states formed
after x-ray absorption between the 3d valence
holes and the 2p core hole [71, 72].
The metals are usually ferromagnetic and their
magnetic properties are best studied with X-
Ray Magnetic Circular Dichroism (XMCD)
spectroscopy, while the oxides are usually
antiferromagnetic and are studied with X-Ray
Magnetic Linear Dichroism (XMLD)
spectroscopy.
8.44 X-Ray Magnetic Circular Dichroism
(XMCD)
The concepts of XMCD spectroscopy, was
pioneered by Gisela Schütz et al. in 1987. The
first X-ray absorption sum rule links the total
intensity of the L3 and L2 resonances with the
number N of empty d states (holes) (Fig-100).
The d valence shell can hold up to 10 electrons
which are filled into band states up to the
Fermi level and the number of filled states is
therefore 10 -N. For a magnetic material the d
shell has a spin moment which is given by the
imbalance of spin-up and spin-down electrons
or equivalently (except for the sign) by the
imbalance of spin-up and spin-down holes.
The XMLD effect is large only in cases where
the absorption edge exhibits multiple structures
shown in (Fig-100) [71, 72].
Fig- 100 Size of magnetic dichroism effects.
To measure the difference in the number of d
holes with up and down spin, the x-ray
absorption process is made spin dependent.
This is done by use of right or left circularly
polarized photons which transfer their angular
momentum to the excited photoelectron. The
photoelectron carries the transferred angular
momentum as a spin or an angular momentum,
or both (Stohr & Wu). If the photoelectron
originates from a spin-orbit split level, e.g. the
p3/2 level (L3 edge), the angular momentum of
the photon can be transferred in part to the spin
through the spin-orbit coupling.
Right circular photons (RCP) transfer the
opposite momentum to the electron as left
circular photons (LCP) photons, and hence
photoelectrons with opposite spins are created
in the two cases. Since the p3/2 (L3) and p1/2
(L2) levels have opposite spin-orbit coupling,
the spin polarization will be opposite at the two
edges. In the absorption process, "spin-up" and
"spin-down" are defined relative to the photon
helicity or photon spin [71, 72].
Page 87 of 154

In Fig-101 the transitions occur from the spin-
orbit split 2p core shell to empty conduction
band states. In conventional X-ray absorption
the total transition intensity of the two peaks is
proportional to the number of d holes (first
sum rule). By use of circularly polarized X-
rays the spin moment (b) and orbital moment
(c) can be determined from linear
combinations of the dichroic difference
intensities A and B, according to other sum
rules [71, 72].
Since spin flips are forbidden in electric dipole
transitions, spin-up (spin-down) photoelectrons
from the p core shell can only be excited into
spin-up (spin-down) d hole states.
Fig-101 Electronic transitions in conventional L-edge x-
ray absorption (a) X-ray magnetic circular dichroism (b,
c) one-electron model.
Hence the spin-split valence shell acts as a
detector for the spin of the excited
photoelectron and the transition intensity is
simply proportional to the number of empty d
states of a given spin. The quantization axis of
the valence shell "detector" is given by the
magnetization direction. The size of the
dichroism effect scales like cos θ, where θ is
the angle between the photon spin and the
magnetization direction.
The maximum dichroism effect (20%) is
observed if the photon spin direction and the
magnetization directions are parallel and anti-
parallel as shown on the left side of Fig-102.
When the photon spin and the magnetization
directions are perpendicular the resonance
intensities at the L3 and L2 edges lie between
those obtained for parallel and anti-parallel
alignments [71, 72].
The L3 and L2 resonance intensities and their
differences for parallel and anti-parallel
orientation of photon spin and magnetization
directions are quantitatively related by sum
rules to the number of d holes and the size of
the spin and orbital magnetic moments. Angle
dependent measurements in external magnetic
fields give the anisotropies of the spin density
and orbital moment [71, 72].
8.45 X-Ray Magnetic Linear Dichroism
(XMLD)
XMLD spectroscopy was pioneered by Gerrit
van der Laan et al. in 1986. The electric field
vector E of linearly polarized X-rays acts as a
search light for the number of valence holes in
different directions of the atomic volume. The
anisotropy of the charge in the atomic volume
is caused by anisotropy in the bonding, i.e. by
the electrostatic potential.
In the absence of spin order, linear dichroism
NEXAFS spectroscopy can only determine
charge order in systems where the absorbing
atom has lower than cubic symmetry.
However, in the presence of spin order the
spin-orbit coupling leads to preferential charge
order relative to the spin direction even in
Page 88 of 154
cubic systems. This effect is the basis for the
determination of the spin axis in ferromagnetic
and especially antiferromagnetic systems by
means of x-ray magnetic linear dichroism
(XMLD) spectroscopy [71, 72].
Since the electric field vector oscillates in time
along an axis and the radiation may be
absorbed at any time, linearly polarized x-rays
are only sensitive to axial not directional
properties.
The orientation of the antiferromagnetic or
ferromagnetic axis, but the spin direction itself
cannot be determined. Fig-102 shows the
origin of the XMLD effect in NiO.
Fig-102 Origin of XMLD for NiO
In Fig-102 the electronic configurations
involved in the x-ray absorption process is
shown in the Left. In the ground state there are
two d holes (d2 hole configuration) and their
energy levels are determined by multiple and
crystal field effects. In the final state, a 2p hole
is created by x-ray absorption and one d hole is
filled by the excited electron.
The resulting pd hole configuration again gives
rise to multiple splitting and the XAS spectrum
reflects the multiple structure. In the
paramagnetic state the absorption spectrum of
NiO does not exhibit polarization dependence
because of cubic symmetry. In the
antiferromagnetic state the spin-orbit coupling
leads to a distortion of the charge density and
an XMLD effect is observed [71, 72].
Because of the cubic symmetry of the NiO
lattice the charge distribution around the atoms
is nearly spherical and no linear dichroism
effect exists above the Néel temperature (520
K), where NiO is paramagnetic. At room
temperature, NiO is antiferromagnetic and the
Ni spins are oriented in the (1, 1, 1) plane
along three possible directions in the fcc
lattice. There is no net magnetic moment
because an equal number of spins point into
opposite directions, so only a preferential
magnetic axis exists.
The alignment of the local atomic spins along
this axis breaks the cubic symmetry of the
charge through the spin orbit coupling. As a
consequence the charge exhibits a small
anisotropy in the unit cell, i.e. it is no longer
spherical but shows an ellipse-like distortion
about the magnetic direction. This charge
anisotropy leads to an asymmetry of the x-ray
absorption signal through the search light
effect [71, 72].
The maximum XMLD difference is obtained
for E parallel versus E perpendicular to the
magnetic axis, as shown in Fig-103. In contrast
to the XMCD effect the XMLD effect has a
cos 2θ dependence, where θ is the angle
between E and the magnetic axis.
Page 89 of 154
In general, the XMLD effect is small in 3d
metals owing to the small size of the spin orbit
interaction and the large band width, resulting
in small charge anisotropy when the d states
are summed over the Brillouin zone.
However, a sizeable XMLD effect (of order
10-30%) may be observed in the presence of
multiplet splitting. At a particular multiplet
energy only selected d valence states are
probed through matrix element effects that
enhance the XMLD effect. Each multiplet is a
strongly coupled spin-orbit state whose spatial
extent is non-spherical, giving rise to the large
XMLD effect.
In Fig-102 the XMLD effect is especially
visible at the Ni L2-edge where a sizeable
difference is observed for E parallel (green)
versus perpendicular (red) to the magnetic axis.
Since x-ray linear dichroism can arise from
electric and magnetic asymmetry s, magnetic
order effects can be distinguished from Ligand
field effects through temperature dependent
measurements.
Circularly polarized x-rays have directionality
and they can detect the direction of the spin
and orbital moments which is utilized in
XMCD microscopy of ferromagnets. The
dependence of the XMLD intensity on the
relative orientation of the electric field vector
and the magnetic axis can be used for XMLD
imaging for antiferromagnets [71, 72].
Electron diffraction
Electron diffraction is a valuable technique for
studies in solids. The differences entail the
small wavelength of electrons and the charge
carried by them. The smaller wavelength
makes it possible to record extensive sections
of the reciprocal lattice directly with a small
stationary crystal. Because of the charge,
interaction of electrons with atoms is
considerably stronger than that of X-rays, thus
making it possible to record electron
diffraction patterns almost simultaneously.
One can investigate defect ordering,
superstructures, and fine particle samples [20, 72,
and 73]
.
Neutron diffraction
Thermal neutrons with a velocity of about
4000 m/s associated with a wavelength of ~ 1.0
Ǻ are used in neutron diffraction experiments.
Neutron diffraction is particularly useful in
locating light atoms such as hydrogen in
crystals.
Neutron diffraction provides an experimental
means whereby the different magnetic
structures can be determined. Inelastic neutron
scattering by crystals is used in the study of
quantized vibrational modes (phonons) and
dynamics in solids [20, 72, and 73].
8.46 Piezoresponse force microscopy
Piezoresponse Force Microscopy (PFM) is a
scanning probe microscopy (SPM) technique
based on the reverse piezoelectric effect, where
a (piezoelectric) material expands or contracts
upon applying to it an electric field [20, 72, 73].
PFM is an Imaging Technique classified under
Derivative Imaging Modes. It is a derivative of
the Primary Imaging Mode called Contact
Mode AFM. In PFM, the AFM probes a
sample’s mechanical response to an applied
electric field. The AFM tip used in PFM is
usually made of, or is coated with, a
conductive material, as this conductivity
Page 90 of 154
enhances the electrical contact between the tip
and the sample.
Fig- 103 Piezoresponse Force Microscopy Setup
An AC modulation with an optional DC offset
bias is applied to the tip, which is in contact
with the sample surface, and the piezoresponse
of the sample is measured from the deflection
of the AFM cantilever [20, 72, and 73].
This measurement uses a lock-in amplifier
(Fig-103). The frequency of the applied ac
voltage is typically far from (below) the
fundamental resonance frequency of the AFM
cantilever so as to avoid driving the cantilever
into resonant oscillations [71, 72].
The Utility of PFM
PFM is one of the most important tools that
enables measurements and characterization of
piezoelectric behavior of materials on the
nanometer, and sub-nanometer scale. There is
no other tool currently available that can
routinely and with the same ease measure the
electromechanical response of a material on
the level of individual nanometer-scale grains.
The PFM has been shown to delineate regions
of different piezoresponse with subnanometer
lateral resolution.
In Fig-104, the PFM image (phase signal, right
image) shows contrast that delineates regions
of differing piezoresponse on the surface of a
Lithium Niobate sample, whose topography
(left image) reveals no features corresponding
to those in the piezoresponse image.
The PFM signal in this image is recorded from
the vertical movement of the AFM tip, but
similarly, the lateral movement of the tip may
be recorded (as in Lateral Force Microscopy)
to construct a map that is descriptive of in-
plane polarization of the various regions on the
sample surface.
Fig- 104 comparison AFM and PFM images
PFM is very useful in investigating the
nanometer-scale piezoelectric properties of
ferroelectrics. Ferroelectric thin films are the
subject of intense research and development
for their optoelectronic, sensor, and high-
density memory applications. The lateral
resolution of PFM provides highly localized
information about the electromechanical
behavior of thin ferroelectric films. The PFM
can be used to interrogate a given nanometer-
scale domain in an island for its piezoelectric
response; if there is a piezo response, this
implies ferroelectricity.
Page 91 of 154
PFM Spectroscopy is a non-imaging technique
that compliments PFM imaging. In PFM
Spectroscopy, the piezoresponse of a given
location on the sample can be mapped versus
the dc bias. This technique can also be used to
study hysteretic characteristics of the
piezoresponse [72-75].
8.47 Transmission Electron Microscopy
The electron microscope is the most versatile
instrument available to study the ultrastructure
of materials, to identify new or known phases,
and to simultaneously yield information on
composition. Usually electron diffraction and
imaging are employed together in transmission
electron microscopy (TEM). These capabilities
are further enhanced in a scanning
transmission electron microscope (STEM).
TEM generally produces a projected image
wherein all depths of thin specimens are in
focus at the same time, making it difficult to
interpret surface features of specimens to
operate at different temperatures, in different
atmospheres [20, 72-75].
8.48 Scanning Electron Microscopy
In scanning electron microscopy (SEM), a
finely focused electron beam probe moves
from one point on the specimen to the next to
form a faster pattern, similar to television
imaging. The most important aspect of electron
microscopy in the study of metal oxide is its
ability to elucidate problems that are beyond
the capability of X-ray or neutron
crystallography. High resolution electron
microscope (HREM) images show local
structures of crystal in great detail. Many other
techniques are employed for the study of metal
oxides. Some of the important ones are
extended absorption fine structure (EXAFS)
spectroscopy, solid state NMR spectroscopy,
electron spin resonance (ESR) spectroscopy,
and scanning tunneling microscopy (STM) [20,
72-75]
.
8.50 Classification of Thin Films
Thin Film are classified based on their
properties as follows
o Magnetic Thin Films
o Ferro / Ferri Electric Thin Films
o Multiferroic thin films
o Magnetoelectric thin films
o Magnetoelastic thin Films
o Piezoelectric thin films
They can be of varying thickness from 10µm
to 1nm based on its application requirements.
8.51 Magnetic thin films
Thin magnetic films originated from the
studies of their effects on light, today, they are
being layered to make complex structures with
unique magnetic properties. Devices based on
these structures are revolutionizing electronic
data storage, due to growing applications in
magnetic sensors and in magnetic storage
media like computer disks and random-access
memories. Magnetic random-access memories
(MRAMs) based on structures of magnetic
metallic films interspersed with nonmagnetic
metallic or insulating interlayer could be the
next generation in magnetic-storage
technology, replacing the semiconductor-based
dynamic random-access memories (DRAMs)
that are now the standard [76].
Advantages of MRAMs,
o Non-volatility (they retain information
when the computer is switched off).
o High storage density.
o Low energy consumption.
o MRAM devices would be smaller.
o Faster.
o Cheaper.
Page 92 of 154
o More robust in extreme conditions such as
high temperature, or high-level radiation or
interference.

Thin magnetic films was suggested as a

replacement for core as early as 1955, and the
first research results were presented in 1959,
but problems with reliability of film-based
MRAMs led to the adoption of DRAMs.
Unlike conventional RAM chip technologies,
in MRAM data is not stored as electric charge
or current flows, but by magnetic storage
elements.

The elements are formed from two

ferromagnetic plates, each of which can hold a
magnetic field, separated by a thin insulating
layer. One of the two plates is a permanent Fig- 105 Data storage applications
magnet set to a particular polarity; the other's
field will change to match that of an external Now MRAMs are in wide spread application
field. A memory device is built from a grid of in the data storage industries as illustrated in
such "cells", but the device power consumption (Fig-105) [76, 78].
was high [77].

The study of the physical properties of

ferromagnetic thin film structures and the
discovery of new techniques for fabricating
these entities make up the field of layered
magnetic structures. Ferromagnetic films can
be combined with all kinds of other layers with
different magnetic and electronic properties to
obtain interesting and practical devices.
Giant magnetoresistance (GMR), tunneling
magnetoresistance (TMR) and interlayer
coupling all involve the transfer of spin-
polarized electrons from one ferromagnetic
layer across an interface to another, and studies
of such processes are giving rise to whole new
fields of study, including spintronics and
magnetoelectronics [75-78].
8.52 Spintronics
Spintronics is an emerging technology which
exploits the quantum spin states of electrons as
well as making use of their charge state. The
electron spin itself is manifested as a two state
magnetic energy system. The discovery of
giant magnetoresistance in 1988 by Albert Fert
et al. and Peter Grünberg et al. independently
is considered as the birth of Spintronics.
Generally, all conventional electronic devices
depend on the transport of electrical charge
carriers (electrons) in a semiconductor such as
silicon. The information processing is done by
utilizing circuits using transistors that work by
transfer of electrons [79].
A Field-Effect-Transistor (MOSFET) consists
of a source and a drain, two highly conducting

Page 93 of 154
n-type semiconductor regions, which are
isolated from the p-type substrate by reversed-
biased p-n diodes. A metal (or poly-crystalline)
gate covers the region between source and
drain and the flow of electrons from the source
to the drain is controlled by the voltage applied
to the gate and the gate voltage changes
electron density (Fig-106).
Fig- 106 Metal oxide field effect transistor
With the advancement in technology, the
devices are diminishing in size and increasing
in speed. The number of transistors on an IC
chip doubles every 12 months-following the
Moore’s law [80, 81]. Moore’s law will
subsequently lose momentum as the size of
individual bit approaches dimensions of an
atom. For this reason and to provide
multifunctionality to the devices, investigators
are trying to combine both, charge and spin
degrees of freedom of electrons, to create a
remarkable new generation of devices which
will be smaller, more versatile and more robust
than those currently making up silicon chips
and circuit elements. Thus emerges a new field
of electronics called spin electronics or
Spintronics [81, 82].
Spintronics describes technology that makes
use of the spin state of electrons. Electrons
exhibit the basic properties of spin, charge, and
mass. When the intrinsic spin of an electron is
measured, it is found in one of two spin states,
known as spin up and spin down. The Pauli
Exclusion Principle states that the quantum-
mechanical wave function of two paired
fermions must be antisymmetric, no two
electrons can occupy the same quantum state,
implying that an entangled pair of electrons
cannot have the same spin.
The advantage of spin over charge is that spin
can be easily manipulated by externally
applied magnetic fields, a property already in
use in magnetic storage technology. Another
significant property of spin is its long
coherence, or relaxation time (nanoseconds,
compared to tens of femtoseconds during
which electron momentum decays), when
created, it tends to stay that way for a long
time, unlike charge states, which are easily
destroyed by scattering or collision with
defects, impurities or recombination [81].
These characteristics open the possibility of
developing devices that could be much
smaller, consume less power and will be more
powerful for certain types of computations
which is not possible with electron-charge-
based systems. It is widely expected that new
functionalities for electronics and photonics
can be derived if injection, transfer and
detection of carrier spin can be controlled at
room temperature [80].
Spintronic devices
Spintronic devices came into action after the
discovery of powerful effect called “Giant
magnetoresistance (GMR)” in 1988 by French
Page 94 of 154
and German physicists [84]. It results from
subtle electron-spin effects in ultra-thin
'multilayers' of magnetic materials, which
cause huge changes in their electrical
resistance when a magnetic field is applied. It
is a sandwich structure with alternating layers
of magnetic and nonmagnetic metal (Fig-107).
Fig- 107 Typical GMR sandwich structure
Depending upon the relative orientations of the
magnetizations in the magnetic layers, the
electrical resistance changes from small
(parallel magnetizations) to large (antiparallel
magnetizations). The magnitude of this change
is twice the order of magnitude larger than is
possible with conventional materials, hence the
name “giant magnetoresistance” [81].
To make a spintronic device, the primary
requirement is to have a system that can
generate a current of spin polarized electrons,
and a system that is sensitive to the spin
polarization of the electrons. Most devices also
have a unit in between that change the current
of electrons depending on the spin states. The
simplest method of generating a spin-polarized
current is to inject the current through a
ferromagnetic material. The most common
application of this effect is a giant
magnetoresistance (GMR) device. Unlike
traditional IC’s in which signals are
determined by the charge of electrons,
Spintronics devices utilize both the spin and
the charge of electrons for increased
functionality. Potential benefits of using spin
currents include increased speed of devices and
decreased power consumption. IBM identified
that the read heads incorporating GMR
materials would be able to sense much smaller
magnetic fields, allowing the storage capacity
of a hard disk to increase from 1 to 20 gigabits
[85]
.
In 1997, IBM launched GMR read heads, into
the market. Researchers have found further
possibilities of spin valves which can be made
to act as switches by flipping the
magnetization in one of the layers. This allows
information to be stored as 0s and 1s
(magnetizations of the layers parallel or
antiparallel) as in a conventional transistor
memory device. Another application is a
magnetic version of a random access memory
(MRAM) device used in computers [86].
MRAM is rapidly developing as a technology
because it can allow quantum computing by
use of spin of individual particles to process
information, is known as a quantum bit or
qubit. It is amazing to know that only 34 qubits
are required to represent the total amount of
information stored in a 10 Gb hard rive [80].
With the exception of MRAM, none of the
spintronic devices such as spin based light
emitting diodes (spin LEDs), resonant
tunneling diodes (spin RTDs), field effect
transistors (spin FETs), and spin based single
electron devices based on quantum dot arrays
can be fabricated without the ability to
generate, maintain, and propagate long lived
spins in a semiconductor [80]. All spintronic or
more specifically semiconductor spintronic
devices act according to the simple scheme:
(1)information is stored (written) into spins as
a particular spin orientation (up or down), (2)
the spins, being attached to mobile electrons,
Page 95 of 154
 [87]
carry the information along a wire, and (3) the information is read at a terminal .

Fig- 108 Application of Spintronics

The long coherence time of spin makes
spintronic devices particularly attractive for
memory storage and magnetic sensor
applications, and, potentially for quantum
computing where electron spin would
represent a bit (called qubit) of information [79].
The basic idea behind semiconductor based
spintronics is to add the characteristics of
magnetic devices to existing devices such as
light-emitting diodes and field effect
transistors [81]. This would lead to technologies
such as memory and microprocessor functions

Page 96 of 154
integrated on the same chip, magnetic devices
with gain and integrated sensors with on-chip
signal processing and off-chip optical
communications. A technology tree which
summarizes the spin-based devices is shown is
shown in Fig-108.
Recent Progress in Spintronics
In the past few years, a new set of
magnetoelectric multiferroics such as TbMnO3
and Ni3V2O8 has been discovered and it is
under intense research in the field of
spintronics for the potential novel applications
as discussed below [40]. Researchers are now
trying to use non-equilibrium thin film growth
techniques to develop new materials for
Spintronics applications and to perform
detailed characterization to understand the
correlation between the structural, magnetic,
and electronic properties of materials such as
complex oxides and diluted magnetic
semiconductors.
The complex oxides (e.g. perovskites) have
received renewed interest due to their novel
magnetic, electronic, and optical properties,
including colossal magnetoresistance and
predictions that they are half-metallic (i.e.
possess a complete spin polarization of the
carriers). These properties are particularly
useful for sensor applications and the
development of devices based on the transfer
of spin currents. Moreover, sophisticated
multi-functional sensors can be built by using
the coupling between layers with different
properties (e.g. ferromagnetism,
magnetostriction, and piezoelectricity).
Considerable research is being done to study
the interactions between layers with different
ferroic properties and to explore the existence
of new phenomena at surfaces and interfaces
not found in the constituent materials. The
ferroelectric order by magnetic phase transition
in TbMnO3 in the absence of magnetic fields is
discussed below [40].
8.521 Magnetoelectric multiferroic Thin
Films -TbMnO3 and Ni3V2O8
In these magnetoelectric multiferroics,
ferroelectric order develops upon a magnetic
phase transition into a spiral magnetic ordered
phase. In addition, these systems show large
magnetoelectric effects accompanied by
metamagnetic transitions. Non-collinear spiral
magnetism is the key to understand the
magnetoelectric properties in these systems.
The reported studies [40] presented here indicate
that spiral magnets are promising candidates
for magnetoelectrics showing large magneto
electric effects at low magnetic fields.
Magnetic and ferroelectric properties of
TbMnO3
TbMnO3 is an example of magnetoelectric
multiferroics that exhibit large magnetoelectric
response [88].
Fig- 109 Structure of TbMnO3
The crystal structure of TbMnO3 is the
orthorhombically distorted perovskite structure
(the space group Pbnm and crystal symmetry
mmm) at room temperature, as illustrated in
Page 97 of 154
(Fig-109). The crystal symmetry has an
inversion center, and the system is nonpolar at
room temperature, but at lower temperatures,
the system shows successive magnetic phase
transitions.
Fig- 110 (a) and (b) Nonpolar behavior of TbMnO3 at
room temperature
Temperature profiles of magnetization M at a
magnetic field of 0.5 T, specific heat divided
by temperature, and electric polarization along
the c axis for a single crystal of TbMnO3 is
shown in Fig-110a and 110b.
The First anomaly
o According to neutron diffraction studies
the Mn moments in TbMnO3 undergo an
antiferromagnetic transition at TN ~ 41 K.
This ordering corresponds to the anomaly
in magnetization and specific heat at ~41 K
{Fig- 110 (a) and (b)}.
For the magnetic structure below TN, the Mn
moments are aligned along the b axis and show
sinusoidal order with a propagation wave
vector (0, kMn, 1) in the Pbnm orthorhombic
unit cell (Fig-111). The kMn (~0.29) is
insufficient at TN and decreases with
decreasing temperature [89, 90].
Fig- 111 Collinear sinusoidal spin structure in
paraelectric phase
The second anomaly
o The second anomaly is observed in
magnetization and specific heat at TC ~ 28
K (Fig-110a). Below TC, kMn ~ 0.28 shows
little temperature dependence. In TbMnO3,
ferroelectric order with spontaneous
polarization along the c axis develops at TC
~ 28 K (Fig-110b).
Third anomaly
o Upon further decreases in temperature, the
temperature dependence of the specific
heat shows the third anomaly at ~7 K,
where the Tb3+ moments show long-range
ordering with a propagation vector (0,
~0.42, 1) different from that of Mn
moments. At approximately this
Page 98 of 154
 temperature, the electric polarization also
exhibits a small anomaly.
These results suggest an intimate connection
between magnetism and ferroelectricity in
TbMnO3.
At the lowest temperature, the magnitude of
electric polarization is ~ 6 to 8 × 10−4C m−2.
The spontaneous polarization of TbMnO3 is
rather small as compared with that of
conventional perovskite ferroelectrics.
Fig- 112 Non collinear spin structure in ferroelectric
phase
The sinusoidally modulated magnetic structure
model was proposed by Quezel et al. [89] for
both the antiferromagnetic paraelectric phase
(TC ≤ T ≤ TN) and antiferromagnetic
ferroelectric phase (T ≤ TC).
However, a recent neutron diffraction
measurement by Kenzelmann et al. [91]
suggests that the magnetic structure below TC
is not the sinusoidal structure rather, is a
transversely modulated spiral magnetic
structure or elliptically modulated cycloidal
spiral magnetic structure (Fig-112).
This spiral spin structure has also been
confirmed in a similar rare-earth manganite,
Tb1−x DyxMnO3, for which the commensurate
propagation wave vector (kMn = 1/3) is
observed at ferroelectric phase by a model-free
analysis via the use of single-crystal neutron
diffraction data.
The major difference between the
antiferromagnetic paraelectric phase (TC ≤ T ≤
TN) and antiferromagnetic ferroelectric phase
(T ≤ TC) is the existence of magnetic moments
along the c axis in the ferroelectric phase (Fig-
112), which does not exist in the paraelectric
phase (Fig- 111), which means that all Mn
moments are aligned along the b axis in the
paraelectric phase making the magnetic
structure collinear when the system is
paraelectric.
In contrast, the magnetic structure in the
ferroelectric phase shows an elliptically
modulated non-collinear spiral spin structure.
This appearance of the spiral spin structure
accompanied by ferroelectric phase transition
is the ‘origin of ferroelectricity in TbMnO3’,
which is discussed below.
Magnetic Control of Electric Polarization
and Dielectric Constant
The magnitude of electric polarization P in
TbMnO3 is much smaller than that in
conventional perovskite ferroelectrics and the
ferroelectricity of TbMnO3 can be controlled
by a magnetic field H [88, 92]. It has been
reported that by applying magnetic fields along
the b-axis the magnetic-field dependence of
Page 99 of 154
electric polarization along the c-axis (Pc) and
the a-axis (Pa) is at 9 K and 15 K for a
TbMnO3 single crystal Fig- 113a and 113b.
Fig- 113 Switching of the direction of electric
polarization by the application of Magnetic field
Through the application of a magnetic field of
4 to 8T, Pc is suppressed, whereas Pa is
induced. These results show that the
spontaneous polarization is switched (or
“flopped”) from the direction along the c-axis
to that of the a-axis which means that the
direction of the spontaneous polarization in
ferroelectric TbMnO3 can be switched by 90◦
by tuning the magnitude of magnetic field
(electric polarization flop) [92]. As displayed in
Fig-114, the electric polarization flop is
attributed to a metamagnetic transition.
In addition, the magnetic-field effect on
electric polarization varies sensitively with the
direction of a magnetic field relative to the
crystallographic axes. Fig-114 shows the
isothermal magnetization and Pc as a function
of magnetic fields at selected temperatures.
Single or double metamagnetic transitions can
be seen in M–H curves, depending on the
orientation of magnetic fields. With the
application of a magnetic field along the a-
axis, a double metamagnetic transition has
been observed (Fig-114a).
The first transition shows a distinct jump of M
at ~1.7 T, and the second transition exhibits
only a small change in M at ~10 T (Fig-114a).
The application of a magnetic field along the b
axis also gives rise to double transitions at ~1
T and ~4.5 T at 4K (Fig-114b).With increasing
temperatures, the steps in the M–H curves
become indistinct. In both configurations (H //
‘a’ and H // b), Pc is suppressed at the second
metamagnetic transition field.
This suppression of Pc is attributed to the
electric polarization flop from P // c to P // a.
According to recent in-field neutron and X-ray
diffraction measurements [93,94], the electric
polarization flop coincides with a first-order
transition to a commensurate but still long-
wavelength magnetic modulated phase with
propagation vector of (0, 1/4, 1). For the in-
field P // a phase, there are several proposed
magnetic structure models, including spiral and
non-spiral spin structures [93, 94].
Page 100 of 154
 Fig- 114 Magnetization and (d–f) magnetic-field-induced changes in electric polarization along the c axis for TbMnO3
crystals
The application of a magnetic field along the c
axis causes a single metamagnetic transition
above 5 T, as shown in Fig-114c. Comparison
of the M–H curves with the P–H curves (Fig-
114f) reveals that the metamagnetic transition
gives rise to the suppression of Pc. The
observed feature in the H // c configuration is
similar to that in H // ‘a’ and H // b, the effect
of magnetic fields along the c axis is distinct
from that along the ‘a’ and ‘b’ axes. The
electric polarization vanishes for all
crystallographic directions by the application
of a high magnetic field along the c axis. This
means thatTbMnO3 loses its ferroelectricity by
the application of sufficiently large magnetic
fields along the c axis.
A recent neutron diffraction measurement
revealed that the suppression of ferroelectricity
in a magnetic field along the c axis is related to
the disappearance of the incommensurate
antiferromagnetic ordering of Mn spins and the
appearance of a simple commensurate
antiferromagnetic ordering with the (0, 1, 0)
magnetic Bragg reflection. These results
clearly demonstrate the strong interplay
between long-wavelength magnetic order and
ferroelectricity in TbMnO3. The possible
Page 101 of 154
mechanism of the magnetic-field effect on
ferroelectric properties is discussed in more
detail below. When the Tb site in TbMnO3 is
replaced by other trivalent rare-earth ions
having similar ionic radius to Tb (e.g., Gd, Dy,
and Eu1−xYx), similar ferroelectric properties
related to magnetic order and its magnetic-field
effect can be observed [95]. In DyMnO3, which
shows ferroelectricity below TC ~19 K, a
relatively large spontaneous polarization
appears along the c axis (~2 × 10−3 C m−2)
(Fig-115a ). In addition, the electric
polarization flops from P // c to P // a by the
application of magnetic fields along the ‘a’ and
c axes, as observed in TbMnO3 [95].
Fig- 115 Giant magnetoelectric and magneto-capacitive effects
These results show that the magnetic-field-
induced polarization flop phenomenon (Fig-
115c) leads to a gigantic magneto-capacitive
effect with a change of dielectric constant up to
ε(H)/ε(0) ~ 500% (Fig-115d ) in DyMnO3.
When the media include a nonlinear dielectric
such as Ba1−xSrxTiO3, applying an electric field
changes its dielectric constant [40]. The
materials showing this effect can be considered
electric-field-tunable elements for high-
frequency devices. Similarly, using
magnetoelectric multiferroic materials, we can
achieve the dielectric constant to be tuned by a
magnetic field instead of an electric field.
Page 102 of 154
ELECTRIC POLARIZATION INDUCED
IN SPIRAL MAGNETS
Spiral Configurations
The appearance of a spiral magnetic structure
accompanied by ferroelectric order presented
in the above section helps in understanding the
origin of the ferroelectricity in TbMnO3. The
term spiral means that the spin vectors lie
within a plane such that the components of the
spin along two axes at right angles in the plane
have a periodic variation along some arbitrary
direction in the crystal as per Cox et al. [96].
Fig- 116 Schematic illustrations of types of magnetic structure with a long wavelength
If the spin rotation axis is perpendicular to the
propagation vector of spiral, the resulting
arrangement is termed a cycloidal spiral
structure (Fig-116c). A rather more
complicated system is conical spiral, in which
a ferromagnetic component coexists with a
Types of Spiral structures
Fig-116 shows the (a) collinear sinusoidal and
(b–e) various non-collinear spiral magnetic
structures on a one-dimensional array of
magnetic moments S. Here, eij is the unit
vector connecting the neighboring i and j sites
and is along the propagation vector q of the
spiral structure. (Si × Sj) is parallel to the spin
rotation axis. If the spin rotation axis is parallel
to the propagation vector, the arrangement
yields a screw spiral structure (Fig-116b).
screw (Fig-116d) or cycloidal (Fig-116e)
component. These conical structures are
generally obtained by the application of weak
magnetic fields to screw or cycloidal spiral
structures [40].
Page 103 of 154
Magnetoelectric Effect in Screw Spin
System
In the 1980s, Siratori and colleagues [97, 98]
discussed the magnetoelectric effect of a screw
spiral magnet (Fig- 116b). In screw spiral
magnets, there are two domains in terms of the
handedness of screw: left-handed and right-
handed as shown in Fig-117. These two-
domain structures are converted into each other
by space inversion operation. However, these
two structures never coincide with each other.
This can occur only if space inversion is not a
symmetry operation. Inversion symmetry is
Fig-117 Propagation vector of the screw structure
In contrast, a second-order magnetoelectric
effect is allowed. When a weak magnetic field
is applied along the propagation vector in the
screw spiral, the magnetic structure becomes
conical, as illustrated in Fig- 116d. Then, time
reversal is also broken, and the first-order
magnetoelectric effect can appear. In spiral
broken in screw spiral magnets, which is also
applicable to any spiral magnetic structure with
spin helicity. By contrast, time reversal plus
half-period translation along the propagation
vector of screw are a symmetry operation in
the screw spiral.
Therefore, the first-order magnetoelectric
effect where αij is the
magnetoelectric coefficient), which requires
breaking of both space inversion and time
reversal, is not allowed in screw spiral
magnets.
magnets, the sign of the magnetoelectric
coefficient, i.e., the direction of H-induced
electric polarization can be reversed by
changing the handedness of the spiral. Thus,
the interaction between two neighboring
magnetic moments (vectors Si and Sj) has to be
antisymmetric for the moment exchange.
Page 104 of 154
Siratori and colleagues [97, 98] pointed out that
the lowest-order antisymmetric spin coupling,
i.e., Dzyaloshinskii-Moriya (DM) interaction
plays an important role in the magnetoelectric
effect of spiral magnets.
moments reverses the sign of the effect in the
asymmetric DM interaction, the sign of the
induced electric polarization can be switched
by a reversal of spin helicity (Fig-118b). This
effect may exist locally in normal canted
antiferromagnetic systems, as shown in Fig-
118c.

However, in configurations in which the

Ferroelectricity Induced by Cycloidal Spiral canting angle of the moments aligns alternately
Magnetic Order (CW-CCW-CW-CCW . . ., where CW and
Recent theoretical studies successfully explain CCW denote clockwise and counterclockwise,
the mechanism of ferroelectricity in a new respectively), the effect is canceled out
class of magnetoelectric multiferroics such as macroscopically.
TbMnO3 by means of both microscopic and
phenomenological approaches. A key factor in
the ferroelectricity of these materials lies in
their non-collinear spiral magnetic structures
with a cycloidal component. Katsura et al first
proposed a microscopic mechanism of the
ferroelectricity in these systems, that spin
current (or vector spin chirality’s; Si × Sj),
induced between non-collinearly coupled spins
because of the Aharonov-Casher effect [99],
leads to the electric polarization.

This can be regarded as an inversed effect of

the DM interaction in which two non-
collinearly coupled magnetic moments
displace the oxygen sandwiched by the two
moments through the electron-lattice
interaction. Fig-118 depicts the relationships
among non-collinearly coupled magnetic
moments, oxygen displacement, and resultant Fig- 118 Schematic drawings of the change of local
change of local electric polarization. As shown electric polarization induced by spin canting
in Fig- 118a, when the magnetic moments are
aligned in a cycloidal spiral manner, the These recent theoretical studies have deduced
direction of local electric polarization induced the general relation between the electric
by the inversed DM effect is uniform in the polarization and the magnetic moments in a
system, and the total electric polarization can system with spiral magnetic structures from
be finite. Because the exchange of two symmetry considerations, as described in the
following equation.

Page 105 of 154

 rotation axis changes from the a axis to the
c axis by the application of magnetic fields.

o The second possibility involves the

Where γ is the constant, which is proportional
ferroelectricity attributed to a symmetric
to the spin-orbit coupling and superexchange
interaction, so-called exchange striction (~
interactions. In this equation, vector eij is
vector SI × vector Sj). In this scenario, the
along the propagation vector of a spiral
field-induced phase is a non-spiral
structure, and vectors Si × Sj is parallel to the
magnetic structure with a commensurate
spin rotation axis. The above equation
propagation vector (0, kMn = 14, 1) and
indicates that a finite electric polarization can
possesses a periodic modulation of vector
appear when adjacent magnetic moments are
Si · vector Sj. The modulation induces the
coupled non-collinearly in a spiral manner and
lattice distortion with a nonzero wave
when the spin rotation axis is not parallel to the
vector (0, 2kMn, 0) through exchange
propagation vector. For example, the cycloidal
striction and leads to ferroelectricity.
spiral magnetic structure shown in Fig-119c
meets these requirements. In addition, the
However, further detailed investigations of the
direction of induced electric polarization is
crystallographic and magnetic structures in
perpendicular to the spin rotation axis and the
magnetic fields are needed to confirm the
propagation vector of the spiral and can be
origin of ferroelectricity with P // ‘a’ at
reversed by the change in the helicity of the
magnetic fields along the ‘a’ and ‘b’ axes.
spiral.
The analysis and review of the report confirms
The ferroelectricity (at zero magnetic fields) of
that in spiral magnets, inversion symmetry is
TbMnO3, in which ferroelectric order exists
broken owing to magnetic order, and some
only in the cycloidal spiral phase and the
spiral-ordered structures such as a cycloidal
electric polarization, appears in the direction
make the system polar.
along the c axis, which is perpendicular to both
the spin rotation axis (//a axis) and the
This means that the system becomes
propagation vector of the spiral (//b axis). In
ferroelectric when magnetic order develops.
addition, the suppression of ferroelectricity by
The ferroelectricity in a new class of
the application of a magnetic field along the c
magnetoelectric multiferroics such as TbMnO3
axis can be explained by the disappearance of
and Ni3V2O8 can be explained in terms of this
the cycloidal spiral structure. As for the
scheme.
mechanism of the electric polarization flop
induced by external magnetic fields along the
Because spiral order often arises from the
‘a’ and b axes, two possibilities have been
competition between nearest-neighbor and
considered.
further-neighbor magnetic interactions,
systems containing competing magnetic
o The first possibility is that the field-
interactions (spin frustration) are promising
induced phase with P along the ‘a’ axis is
candidates for magnetoelectric multiferroics.
also a cycloidal spiral but that the spin

Page 106 of 154

Thus, it is no longer so difficult to find new
magnetoelectric multiferroics. Indeed, on the
basis of this strategy several new
magnetoelectric multiferroics related to spiral
magnetic orders have been discovered in the
past few years. The magnetically induced
electric polarization in these systems can be
controlled by fine tuning of the subtle balance
of competing magnetic interactions, for
example by magnetic fields and by chemical
substitution [40].
Thus, large magnetoelectric effect
accompanied by a metamagnetic transition is
realized by relatively low magnetic fields in
these systems. Through the use of these
magnetoelectric multiferroics, ferroelectric
order can be either induced or suppressed by
the application of a magnetic field.
Furthermore, the direction of the ferroelectric
polarization vector by 90◦ and 180◦ can be
switched or even turned full circle by the use
of magnetic fields.
The intimate relationship between magnetism
and ferroelectricity in non-collinear spiral
magnets presented in this article also suggests
that the investigation of electric properties such
as dielectric constant and electric polarization
can be a new tool with which to study
nontrivial magnetic properties in frustrated
spin systems that often favor non- collinear
magnetic structures [40].
8.53 Diluted magnetic semiconductors
(DMS)
DMS have recently attracted huge research
attention because of their potential application
for spintronics devices [100, 101]. In the modern
computer age, devices continue to diminish in
size to achieve higher speeds. As this
shrinkage occurs, the design parameters are
impacted in such a way that the materials in
current use are pushed to their limits [102].
Several long-term alternative concepts are
being investigated that would reduce the
device size, power consumption, and exploit
multifunctional properties of materials.
One of the hot topics today is to use the spin of
electrons, holes, nuclei, or ions to gain new
functionalities in both analog and digital
electronics as discussed in the above section-
3.2. The charge, mass and spin of electrons
form the foundation of present information
technology. The integrated circuits and the
high frequency devices made of
semiconductors, used for information
processing, use only the charge of electrons
while the storage of information is done by
magnetic recording using spin of electrons in a
ferromagnetic metal [103, 104]. But tomorrow's
information technology may see magnetism
(spin), and semiconductivity (charge)
combined in one device that exploits both
charge and 'spin' to process and stores the
information. We may then be able to use the
capability of mass storage and processing of
information in the same device. Such a device
will be called as “Spintronic device” [105].
This could not be realized so far because the
semiconductors currently used in integrated
circuits, transistors and lasers, such as silicon
and gallium arsenide are nonmagnetic.
Moreover, in order to have a useful difference
in the energy between the two possible
electron spin orientations (up and down), the
magnetic fields that would have to be applied
are too high for everyday use [102]. There are
semiconductors, which have a periodic array of
magnetic elements eg. Europium,
Page 107 of 154
chalcogenides and semiconducting spinels but
their crystal structure is quite different from
that of Si and GaAs. Also their crystal growth
is very difficult. Hence they are not ideal for
spintronic applications [102].
One of the approaches to drive a
semiconductor ferromagnetic is to introduce
magnetic ions like Mn, Cr, Co and Fe into non-
magnetic semiconductors. In these
ferromagnetic semiconductors, a part of the
lattice is made up of substitutional magnetic
atoms. Hence they are called diluted magnetic
semiconductors (DMS) [105].
Several researchers have since then reported
observation of room temperature
ferromagnetism in doped semiconductors. A
considerable attention has been paid to
semiconductors doped with ferromagnetic
metals (Co, Fe, and Ni). In these types of
systems, the fundamental issue of much
concern is that the ferromagnetic ordering
could be a result of metal precipitates e.g., Co
in Co doped TiO2 and Co doped ZnO [111, 112,
113]
. Moreover, a definite picture regarding the
actual mechanism of ferromagnetic ordering in
these systems has not been established.

In recent years there has been an extensive
research towards introducing ferromagnetic
property at room temperature in
semiconductors to realize new class of
spintronic devices such as spin valves,
transistors, spin light emitting diodes, magnetic
sensors, non-volatile memory, logic devices,
optical isolators and ultra-fast optical switches.
The potential advantages of spintronic devices
will be higher speed, greater efficiency, and
better stability, in addition to the low energy
required to flip a spin [105].
A ZnO based DMS would be very promising
because of its widespread applications in
electronic devices, such as transparent
conductors, gas sensors, varistors, surface
acoustic wave devices, optical wave guides,
acousto-optic modulators/deflectors, ultra
violet laser source, and detectors [114]. Out of
all the transition metals (TM), the doping of
Mn in ZnO is most favorable because Mn has
the highest possible magnetic moment [115] and
also the first half of the d-band is full, creating
a stable fully polarized state.

Most of the past work on DMS has focused on
(Ga,Mn)As and (In,Mn)As. But the highest
reported Curie Temperature (Tc) in the single
phase samples grown by MBE range from ~ 35
to 172 K [108, 109].
This search for a room temperature
ferromagnetic Semiconductor,
momentum, following a theoretical prediction
by Dietl et al., that ZnO and GaN would
exhibit ferromagnetism above
temperature on doping with Mn, provided that
the hole density is sufficiently high [110].
The theoretical studies on Mn doped ZnO also
proved its novelties in the fabrication of room
temperature spintronic devices. A Tc higher
than 300 K for p-type ZnO has been predicted
theoretically, but this has not been
experimented. Moreover, Mn is known to be
antiferromagnetic [116], which makes this
gained system more clean in terms of metal precipitate
induced ferromagnetism, which is the subject
of great controversies in DMS.
room
Despite uncertainty in the mechanism of
ferromagnetism in doped semiconductors, and

Page 108 of 154


the fact that the obtained magnetization is
lower than the theoretically predicted value in
most of the reports, the results reported so far
provide a pathway for exploring the Mn doped
DMS. It is however, imperative to understand
the phenomenon and the factors affecting the
magnetization value in order to realize
commercially applicable devices.
History of DMS
The study of dilute magnetic semiconductors
started in late 1960s [118, 119] resulted in various
exciting findings. Among the most extensively
studied ferromagnetic semiconductors were
Eu-Chalcogenides (e.g., EuSe, EuS, EuO) and
Cr-Chalcogenide spinels (e.g., CdCr2Se4,
CdCr2S4). In these magnetic semiconductors
exchange interactions between the electrons in
the semiconducting band and the localized
electrons at the magnetic ions led to a number
of interesting properties like red-shift of band
gap when ferromagnetism sets in. In spite of
the numerous studies carried out on these
materials, no practical applications have been
realized. A low Curie temperature hampered
the application and extreme difficulty in
growing these crystals hindered further studies
on these materials [119].
The next generation of DMS began in early
1980s with the appearance of dilute magnetic
semiconductors based on II-VI compounds
together with those based on IV-VI compounds
[118]
. The materials of the type (e.g.
CdVIxIIxBMnA−1VIB1-x Mn xTe, Cd1-x
Mnx Se, Hg1-xMnxTe) were of much interest
because of several distinct reasons. Their
ternary nature gave the possibility of tuning the
lattice constant and band parameters by
varying the composition of the material, thus
making it possible to engineer their band gap
[107]
. The substitutional Mn atoms in A2B6
lattice are also characterized by highly efficient
electroluminescence, which makes alloys
important in the context of optical flat panel
display applications. Furthermore, the strong
exchange interactions between sp band
electrons and d electrons associated with
Mnx2xMnA−1++ resulted in interesting optical
and electrical properties like giant Faraday
rotation and magnetic and field induced metal-
insulator transition [107].
In these materials the valence of cations
matches that of common magnetic ions like
Mn. This phenomenon makes this type of
DMS relatively easy to make in bulk and thin
epitaxial layers. Many fundamental studies
were done on these systems but not much
application could be realized except for optical
isolators [118]. The magnetic interactions in
these DMS is dominated by antiferromagnetic
coupling of Mn spins, which results in
paramagnetic, antiferromagnetic or spin glass
behavior [118]. A ferromagnetic DMS based on
II-VI materials could not be realized until
recently by A. Hauri et al. (Tc~2K) [120].
Moreover, II-VI based DMS have been
difficult to dope to create p-and n-type, which
made it difficult to study their transport
properties and hence makes it less attractive for
applications [119].
Another group of materials, IV-VI materials
(such as PbMnTe, nMnTe and GeMnTe) also
attracted attention because of free carrier
induced magnetism. Unlike II-VI DMS, these
materials can be grown with higher
concentration of free band carriers. Their
magnetic properties can be controlled by
modifying the carrier concentration through
control of native defects. Story et al.
Page 109 of 154
demonstrated for the first time, effect of carrier
concentration on magnetic properties of
PbSnMnTe [121]. They reported a ferromagnetic
ordering in this material up till 4 K and the Tc
could be increased by increasing the carrier
concentration. However, giant moment often
talked about in certain metallic alloys of
transition metals cannot be formed in IV-VI
alloys because of the diamagnetism of the host
crystal. Recently ferromagnetic transition
temperature as high as 100 K was reported in
Fe doped GeTe films [122].
The other class of semiconductors that is III-V
semiconductors like GaAs and InAs had major
markets in IR LEDs and lasers and magnetic
[104]
sensors respectively . Magnetism,
especially ferromagnetism, has not been a part
of activity in these semiconductors because of
the lack of material technologies that would
allow introduction of magnetic cooperative
phenomena into III-V heterostructures [120].
The equilibrium solubility of transition metal
atoms into these semiconductors is very low
~1018cm-3 [123] or less. Beyond a certain
doping level, the surface segregation, and in
extreme cases phase separation would occur
and impede further incorporation of high
concentration of magnetic ions into the
crystals. Therefore, preparation of ternary
alloys to form DMS of III-V semiconductors is
an extremely difficult task. No DMS based on
these materials was formed until Ohno et al.
reported ferromagnetism in epitaxial films of
InMnAs grown by Molecular Beam Epitaxy
(MBE) in 1992 and GaMnAs (Tc~110 K) in
1996 [124, 125]. The low temperature used to
grow a crystal by MBE prevents formation of a
secondary phase. Since then both these
systems have been investigated extensively in
an attempt to increase the ferromagnetic
transition temperature to more practical limits.
Till date the highest reported Curie
temperature in Mn δ-doped GaMnAs
heterostructures is ~172 K by Nazmul et al.
[109]
. Besides II-VI, IV-VI and III-V
semiconductors based DMS; room temperature
ferromagnetism was reported in II-IV-V2 type
chalcopyrite compound CdGeP2 doped with
Mn. [118]. It is easier to achieve p-type doping
in ternary semiconductors with chalcopyrite
type structure. Also II-IV-V2 semiconductors
are reported to have higher carrier mobility,
which is important for device applications [118].
Another important discovery was a group IV
ferromagnetic semiconductor MnxGe1-x by
Park et al. in 2002 [126]. It followed a prediction
based on mean field solution of Zener model
that ferromagnetic (FM) order can be stabilized
in group-IV semiconductors like Si, Ge and
Si1-xGex. The single crystal MnxGe1-x films on
Ge and GaAs (001) substrates have Curie
temperatures varying linearly with the Mn
concentration from 25 K to 116 K.
Process of doping DMS
DMS are semiconductors which have been
doped with a few percent of a magnetic
impurity. These materials allow for the linking
of magnetic and electronic devices on a single
microelectronic platform. Two important
requirements for spintronic applications
include the ability to control the spin properties
of these materials through external means such
as an applied voltage and to attain room
temperature magnetism. Predictions that
moderate dopant levels of 5% result in room
temperature magnetism in ZnO and GaN has
spurred significant work in doping a wide
variety of oxides and nitrides. However, the
Page 110 of 154

results to date remain highly controversial with
widely varying reports and uncertainty about
the origin of the magnetism observed in these
films.
Recent work on spintronics focuses on
achieving practical magnetic ordering
temperatures in technologically useful
semiconductors. While the progress in
synthesizing and controlling magnetic
properties of III-arsenide semiconductors has
been astounding, the reported Curie
temperatures are too low (~172 K) [109] to have
a significant practical impact. A key
development that focused on wide band gap
semiconductors as being the most promising
for achieving high Curie temperatures was the
work of Dietl et al. They employed Zener
model of ferromagnetism to predict Tc values
for several materials. The schematic showing
the predicted Tc values is given below [106].
Fig-119 Tc for Various doped semiconductors
The Tc exceeding room temperature for
semiconductors such as GaN and ZnO
containing 5% Mn and a high hole
20 -3
concentration (3.5 x 10 cm ) initiated intense
research to realize a room temperature DMS
based on wide band gap semiconductors.
Tremendous progress has been made in the
realization of high quality epitaxial layers of
DMS films and in the theory of
ferromagnetism in these dilute magnetic
semiconductors.
8.54 Mechanisms of ferromagnetism
It is an important challenge of materials
science to understand the ferromagnetism in
magnetic semiconductors and to develop
functional semiconductor systems with the
Curie temperatures Tc exceeding comfortably
the room temperature.
The fact that the DMS are ferromagnetic and
independent of their weakly metallic or
strongly insulating nature implies a robust
character for the underlying mechanism
leading to the long range magnetic order in
these systems. Clearly the ferromagnetic
mechanism should not depend crucially on the
carrier system being “free” valence band holes
since the strongly insulating DMS systems do
not have any free holes. The currently accepted
picture for DMS ferromagnetism is that it is
the local antiferromagnetic coupling between
the carriers (i.e., holes in GaMnAs) and the Mn
magnetic moments that leads to long range
ferromagnetic ordering of Mn local moments.
The carrier system also becomes spin-polarized
in the process with the carrier magnetic
moment directed against the Mn magnetic
ordering by virtue of the antiferromagnetic
hole-Mn coupling, but the total magnetic
moment of the spin polarized carriers is
extremely small since nc<<ni and |S| > |s|
Page 111 of 154
where S is the Mn, s the hole spin, nc and ni are
carrier and local moment densities
respectively. The relevant DMS effective
magnetic Hamiltonian can be written as [127].
Where S(r) and s(r) are respectively the Mn
and hole spin densities. The coupling J(r)
between Mn local moments and hole spins can,
in principle, be ferromagnetic (J < 0) or
antiferromagnetic (J > 0), but the effective
interaction between the Mn local moments
mediated by the holes (through HM) is always
ferromagnetic. The magnitude of J must come
from a first principles band structure
calculation or from experiments.
Oxide based DMS
Compared to non-oxide semiconductors, the
oxide semiconductors have many advantages.
Their wide band gap makes them transparent
and also suitable for applications with short
wavelength. They can be easily grown at low
temperature even on a plastic substrate and are
ecologically safe and durable besides being
low in cost. In addition, strong
electronegativity of oxygen is expected to
produce strong p-d exchange coupling between
band carriers and localized spins, a prerequisite
for DMS [128]. Summarized below are some of
the reports on oxide semiconductor based
DMS.
TiO2 based DMS
TiO2 has been widely studied for its unique
physical and chemical properties like high
refractive index, optical transmittance in the
visible and near-infrared region, high dielectric
constant and photo catalysis for water
cleavage. TiO2 are wide band gap
semiconductors that exist in three kinds of
crystal structures rutile, anatase, and brookite.
Anatase TiO2 has high mobility of n-type
charge carriers when doped with several
percents of Co are ferromagnetic at room
temperature as shown by Matsumoto et al. [129].
SnO2 based DMS
SnO2 is ‘n-type’ semiconductor with a wide
band gap of ~3.6 eV which has its application
as a transparent conducting electrode in solar
cells [129] and gas sensors. It has a rutile
structure with octahedral coordination similar
to anatase TiO2. Large n-type carrier
concentration up to 1021 cm-3 can be achieved
by antimony doping. The effective electron
mass is quite large ~0.3me. These
characteristics are important for strong
magnetic exchange interactions in terms of
carrier induced magnetism. Epitaxial films of
Mn doped rutile-SnO2 were fabricated by PLD.
Co doped ZnO
ZnO based DMS have wide band (3.3eV) gap,
and large excitation energy (60meV) [131, 132]. It
is a well-known piezoelectric and electro-optic
material, and can be easily deposited in thin
film form. It has wide applications in
electronic devices such as transparent
conductors, thin film gas sensors, varistors,
surface acoustic wave (SAW) devices, optical
wave-guides, acousto-optic modulators /
deflectors, ultraviolet LASER sources, and
ultraviolet detectors [113]. It is n-type
semiconductor with the room temperature hall
mobility in ZnO single crystals in the order of
200cm2V-1s-1.
Electron doping via defects originates from Zn
interstitials in the ZnO lattice. The intrinsic
Page 112 of 154
defect levels that lead to n-type doping lie
approximately at 0.05eV below the conduction
band. There is also interest in developing the
use of ion implantation of ZnO for device
doping, and isolation, as well as investigating
the effectiveness of different transition metals
for magnetic doping.
Mn doped ZnO
Theoretical predictions of researchers revealed
that, FM ordering in TM doped ZnO can be
achieved without using any additional carriers
with V, Cr, Fe, Co and Ni [133], whereas with
Mn doping additional p-type doping is needed
[109]
. Despite this Mn remains the primary
dopant of interest because solubility of Mn in
ZnO is larger than 10 mol% and the electron
mass is as large as ~0.3me, where me is the free
electron mass. In fact, Fukumura et al. showed
that Mn atoms could be doped into ZnO up to
35 % by PLD technique without phase
segregation [131]. Therefore, the amount of
injected spin in the host material can be very
large with Mn doping. Moreover, Mn is known
to be antiferromagnetic, which makes this
system more clean in terms of metal precipitate
induced ferromagnetism, which is the subject
of great controversies in DMS (eg in Co doped
TiO2, Co doped ZnO)
The model by Dietl et al predicts that the
transition temperature in dilute magnetic
semiconductors (DMS) will scale with a
reduction in the atomic mass of the constituent
elements due to an increase in p – d
hybridization and a reduction in spin–orbit
coupling. The theory predicts a TC greater than
300 K for p-type ZnO doped with Mn
mediated by heavy p-type doping, with TC
dependent on the concentration of magnetic
ions and holes [109].
In view of these findings one can say that
carrier concentration is not the only parameter
that influences the magnetic properties of Mn:
ZnO. This is consistent with work by
Theodoropoulou et al. who found that FM in
ZnO films deposited by reactive magnetron
sputtering was strongly dependent on
parameters such as growth temperature, O2
partial pressure, and type of substrate (only
films deposited on Al2O3 substrates were FM).
Non-optimized growth conditions produced
weakly paramagnetic behavior [134].
Spin valve
The most successful Spintronics device to date
is the spin valve, due to their widespread
application in hard disk read/write heads. This
device utilizes a layered structure of thin films
of magnetic materials, which changes electrical
resistance depending on applied magnetic field
direction. In a spin valve, one of the
ferromagnetic layers is "pinned" so its
magnetization direction remains fixed and the
other ferromagnetic layer is "free" to rotate
with the application of a magnetic field.
Future applications
Future applications may include a spin-based
transistor which requires the development of
magnetic semiconductors exhibiting room
temperature ferromagnetism. One possible
material candidate is manganese doped gallium
arsenide GaMnAs. The operation of MRAM or
magnetic random access memory is also based
on spintronic principles. Spintronics-based
non-volatile 3D optical data storage has also
been proposed.
Page 113 of 154
8.60 Ferroelectric Thin Films
Introduction
With an ever-expanding demand for data
storage, transducers, and microelectro-
mechanical (MEMS) systems applications,
materials with superior ferroelectric and
piezoelectric responses are of great interest.
The lead zirconate titanate (PZT) family of
materials has served as the basis for such
applications until now. Applications of the
piezoelectric effect have expanded into many
fields since Curie brothers discovered this
effect in 1880-1881. Since then, based on the
type of piezoelectric materials, four stages of
historical developments may be identified. The
first material was single crystal quartz, the
second was single-crystal Rochelle salt, the
third was barium titanate ceramics, and the
fourth was lead-zirconate-titanate (PZT)
ceramics [135].
Quartz crystals were first used for underwater
transducers during World War I, and then for
quartz crystal oscillators. Rochelle salt was
used for underwater transducers and
phonograph pickups. Barium titanate ceramics
were discovered at the end of World War II
and were first used for underwater transducers,
communication devices, and dielectric
components such as capacitors. PZT ceramics
were discovered in 1954 and replaced barium
titanate ceramics in all fields of piezoelectric
applications.
At present, single-crystal quartz is still the
most important piezoelectric material. Of the
ceramic materials, PZT ceramics are the most
widely used because of their high
electromechanical coupling factor, good
frequency-temperature characteristics, and
suitable quality factor.
The History and origination of PZT
The origin of PZT dates back from the study of
Barium Titanate (BaTiO3). BaTiO3 ceramics
were discovered by E. Wainer and N. Salomon
[136]
in the USA in 1942, by T. Ogawa [137] in
Japan in 1944, and by B. M. Vul [138] in the
Soviet Union also in 1944. All discoveries
were made independently with no
communication between the researchers
because of World War II. At first, the
discoverers suggested that barium titanate
ceramics were typical ferroelectric materials
and had no specific piezoelectric advantages.
However, in 1947, S. Roberts [139] of the USA
discovered the piezoelectric properties of the
material resulting from poling the material
with a high DC voltage. This prompted W. P.
Mason [140] and others to study the
piezoelectric properties of the material. By the
early 1950s, piezoelectric transducers based on
barium titanate ceramics were becoming well
established in a number of consumer and
military applications.
Piezoelectric barium titanate ceramics were
good materials for electro-mechanical
transducers because of their non water
solubility, high coupling coefficient, and ease
of production.
However, this material had serious weak points
as described below.
o Poor temperature coefficient of resonance
frequency caused by the second phase
transition of crystal [135] just below room
temperature.
o The second problem was excessive aging
because of the material’s low Curie point.
Page 114 of 154
Many researchers tried to improve the
temperature characteristics by shifting the
second phase transition. One method was to
add other materials such as Ca or Pb.
Especially, the addition of Pb had a drastic
effect in shifting the Curie point to a
temperature >120◦C and the second phase
transition to <-20◦C. Study of the phase
transition in lead titanate and lead zirconate led
to the discovery of PZT ceramics, which had
much better temperature and aging
characteristics than barium titanate [135].
Emergence of ferroelectric thin-film
Until very recently, ferroelectrics have been
used in the form of bulk ceramics and, where
available, as single crystals. These materials
have proved to be robust and reliable solution
for producing thin layers.
Since the 1980s, various methods have been
developed [141] to fabricate ferroelectrics in the
form of thin films. The availability of thin-film
ferroelectrics has encouraged the re-
examination of previously unrealizable
designs, resulting in the integration of
ferroelectrics with semiconductor circuits, and
architectures combining the excellent
properties of ferroelectrics with
micromachined silicon.
Ferroelectricity
Ferroelectricity is a physical property of a
material whereby it exhibits the spontaneous
polarization (Charge), by either Mechanical /
Thermal / electrical field as listed below [142,
143]
.
o Piezoelectrics: Charge generation by
mechanical fields
o Pyroelectrics: Charge generation by
thermal fields
o Ferroelectrics: Charge generation by
electrical fields
Crystal Symmetry
The lattice structure described by the Bravais
unit cell of the crystal governs the crystal
symmetry and they all can be grouped together
into 230 microscopic symmetry types or space
groups based on the symmetry elements [13,
14]. In the physical properties of crystals, only
the orientations of the symmetry elements and
not their relative positions are important.
Hence, if only the orientations of the symmetry
elements are taken into account, then the
macroscopic symmetry elements in crystals
reduce to a center of symmetry, mirror plane,
1-, 2-, 3-, 4- or 6- fold rotation axes and 1-, 2-,
3-, 4- or 6- fold inversion axes. A combination
of these symmetry elements gives us the
macroscopic symmetry also called as point
groups. It can be shown by the inspection of
the 230 space groups that there are just 32
point groups. The seven crystal systems can be
divided into point groups according to the
point group symmetry they possess (Fig-120)
[142, 143]
.
Fig-120 Symmetry based Phenomenon of Ferroelectric
material
Page 115 of 154
The thirty-two point groups can be further
classified into
o Crystals having a center of symmetry and
o Crystals which do not possess a center of
symmetry.
Crystals with a center of symmetry include the
11 point groups labeled as centrosymmetric
and these point groups do not show polarity.
The remaining 21 point groups do not have a
center of symmetry (i.e. non-centrosymmetric)
which possesses one or more
crystallographically unique directional axes.
All non-centrosymmetric point groups, except
the 432 point group, show piezoelectric effect
along unique directional axes. The symmetry
based Phenomenon of Ferroelectricity is
shown in Fig-120 [142, 143].
Structure of Ferroelectric Materials
The feature of all ferroelectrics is the presence
of a field re-orientable spontaneous
polarization. Many ferroelectrics are
characterized by structures incorporating
oxygen polyhedra and the most important of
these is the perovskite structure A2+B4+O3
(Fig-121) [142,].
Fig-121 Crystal structure of Ferroelectric material
This polarization appears as a result of the
small, highly charged B cation being displaced
into a noncentrosymmetric position as the
structure is cooled below the Curie temperature
(TC) [142, 143].
The physical significance of this spontaneous
polarization is that it confers the largest
relative permittivity of any type of capacitor
dielectric, and as well as a field-orientable
polarization, which has been exploited in the
manufacture of a range of piezoelectric and
pyroelectric products.
Ferroelectric Properties
8.61 Piezoelectrics
It is the ability of certain crystalline materials
to develop an electrical charge proportional to
a mechanical stress. All ferroelectrics are
piezoelectric. Piezoelectric materials also show
a converse effect, where a geometric strain
(deformation) is produced on the application of
a voltage. The direct and converse
piezoelectric effects can be expressed in tensor
notation as follows [142, 143].
Page 116 of 154
8.62 Pyroelectrics

Where D is the charge density, deff – effective

piezoelectric coefficient, X is stress, is
strain.

Electrostrictive effect –
Quadratic effect, present for all materials

Piezoelectric coefficient
8.63 Ferroelectrics

Where dijk is the third-rank tensor.

Relation between piezoelectric coefficient and

polarization as illustrated in (Fig-122) [142, 143]

Where, ε - dielectric permittivity, m - index in

the matrix notation.

Major ferroelectric oxides

o Pb-based materials - Pb(Zr,Ti)O3
o Layered perovskites – SrBi2Ta2O9,
Bi4Ti3O12
o BaTiO3-based materials – (Ba,Sr)TiO3

Material Properties for Piezoelectrics - PZT

Direct piezoelectric effect:

Fig- 122 Relationship between dzz and Pz

Converse piezoelectric effect:

Page 117 of 154

For particular case of tetragonal symmetry:

d33=2ε33Q33P3
d31=2ε33Q13P3
d15=2ε11Q44P3

Where D is the charge density, deff – effective

piezoelectric coefficient, X is stress, is
strain and d33 is the amount of polarization
developed along the direction of applied force,
per unit applied force [142, 143].

For Rhombohedral symmetry, as illustrated in

(Fig-123)
Fig- 124 Relationship between dzz and Pz of PZT and
BaTiO3

For polycrystalline materials

Piezoelectric coefficient (d ZZ) and
Polarization (PZ) depends on the sample
symmetry.

d – Actuator figure of merit

g – Sensor figure of merit
Electromechanical coupling factor k is given
by k2 = Stored mechanical/(electrical)
Fig- 123 Rhombohedral PZT
energy/Stored electrical (mechanical) energy,
Comparison between PZT and BaTiO3
The relationship between piezoelectric
coefficient (d ZZ) and Polarization (PZ) are s – Elastic stiffness
detailed in Fig-124 [142- 147].

Page 118 of 154

Ferroelectric materials for piezoelectric applications
Maximum d in systems with morphotropic phase boundary (MPB) - Pb(Zr,Ti)O3 as shown in Fig- 125

Fig- 125 Morphotropic phase boundary (MPB) - Pb(Zr,Ti)O3

Monoclinic phase at MPB

The monoclinic phase of PZT clearly exhibits

the formation of MPB as illustrated in Fig-126
with the following characteristics [148-150].

o Not a sharp boundary between tetragonal

and rhombohedral phases

o An additional monoclinic phase might exist

o There are three different phases with

similar free energies and the polarization
can rotate easily among different directions
Fig- 126 Monoclinic phase at MPB

Page 119 of 154

Current Demerits
A critical drawback of this material, however,
is the presence of lead and the recent concerns
about the toxicity of lead-containing devices
for the statutory compliance of RoHS
(Restriction of Hazardous Substances).
Researchers are trying with Lead Free material
(K0.5Na0.5)1-xLix (Nb1-yTay)O3 to comply with
RoHS, the related properties are illustrated in
Fig- 127.
Recently, the lead-free ferroelectric BiFeO3
(BFO) has attracted a great deal of attention
because of its superior thin-film ferroelectric
properties, which are comparable to those of
Fig-127 Lead Free Piezoelectric materials
the tetragonal, Ti-rich PZT system; therefore,
BFO provides an alternate choice as a “green”
ferro/piezoelectric material. Another advantage
of BFO is its high ferroelectric Curie
temperature (Tc = 850 °C in single crystals),
which enables it to be used reliably at high
temperatures. The ferroelectric domain
structure of epitaxial BFO films are typically
discussed in the context of the crystallographic
model of Kubel and Schmid; however, by
suppressing other structural variants in BFO,
we can obtain periodic domain structures that
may open additional application opportunities
for this material [151].
Page 120 of 154
Pyroelectrics Materials for ferroelectric memories
Pyroelectric Coefficient Vs Relative Dielectric Charge by switching, is shown in Fig-129
Constant is illustrated in Fig-128. The relation
between Pyroelectric Coefficient Vs Relative
Dielectric constant can be expressed as
follows.
Figure of Merit

Fig-129 Charge by Switching in FE Memories

Intrinsic requirements[143-145]
Polarization ↑
Switching speed ↑
Coercive Field ↓
Retention ↓
Fatigue ↓
Fig-128 Pyroelectric Coefficient Vs Relative Dielectric
Imprint ↓
Constant {Substitutions by: Zr (PZT), La (PLT) and
Ca (PCT)}
Extrinsic requirements
Application of Pyroelectric thin films Processing temperature ↓
o Intruder alarm
o Linear pyroelectric arrays CMOS compatibility ↑
o Application in infrared gas spectroscopy Availability ↑
o thin film focal plane array for thermal
imaging [145] Cost ↓

Page 121 of 154

Applications of ferroelectric thin films
Ferroelectric devices are of vast ranges and
many new designs have been proposed and
developed based on the unique properties of
ferroelectric films as shown in Fig-130
Fig- 130 Areas of application of Ferroelectric thin films
o The advent of ferroelectric thin films
provides a practical method of realizing a
new generation of integrated solid state
devices. While memory storage devices
represent the largest potential market, thin-
film pyroelectric, piezoelectric and
frequency agile devices will appear in a
commercial form within the next few years
[145]
. magnetoelastic response requires highly
8.7 Magnetoelectric Thin Films
Magnetoelectric thin film materials are a class
of multiferroics in which charge polarization
and magnetization coexist and are coupled
together. This property has crucial importance
in the construction of actuators and sensors
with high sensitivity. The Magnetoelectric
effect has also been observed in layered
composites such as (Pb,Zr)TiO3 (PZT)–
Tb0.3Dy0.7Fe1.92 (Terfenol-D), PZT-NiFeO4,
polyvinylidenefluoride–Terfenol-D and
laminate Pb(Mg1/3Nb2/3)O3– PbTiO3–Terfenol-
D. These composite materials provide
fundamental advantages when fabricated as
thin films instead of bulk materials by
constructing alternating piezoelectric and
piezomagnetic layers for the fabrication of
compact thin-film magnetoelectric devices as
detailed under Spintronics – TbMnO3, and
BFO model system [147].
8.8 Magnetoelastic Thin Films
Magnetostrictive or Magnetoelastic thin films
have drawn significant interest in sensor and
actuator applications. The thin films
applications are based on a cantilever,
consisting of a magnetostrictive film deposited
onto a non-magnetic substrate.
Amorphous Fe-based thin films are currently
being considered for this purpose as Fe-based
metallic glasses show high values of the
saturation magnetostriction, λs = 10-5.
However, for thin films the magnetostrictive
and magnetic behavior is dependent on several
parameters such as the deposition conditions,
mechanical behavior of the substrate and
substrate thickness.
The development of micro sensors based on
magnetostrictive thin films with flexible
substrates. The behavior of Fe80B20 is being
examined by depositing (using magnetron
sputtering) thin films of the material on
different substrates for this reason [148, 152].
Magnetostriction measurements indicate the
strong dependence of the saturation
magnetostriction with the substrate. Samples
on flexible substrates exhibit a better
performance than samples deposited onto glass
substrates.
Page 122 of 154
8.9 Piezoelectric Thin Films
Piezoelectric thin films of materials such as
lead zirconate titanate (PZT) are detailed in the
piezoelectric section-8.61.
o Piezoelectric thin films also have vast
applications in MEMS devices
incorporating piezoelectric thin films.
There are two ways to evaluate
piezoelectric thin film[147].
o One is to use the direct piezoelectric effect
such as normal loading method which
gives the information prior to the high field
poling process.
o The other is to employ the converse
piezoelectric effect like interferometer,
which by itself leads considerable domain
reorientation in the ‘As’ deposited film
when applying voltage for poling.
Some common piezoelectrics used are listed in
the table below with their K values [145].
9.0 Multiferroic BFO Thin Films –
as a model system
The intense interest towards this fascinating
multiferroic material has been discussed under
the section of Multiferroic crystals in sec. 7.10
In brief BiFeO3 (BFO) is a room temperature
single-phase magnetoelectric multiferroics
reported so far, which shows the highest
ferroelectric polarization, with a ferroelectric
Curie temperature (TC) of ~1,100 K and an
antiferromagnetic N´eel temperature (TN) of
~640K. Both ferroelectricity and anti-
ferromagnetism have long been known in
BiFeO3 single crystals, and recent studies of
BiFeO3 thin films have confirmed the
existence of a large ferroelectric polarization,
as well as a small magnetization, both of which
are consistent with theoretical predictions [153,
154]
.
9.11 Structure and properties of BFO
The structure of BiFeO3 is characterized by
two distorted perovskite unit cells (ar = 3.96 Å,
αr = 0.6°) connected along their body diagonal,
denoted by the pseudocubic <111>, to form a
rhombohedral unit cell (Fig-131) [56, 57].
Fig-131 Schematic of the crystal structure of BFO and
the ferroelectric polarization (arrow) and
antiferromagnetic plane (shaded planes).
Page 123 of 154
Ferroelectric (FE) Properties in Bulk parameters and the coupling between the order
The large displacement of the Bi ions relative parameters showing the existence of a large
to the octahedral FeO6 induces ferroelectricity ferroelectric polarization [160]. Researchers
resulting in two important considerations. have also demonstrated based on theoretical
calculations and through experimental studies
o The ferroelectric polarization lies along the of BFO films on substrates with various
pseudocubic <111> leading to the orientations (Fig-132) that the spontaneous
formation of eight possible polarization polarization in BFO films is along <111> with
variants, corresponding to four structural a magnitude of 90–95 µC/cm2 [155]. The large
variants [54, 57 and 58]. polarization in thin films could be the result of
o The antiferromagnetic ordering of BFO is a change in the switching mechanism in thin
G-type, in which the Fe magnetic moments films compared with the bulk [156], as well as to
are aligned ferromagnetically within {111} epitaxial strain [157].
and antiferromagnetically between adjacent
(111).
BFO is also known to exhibit a spin cycloid
structure in the bulk [54] and the preferred
orientation of the antiferromagnetically aligned
spins is in the (111), perpendicular to the
ferroelectric polarization direction with six
equivalent easy axes within that plane
(Fig.131) [58, 60].Therefore, it is obvious that
there is a coupling between
antiferromagnetism and ferroelectric
polarization.

In the past, the ferroelectric nature of BFO was

unclear, since early reports indicated a rather
low spontaneous polarization in bulk [159]. But,
recent studies of BFO thin films have shown
that canting of the antiferromagnetic sub lattice
is the reason for the existence of a large Fig.-132 Ferroelectric polarization loops measured on
ferroelectric polarization, as well as a small net epitaxial BFO films with different crystallographic
orientations.
magnetization of the Dzyaloshinskii–Moriya
type [55, 60].
At the same time, two limiting factors are
trouble with high leakage currents and
9.12 Ferroelectric Properties in thin films
difficulty in making electrical contacts remain
Polarization
Recent investigations of ferroelectric and to be solved.
magnetic properties of BFO epitaxial thin films Leakage
reveal, the importance of the individual order Ideal ferroelectric behavior has been
demonstrated by recent work with BFO films

Page 124 of 154

grown on DyScO3 (DSO) substrates and sharp
ferroelectric loops is obtained even at low
frequencies (Fig-132) and measurements
[156-158]
indicate low leakage levels
Researchers are intensely investigating to solve
this leakage problem in BFO heteroepitaxial
thin films.
9.13 Electrical control of Magnetic
Properties (AFM)
Switching
Switching is the reorientation of the
polarization to a stable state that remains after
the field is removed. Electrical control of
multiferroic behavior in BFO films relies on
controlling the ferroelectric switching.
The recent report states that the researchers
have observed a coupling between
ferroelectricity and antiferromagnetism in
BiFeO3 thin films, which can be understood to
result from the coupling of both
antiferromagnetic and ferroelectric domains to
the underlying ferroelastic domain structure.
Such a coupling is a crucial first step in the
exploration of approaches to control and
switch magnetic properties using an electric
field [155]. The analysis of their experimental
report is detailed below.
Piezoelectric force microscopy (PFM) is used
to characterize and determine the ferroelectric
domain structure of BFO thin films grown on
STO substrate with SRO bottom electrode [39,
40]
. (Fig- 133a). Fig-133b shows the ferroelectric
In PFM technique, a conductive cantilever
with an ac signal induces an alternating
electrical field between the tip and the SrRuO3
(SRO) bottom electrode. It has been reported
that local converse piezoelectric vibrations
induced by the ac field produce displacements
of the film. Using a locking technique enables
the detection and recording of the sign and
. phase of the piezoelectric vibration, which can
be used in conjunction with crystallographic
information to determine the polarization
direction in the films. Domains with up and
down polarizations give rise to opposite
contrast in out-of-plane (OP)-PFM images and
differences in in-plane components of
polarization produced a torque on the atomic
force microscope (AFM) cantilever creating a
contrast in the in-plane (IP)-PFM images.
However, domains with polarization vectors
along the scanning cantilever’s long axis do
not give rise to any IP-PFM contrast. On the
contrary, domains with polarization pointing to
the right with respect to the cantilever’s long
axis produce an opposite tone to domains with
a polarization pointing to the left. This is
caused by the anti-phase IP-piezo-response
(PR) signals produced by these domains.
By combining the OP- and IP-PFM images,
the polarization direction of each domain (Fig-
133b) was identified, showing an IP-PFM
image of a BFO film grown on a (001) SrTiO3
(STO) substrate. The three contrast levels
observed in the IP-PFM images acquired along
the two orthogonal <110> directions, together
with the uniform OP-PFM contrast indicate
that the domain structure of the BFO films is
characterized by four polarization variants
domain structure for BFO films grown on STO
(110) substrates (imaged with the cantilever
along [110].
The films exhibit two ferroelectric variants
with net polarization pointing ‘down’ over
Page 125 of 154
large areas (Fig- 133a). BFO films grown on polarization direction of the films on STO
STO (111) substrates exhibit one contrast in (111) is perpendicular to the substrate (Fig-
the OP-PFM image and no contrast in the IP- 133a).
PFM image (Fig-133b), suggesting that the

Fig.-133 IP- PFM images of BFO thin film domains

Such domain structures agree well with phase-

field models [42] in which the spatial It has been reported that to switch the films
distribution of the polarization field and its locally, a dc bias is applied to a conducting
evolution is described by time-dependent AFM tip while scanning over the desired area.
Ginzburg–Landau equations [43]. By analyzing the OP and IP contrast changes

Page 126 of 154

following this electrical poling, all three 109°) switching events, while the remainder of
possible switching mechanisms (71°, 109°, and the domains is ferroelectric in nature.
180°) have been observed (Fig-134) [43]. The
red circles indicate the ferroelastic (71° and

Fig-134 OP- and IP-PFM images of (001) BFO/SRO/STO films after switching with schematics showing the three
possible switching mechanisms.

In ferroelectric domains with white contrast in The antiferromagnetic domain structure of

OP and IP-PFM images, 180° switching events
are observed as a reversal in both OP and IP-
PFM image contrasts (changes to black in both
cases). For 71° switching events, only a change
in contrast in the OP image is observed (black
contrast in OP and white contrast in IP). For
109° switching events, we observe the reverse
change in an OP-PFM image (black contrast)
but no response from IP-PFM (gray scale).
BFO can be studied using Photo Emission
Electron Microscopy (PEEM) based on X-ray
magnetic linear dichroism (XMLD) (Fig-135)
[39-42]
. Linear dichroism can arise from any
anisotropy from charge distribution in a
material.
In non-ferroelectric antiferromagnets,
asymmetry of the electronic charge distribution
arising from magnetic order causes a
difference in the optical absorption between

Page 127 of 154

orthogonal linear polarizations of light [39–43].
This is manifested as dichroism in the X-ray
absorption, which can be used to distinguish
different orientations of antiferromagnetic
domains.
Nonmagnetic ferroelectrics should also show
linear dichroism because their polar nature
causes an asymmetric electronic charge
distribution. Therefore, in BFO, both
antiferromagnetic and ferroelectric order
should contribute to the dichroism. These two
contributions can be separated by the
temperature dependence of the XMLD or angle
and polarization-dependent measurements.
From their work, it is found that
antiferromagnetic and ferroelectric domains
are intimately related and match up spatially.
The combination of PFM and PEEM, as well
as the latter’s versatility, is useful for the
further study of multiferroics.
Fig-135 PEEM allows the study of antiferromagnetism
in BFO. Images taken based on XMLD show that the
antiferromagnetic domain structure of BFO exactly
matches the ferroelectric domain structure.
In summary, we have observed a coupling
between ferroelectricity and
antiferromagnetism in BiFeO3 thin films,
which can be understood to result from the
coupling of both antiferromagnetic and
ferroelectric domains to the underlying
ferroelastic domain structure. Such a coupling
is a crucial first step in the exploration of
approaches to control and switch magnetic
properties using an electric field.
9.14 Magnetic properties of Thin Films
The origination and magnitude of magnetism
in BFO thin films is still under intense
research, but some of the recent findings with
possible origins of magnetism are explained in
Fig-136 and promising results are discussed
below.
Fig-136 Possible origins of Magnetism
Wang et al. reported higher magnetization
values for thin films of thickness less than ~
100 nm, which is higher than the previously
reported magnetization values in the bulk
material [157].
o The measurements of magnetic moment
measured by higher resolution
‘Superconducting Quantum Interference
Device’ (SQUID) is about 70 to 80
electromagnetic units (emu)/cm3, which is
higher than their previous measurements
Page 128 of 154
 made using vibrating sample magnetometer
(VSM) as shown in Fig-137b.
o The measurements reported corresponds to
a magnetization of about 0.5 µB/formula
Fig- 137 Magnetization measurements
o Detailed transmission electron microscopy
studies of both planar and cross sections of
the samples of thickness from 30nm, 90nm,
100nm and 120nm of BFO thin films
grown on 001 STO substrates, did not
reveal any second phases.
o Piezo imaging with an atomic force
microscope (AFM) has clearly shown the
existence of piezoelectricity down to at
least 30-nm thickness, although the degree
of leakage goes up with decreasing
thickness.
o X-ray diffraction studies have revealed no
secondary phases.
o They have used Rutherford backscattering
and energy dispersive x-ray spectroscopy
unit, which progressively decreases as the
film thickness is increased to above 120
nm.
to analyze the cation composition and see a
Bi:Fe ratio of 1:1 in the films.
However, the oxygen stoichiometry is difficult
to determine exactly so they have assumed the
nominal oxygen composition to describe the
film (ie- BiFeO3). Such notation does not
imply that the films are free of point defects,
including vacancies, interstitials, or anti-site
defects.
They have been using X-ray absorption
spectroscopy (XAS) and X-ray magnetic
circular dichroism (XMCD) to understand the
origin of higher moments in the thin films.
The measurements shown in Fig-138(a) was
derived with a magnetic field of 800 Oe.
XMCD results from the same series of films
that were used to obtain the structural and
Page 129 of 154
magnetic data above. The signal magnitude,
normalized to the total XAS signal, is a
measure of the magnetic moment in the
sample.
o The data clearly shows that the 30nm thick
film has a distinct magnetic signal, which
progressively decreases as the film
thickness is increased.
o The position of the three peaks also reveals
the mixed oxidation state of the sample by
comparison with a known sample (Fe3O4).
Fig-138 Probing of Origin of Magnetism through
XMCD
In Fig-138(b), the normalized XMCD
spectrum of the 30-nm BFO film to that of a
Fe3O4 film is compared and several key points
that emerge from this comparison are
discussed below.
o First, using the Fe3O4 spectrum as a
fingerprint, it is clearly identified that the
peak at 709.5 eV as the Fe2+ peak, is
consistent with our X-ray photoelectron
spectroscopy results.
o Second, this peak progressively vanishes as
the thickness is increased (Fig-138a).
o Third, the total intensity of the spectrum
from the 30nm BFO film is approximately
15% of the Fe3O4 film, which suggests that
the total moment is also approximately
15% of Fe3O4.
o Finally, the ratio of the three peaks in Fig -
138(b) is not the same as that in Fe3O4, for
which detailed studies have revealed a ratio
for BFO as, Fe2+(oct):Fe3+(tet):Fe3+(oct) =
1:1:1
The noticeable part is that the +2 state vanishes
at thicknesses higher than ~100 nm, associated
with the magnetism decreasing to the level of 8
to 10 emu/cm3.
The researchers [115] have concluded that the
most likely origin of Fe2+ in the thin films is
the presence of oxygen vacancies, which are
typically quite common in perovskites. In fact
the sample films were grown under relatively
reducing conditions and thus favored the
formation of Fe2+. In the absence of Fe2+, their
observations (that is, at thicknesses >120 nm)
and theoretical analysis [120] suggest that the
magnetization should be 8 to 10 emu/cm3,
consistent with the observations of Eerenstein
et al [163].
The presence of Fe2+ in the films suggests the
origination as discussed below
One possibility is a ferrimagnetic arrangement
in which the moments of the Fe2+ ions are
aligned oppositely to those of the Fe3+ ions,
leading to a net magnetic moment. Eerenstein
et al. [163] suggest that an oxygen count of 2.75
(instead of 3) would be required to produce our
experimentally observed moment of 0.5µB/Fe.
This would be the case for high-spin Fe2+, but
the oxygen deficiency required to produce the
observed moment would be much lower if
low-spin Fe2+ were present.
But on the contrary, Wang et al suggests that
such a ferrimagnetic arrangement may be
Page 130 of 154
unlikely; even if Fe2+ and Fe3+ were to couple
ferrimagnetically locally, they would need to
also have long-range ordering or the moments
from locally ferrimagnetic regions would
cancel out. An alternative possible mechanism
is a gradual increase in the canting angle as the
thickness is reduced, which could be driven by
increasing distortions resulting from epitaxial
strain, oxygen vacancies, or both. Clearly, this
aspect is scientifically very interesting and
requires further experimental and theoretical
study.
Fig-139 Thin Film Thickness dependence
The out-of-plane lattice parameter for the BFO
layer progressively increases as the thickness is
decreased, consistent with the expected effect
of epitaxial constraint. In contrast to all their
9.15 Thin Film Thickness dependence
The ferroelectric and magnetic properties of
BiFeO3 (BFO) epitaxial thin films was
reported by Wang et al. [157], they have
reported that they have demonstrated the
thickness dependence of these properties, and
suggested that monoclinic distortion, relaxing
gradually is a likely explanation of these
effects. The heteroepitaxial strain induced a
increasing thickness as explained in Fig-139.
Detailed X-ray studies [157] have shown
evidence for such a monoclinic structure, as
well as no evidence for secondary phases.
prior studies, the recently grown epitaxial BFO
thin films showed a large spontaneous
polarization.
Page 131 of 154
o They suggested the hypothesis that this
change could be directly attributed to the
epitaxially induced change in structure.
o Possibility that the large polarization in
thin films could be the result of a change in
the switching mechanism in thin films
compared with the bulk [156], a change that
could be related to other differences as well
as to epitaxial strain.
o Another possibility, originally suggested
by Teague et al [160], is that the high
leakage in the bulk samples, was reduced
in the films, could have prevented prior
researchers (over the past four decades)
from observing the large value of
spontaneous polarization of BFO.
other <111> axes can result in changes in the
magnetic configuration.
Through a combination of PFM and PEEM, it
has been demonstrated that the coupling exists
between antiferromagnetic and ferroelectric
domains during different ferroelectric
switching events [155].
9.17 FE-AFM-FM Coupling
The demonstration of room temperature
magnetoelectric coupling presents the potential
for ultimately controlling magnetism with an
applied electric field as explained below.

These latter proposals are consistent with

various subsequent measurements of high
polarization of BFO in thin film form [164-166].

9.16 Magnetoelectric (ME) coupling: FE-

AFM
Researchers have demonstrated that there is a
ME coupling in BFO thin films [155] and the
direction of the polarization can be changed by
ferroelectric (180°) and ferroelastic switching
events (71° and 109°). At the same time,
magnetic moments on the Fe ions couple
ferromagnetically within the pseudocubic
{111} and antiferromagnetically between
adjacent planes.

Coupling between the ferroelectric and

antiferromagnetic order in BFO is
accomplished by the rigid alignment of the
antiferromagnetic axis perpendicular to the
polarization direction. Thus, certain types of
71° and 109° rotation of the polarization from
<111> axis to one of a specific set of three
Fig-140, an approach for the electrical control of
ferromagnetism

Page 132 of 154

To use such functionality for device
applications, scalable control of
antiferromagnetism and ferromagnetism is
essential. So, to achieve such a goal, the
researchers have proposed an approach based
on the presence of two coupling mechanisms
(Fig-140a).
o The first is the coupling between
ferroelectricity and antiferromagnetism in
BFO as discussed earlier.
o The second coupling mechanism of interest
is based on a classic exchange coupling
interaction [167] that arises at the interface
between a ferromagnet and an
antiferromagnet (Fig- 140b).
Researchers have used such heterostructures to
tune the properties of ferromagnets for over
five decades. With the addition of a
multiferroic antiferromagnet, we can control
the state of the antiferromagnet electrically and
thereby indirectly control the state of the
ferromagnet by completing the bottom leg of
the coupling triangle in (Fig-140a). Thus the
combination of magnetoelectric coupling in a
multiferroic and exchange coupling between
magnetic materials offers a new approach for
the electrical control of magnetism.
9.18 Epitaxial Strain - RSM
Epitaxial Strain induces modification of
various physical properties in BFO thin films,
when compared to the bulk. Recently Wang et
al. [157] reported an enhancement of the room-
temperature spontaneous polarization in
epitaxially compressed strained thin films of
the ferroelectric compound BiFeO3.
The crystal structure of these films was found
to be monoclinic, in contrast to that of the bulk
material which is rhombohedral. The effect of
a small monoclinic distortion arising from
strain in BFO leads to a break in the magnetic
symmetry and the formation of a preferred
antiferromagnetic axis [42]. This occurrence is
important because it will make the
antiferromagnetic axis to rotate by 90° only for
those ferroelectric switching events that have a
90° rotation of the in-plane component of the
polarization. This indicates the added level of
control exists in the magnetoelectric coupling.
Recent report of experimental work carried out
by the researchers to explore the multiferroic
nature of epitaxially strained BFO thin films
are discussed below. High-quality epitaxial
BFO films have been prepared by pulsed laser
deposition (PLD) [168, 169], radiofrequency
sputtering [160] metal-organic chemical vapor
deposition [160], and chemical solution
deposition on various substrates [167], including
STO, DSO, and LaAlO3, with various
conducting-oxide electrodes such as SRO, (La,
Sr) MnO3, and LaNiO3.
Transmission electron microscopy (TEM) was
used to identify the presence of a highly
coherent and smooth interface between BFO
and the electrode layer and the relevant TEM
image is shown in Fig-141(a). Substrate and
film thickness can be varied to study epitaxial
strain effects in BFO. The out-of-plane lattice
parameter is shown in Fig-141(b) as a function
of BFO film thickness on both STO and DSO
substrates.
It has been observed that because of the lattice
mismatch between BFO and STO, the BFO
lattice is compressed in the in-plane direction
and elongated in the out-of-plane direction;
this strain gradually decreases with increasing
film thickness. Films thinner than ~30 nm, the
Page 133 of 154
out of plane lattice parameters reach a DSO means that the out-of-plane lattice
maximum value implying that a fully epitaxial parameter remains close to the bulk value.
and maximally strained film has been created
and the close lattice match between BFO and

Fig-141 Analysis of TEM images

Page 134 of 154

The effect of strain on the structure of epitaxial
BFO films was measured using high-resolution
X-ray diffraction (HRXRD).
Reciprocal space mapping (RSM)
RSM was used to identify the crystal structure
of the BFO films [172]. The BFO lattice is
isotropically compressed in the plane of the
film because of the lattice mismatch between
STO and BFO. Such an effect can lead to the
formation of a mono clinically distorted
structure for BFO films on STO (001) and
(110) substrates.
The structural variants of a BFO thin film was
characterized by detailed RSM measurements
[172]
. Fig-141c shows a typical RSM for BFO
thin films (<60 nm). The in-plane positions of
the 203PC BFO peaks remain almost identical
to that of the substrate indicating that the films
are fully strained.
rhombohedral structure, the polarization
direction will likely be close to <111>.
It has been reported that they have identified
three different contrasts in these images (Fig-
142).
o For all BFO films, the out-of-plane and in-
plane PFM images can be explained within
the confines of the mono clinically
distorted rhombohedral structure with the
polarization along <111>.
o Using the PFM tip as the top electrode,
they probed the piezoelectric hysteresis of
the films locally, down to a thickness of 2
nm, and found that five BFO unit cells are
switchable [172] .

The splitting between the two peaks reveals the

monoclinic angle to be ~0.7° with the
distortion direction along [152]. Thicker films of
thickness greater than 100 nm exhibited peak
splitting, which indicates a lower symmetry
than the tetragonal structure. The in-plane (H-
direction) position of the 203PC peaks deviates
from the centerline toward smaller values,
while the out-of-plane (L-direction) position
becomes larger than the thinner films.

This means that the structure of the film

becomes more like the bulk through strain
relaxation. It is apparent that the growth of
epitaxially constrained thin films of BFO
results in the formation of a slightly distorted
structure. In the mono clinically distorted Fig-142 PFM images of 9 nm (001) BFO/SRO/DSO
films

Page 135 of 154

The antiferromagnetic properties of epitaxial
BFO have also been investigated by
researchers and reported that magnetic
measurements prove that the cycloidal
structure has been broken, which leads to a
weak ferromagnetic moment arising from
canting of the antiferromagnetic moments in
the system [172].
Furthermore, neutron diffraction has been used
to obtain insights into the microscopic
magnetic structure, confirming the absence of
any bulk-like cycloidal modulation in BFO
thin films [172]. Finally, using PEEM, a break in
the magnetic symmetry, leading to the
formation of a preferred antiferromagnetic
axis, has been proposed which is consistent
with theoretical predictions [171].
thermal equilibrium. The data in sample 2 were
recorded on an electrically switched area,
whereas the others were recorded on un-
switched areas.
We see that in all cases the linear dichroism
signal drops rapidly on heating above room
temperature, with only ~50% of the room
temperature XLD value remaining at the N´eel
temperature; this reduction is recovered on
cooling. The XLD scales with the thermal
average (M2) of the antiferromagnetic order
parameter as shown in Fig-49. The XLD data
in Fig. 49 closely follows this curve up to the
N´eel temperature. The XLD signal does not
change significantly between the N´eel
temperature and 800 K

9.19 Temperature dependence of Thin Films

Researchers have recently reported that they
have demonstrated at room temperature, the
magnetic and ferroelectric components of BFO
thin films are roughly of equal strength and
have the same sign [155]. Their reported
demonstration has been discussed below.

Temperature-dependent measurements using

XLD was made from room temperature to
800K on five samples; numbers 1–3 were
recorded during heating, whereas 4 and 5 were
recorded during cooling as shown in Fig-143.
On heating, the antiferromagnetic contribution Fig-143 Temperature dependence of normalized order
parameters of BFO
to the dichroism must reduce to zero at the
N´eel temperature (~640 K), whereas the
It is known in bulk BFO that the order
ferroelectric contribution can persist up to the
parameter for ferroelectricity does not change
ferroelectric Curie temperature (~1,100 K).
much below its Curie temperature (~1,100 K),
which is illustrated by the plots of Fe and Bi
In all cases the PEEM images were captured
ionic displacements in Fig. 143. To investigate
from the same area of the BiFeO3 film after
the ferroelectric order parameter in the 600nm
waiting 30 min at each temperature to allow
BFO film, we also plot the temperature-

Page 136 of 154

dependent out-of-plane lattice parameter
obtained from X-ray diffraction, and the
ferroelectric polarization obtained using high-
frequency ferroelectric pulse measurements.
Similar to bulk BFO, the 600nm BFO film
shows very little change in the ferroelectric
order parameter from room temperature to 800
K and the order parameter change correlates
with the high temperature XLD signal. A PFM
measurement also confirmed the existence of
stable ferroelectricity in the BFO film up to
800 K. The bulk-like behavior of the order
parameter is consistent with earlier first-
principles computations and with the fact that
minimal lattice strain is expected in the 600nm.
Therefore the researchers have concluded that
the high-temperature XLD signal results from
Fig-144 Schematic of vicinal STO substrates and the corresponding BFO domain structure and polarization variants
the ferroelectric ordering, and the signal below
TN from the sum of the antiferromagnetic and
ferroelectric contributions. So, at room
temperature, the magnetic and ferroelectric
components are of roughly equal strength and
have the same sign [155].
9.20 Controlling domain structure and
switching
The ferroelectric nature of BFO could
dominate the magnetic nature of the system
because of the relative robustness of the
ferroelectric order parameter at normal
operating temperatures for devices. Therefore,
controlling the ferroelectric domain structure
becomes a critical issue for device
functionality.
Page 137 of 154
Vicinal STO substrates
Vicinal STO substrates are used to break the
symmetry of complicated domain structure of
BFO thin films. In order to simplify the
domain structure of BFO films, a break in
symmetry for the ferroelectric variants should
be induced. One way of accomplishing this is
through the use of vicinal STO substrates (Fig-
144a) [172]. The researchers have used vicinal
substrates miscut along the [010] and (110)
directions. The substrates with maximum
vicinal angle along [010] correspond to (110)
substrates, while those with maximum vicinal
angle along [110] correspond to (111)
substrates. By using a substrate with a vicinal
angle along the [010], the domain structure of
BFO films can be limited to exhibit two
polarization variants.
Stripe patterns, created by two polarization
variants 71° apart, with polarization vectors
pointing into the substrate, have been observed
(Fig-144b). Similarly, by using a substrate with
the miscut along the [110], the formation of
one dominant ferroelectric variant can be
induced. The same approach can be applied to
BFO films grown on STO (110). The two-
domain architecture in BFO (110) films can
likewise be controlled and evolved into a
single domain film on the STO (110) surface.
To verify the polarization variants, RSM with
line scanning has been used to confirm the
domain architecture in these samples (Fig.
144c). This, in conjunction with the fact that
epitaxial films on (111) STO with an SRO
bottom electrode also exhibit single domain
behavior, provides us with a set of model thin-
film systems to explore the magnetoelectric
properties further, as well as the interactions
with other layers.
Additionally, multiferroic materials with
electrically controllable periodic domain
structures (Fig-144b) could be of great interest
for applications in photonic devices. In recent
work, an approach to create a one-dimensional
periodic domain structure in epitaxial BFO
films has been demonstrated [173].
A schematic of the constraints imposed by
heteroepitaxy to create long-range order in the
domain structure of BFO is shown in Fig-144d.
To achieve this, they have taken the DSO
lattice which very closely matches the lattice of
BFO and SRO. Further, the small structural
anisotropy in DSO is used to pin the structure
of the SRO layer such that a single domain
variant of SRO is formed under the appropriate
growth conditions. This structurally simplified
SRO film can then be used to provide an
anisotropic strain that excludes two of the four
possible ferroelectric polarization variants and
induces a one-dimensional periodic domain
structure in BFO films (Fig-144e).
Optical diffraction patterns (ODP) obtained
from these PFM images (Fig-144f); yield an
average stripe-domain width of ~200 nm. After
gaining the control of the underlying domain
structure, the next step is to control the nature
of the ferroelectric switching events in BFO. A
combination of phase-field modeling and
scanning force microscopy of carefully
controlled, epitaxial [110] BFO films with a
simplified domain structure reveals that the
polarization state can be switched by all three
primary switching events through selection of
the direction and magnitude of the applied
voltage [172, 173]. Moreover, the instability of
certain ferroelastic switching processes and
Page 138 of 154
domains can be dramatically altered through
proper selection of neighboring domain walls.
Fig-145 Schematic of a planar electrode PFM setup.
For eventual device applications, the use of
coplanar epitaxial electrode geometry has been
proposed to aid in the control of multiferroic
switching in BFO (Fig-145) [173]. PFM has
been used to detect and manipulate the striped
ferroelectric domain structure of a multiferroic
BFO thin film grown on a DSO substrate.
Time-resolved imaging reveals ferroelastic
switching of domains in a needle like region
growing from one electrode toward the other.
Purely ferroelectric switching is suppressed by
the geometry of the electrodes. Such results
demonstrate the ability to control the
multiferroic order in BFO films by exerting
precise control over the ferroelectric order
parameter.
9.210 The future for multiferroics
Exploring the coupling between ferromagnetic
layers and BFO as shown in Fig-146 will be
the future focus of researchers.
Fig- 146 Interaction between a multiferroic BFO and a
ferromagnetic layer
It has been reported that
o Epitaxial BFO/La2/3Sr1/3MnO3 (LSMO)
magnetic tunnel junction heterostructures
have been grown without suppressing the
ferroelectric order in BFO [174, 175].
o Sizeable tunneling magnetoresistance and
exchange-bias effects have been reported
on epitaxial BFO/LSMO, BFO/CoFeB [176],
and NiFe/BFO [177].
It is essential to further investigate the nature
of the coupling mechanism in such
heterostructures and it has been suggested that
PEEM-based measurements can be made in
order to probe this interaction [178]. Promising
research along this direction is under way and
exciting possibilities are waiting for potential
industrial applications.
Page 139 of 154
9.30 Nanotechnology
Nanotechnology involves ‘research and
technological development at the atomic,
molecular, or macromolecular levels, in the
length scale of approximately 1 to 100 nm
range, to provide a fundamental understanding
of phenomena and materials at the nanoscale
and to create and use structures, devices, and
systems that have novel properties and
functions because of their small and/or
intermediate size’ per the official definition of
the US National Nanotechnology Initiative
[179]
. surface energy of the crystalline phase , the
10.1 BFO Heteroepitaxial nano-
structures
Here we focus on multifunctional materials
that have attracted increasing interest in recent
years because of their potential applications in
novel technological devices [180-181]. BiFeO3–
CoFe2O4 is a multifunctional system, with
ferroelectricity (BiFeO3) and ferrimagnetism
(CoFe2O4) that couple with each other through
a stress mediation.
Haimei Zheng, et.al. [197,198] has recently
demonstrated that BiFeO3–CoFe2O4 self-
assembles into nanostructures with CoFe2O4
nanopillars heteroepitaxially embedded in a
BiFeO3 matrix on (001) SrTiO3 substrates,
which show considerable magnetoelectric
coupling [182] in which the substrate orientation
can be used to control the morphology of two
phase nanostructures by inverting from an
arrangement of spinel nanopillars in a
perovskite matrix to perovskite nanopillars in a
spinel matrix. The reported details of their
research work are discussed below.
The ferroelectric and magnetic properties as
well as the degree of the coupling are critically
dependent on the morphology of the
nanostructures, including domain patterns and
shapes as well as the interfaces. In order to
pursue the enhanced multifunctionality,
significant effort has been made by researchers
on understanding the growth mechanism and
controlling the morphology of the
nanostructures.
The fundamental issue of heteroepitaxy is the
morphology adopted by a crystalline material
during nucleation on a substrate surface. Based
on the surface energy terms, i.e., substrate
surface energy , interface energy , and
equilibrium shape of a crystalline nucleus on a
substrate can be determined using the
Winterbottom construction [183].
The expected configuration of the crystalline
nucleus on the substrate is a Wulff shape that
has been cut off by the substrate, translated by
the signed distance from the origin where
is the wetting strength, which is the
energy difference obtained by replacing the
substrate surface with an interface and is
expressed as,
In the BiFeO3–CoFe2O4 system, BiFeO3 has a
distorted perovskite structure (R3c) [184] and
CoFe2O4 has a cubic spinel structure (Fd3m).
CoFe2O4 is characterized by the lowest surface
energy of {111} surfaces, which is reflected in
an equilibrium shape of an octahedron
bounded by eight {111} facets [185, 186]. In
contrast, most perovskite phases have the
lowest energy surfaces of {001} surfaces and a
corresponding equilibrium shape of a cube
Page 140 of 154
dominated by six {100} facets [187–190].
Because of the difference in the surface energy
anisotropy in BiFeO3 and CoFe2O4 the two
phases can display different growth modes on
a substrate surface.
They have estimated the morphology of the
BiFeO3-CoFe2O4 nanostructures grown on a
substrate surface using the Winterbottom
construction. Fig-147 is the Winterbottom
Fig-147 Schematics of perovskite-spinel nanostructures on (100) and (111) surfaces
construction of the BiFeO3 and CoFe2O4
phases nucleating on single crystal substrates
as a function of the substrate orientation.
They assumed a wetting strength of Dc = c2 for
both phases. On a (001) oriented substrate,
BiFeO3 wets the substrate completely and
follows a layer-by-layer growth; in contrast,
CoFe2O4 partially wets the substrate and forms
islands bonded by four {111} surfaces.
Page 141 of 154
In the consequent growth, each phase grows on
top of its own phase, which leads to CoFe2O4
pillars embedded in a BiFeO3 matrix. On a
(111) oriented substrate, CoFe2O4 displays
layer-by-layer growth and BiFeO3 forms
islands characterized with three {100}
surfaces. At a later growth stage, BiFeO3
grows into pillars embedded in a CoFe2O4
matrix. When the substrate orientation is not
parallel to the lowest energy surface of either
phase, both BiFeO3 and CoFe2O4 phases could
have comparable wetting configuration with
similar nucleation barriers. In this case, both
phases have island growth modes, for example,
on a (110) oriented substrate. As a
consequence of the competing wetting
conditions, the film can form a maze pattern in
which neither phase can be identified as the
matrix or pillars. Based on the above inference,
they have explored the growth of the BiFeO3 –
CoFe2O4 nanostructures on SrTiO3 substrates
with (001), (111), or (110) orientations. On
each substrate, they have studied the effects of
changing the volume fraction of the two phases
(65:35, 1:1, and 33:67 of BiFeO3/ CoFe2O4) on
the nanostructures. Because the morphologies
of the BiFeO3 – CoFe2O4 nanostructures are
critically dependent on the growth conditions,
the growth kinetics of the nanostructures have
also been studied. The magnetic and
ferroelectric properties as well as the coupling
of the BiFeO3 – CoFe2O4 nanostructures that
depends on the morphologies of the
nanostructures are also reported.
The morphologies of the BiFeO3 – CoFe2O4
nanostructures (volume fraction of 1:1) grown
on (001)-, (111)-, and (011)-oriented SrTiO3
substrates are shown in Fig-148. On the (001)
SrTiO3 substrate, CoFe2O4 forms nanopillars
embedded in a BiFeO3 matrix (Fig-148a–d).
Rectangular shaped CoFe2O4 nanopillars and
{110}-type interfaces with the matrix was
observed in Fig-148a). CoFe2O4 nanopillars
change their shape across the film thickness,
which is shown in the cross-sectional
transmission electron microscopy (TEM)
images and the schematic of a pillar (Fig-
148b–d). Within a 100 nm film thickness, the
width of the CoFe2O4 pillar increases, resulting
in an inverted cone shape at the substrate
interface. The rest of the pillar maintains
roughly the same lateral dimensions within the
BiFeO3 matrix. There are sharp interfaces
between the two phases as well as between the
substrate and the two phases. No obvious
interdiffusion was observed across the
interface from energy dispersive spectroscopy
(EDS) studies. On the top of the film, the
CoFe2O4 pillar forms an island with
characteristic facets. The facet planes are 54.7°
with respect to the (001) plane indicating
{111}-type facets.
The structure of the matrix phase and the pillar
phase is inverted in the nanostructures grown
on a (111) SrTiO3 substrate. BiFeO3 forms
triangular shaped nanopillars embedded in a
CoFe2O4 matrix (Fig-148e–h). All the BiFeO3
nanopillars have the same crystallographic
orientation and have {112} interfaces with the
CoFe2O4 matrix. Similar inverted cone shaped
BiFeO3 pillars at the substrate interface were
observed. Fig-148f is a cross-sectional TEM
image of a single BiFeO3 pillar from a 100 nm
thick film. The lateral dimensions of the
BiFeO3 pillar continuously increase from the
substrate interface and reach a constant value
at a certain film thickness. A high-resolution
TEM image of the interface between a BiFeO3
pillar and matrix shows the change of the slope
Page 142 of 154
(Fig-148g). BiFeO3 pillars form islands with
{100} facets on the top of the film.
As it was predicted from the above
Winterbottom construction, a maze pattern
with entangled BiFeO3 and CoFe2O4 phases
was observed on a (011)-oriented SrTiO3
substrate (Fig-148i–k). Fig-148i is a plan-view
Fig-148 Morphologies of BiFeO3 - CoFe2O4 nanostructures
TEM image showing the morphology of the
nanostructures. The corresponding electron
diffraction pattern shows only BiFeO3 and
CoFe2O4 phases that are epitaxial to the
substrate (Fig-148j). A cross-sectional TEM
image shows that both phases grew from the
substrate surface to the top of the film (Fig-
148g).
Page 143 of 154
Unlike the nanostructures grown on (001) and film thickness. The atomic force microscopy
(111) substrates, the two phases on the (110) (AFM) phase-contrast images and their
substrate keep a relatively constant volume schematics show the topographic facets of
fraction across the film thickness. The BiFeO3–CoFe2O4 nanostructures with a 1:1
“columnar” shape of both phases in the cross volume fraction grown on (001), (111), and
section suggests that a similar morphological (110) oriented SrTiO3 substrates (Fig-149).
pattern is maintained in the film close to the
substrate interface and on the top of the film.
The distinct different morphologies of the
BiFeO3–CoFe2O4 nanostructures on (001),
(110), and (111) oriented substrates are
consistent with the Winterbottom construction
in Fig- 147. The large difference in the surface
energy anisotropy of the BiFeO3 and CoFe2O4
phases results in the different nucleation modes
of the two phases on a substrate. On both the
(100) and (111) oriented substrates, the wetting
phase covers a large area of the substrate and
the partially wetting phase forms islands at the
initial nucleation stage.

They have observed the early stage

morphologies of the nanostructures in 5 nm
film thickness, which shows the relatively
small dimensions of the islands. The
subsequent growth establishes the area fraction
of the two phases close to the volume fraction
of the two phases. The facets of the pillars
close to the substrate interface prefer the
Fig-149AFM images of BiFeO3 -CoFe2O4 nanostructures
lowest energy interfaces of the two phases. We
have also observed that the facet is the (111)
surface of the CoFe2O4 phase in Fig-148c. The facets and interfaces of islands have been
However, different facets have also been identified based on both AFM and TEM
observed in other pillars. For the studies. On the (001) oriented substrate,
nanostructures grown on (110) substrates, CoFe2O4 forms islands and BiFeO3 is flat at
because the two phases have similar wetting the film surface. CoFe2O4 islands have (001)
conditions (and similar island growth modes), end facets and (111), (1 1), ( 1) and ( 11)
the area fraction of the two phases is side facets. The interfaces with the BiFeO3
established at an early stage and there is no matrix are {110} planes. The aspect ratio of
distinct change in their area fraction within the the islands, h/a (defined in Fig-149a), is

Page 144 of 154

dependent on the growth temperature (T) and
growth rate (v). On the (111) substrate, BiFeO3
forms islands and CoFe2O4 has a flat surface.
BiFeO3 islands have a (111) end facet (with a
negligible area fraction) and (001), (010), and
(100) side facets.
The interfaces with the CoFe2O4 matrix are
{112} planes. On the (110)-oriented substrate,
both BiFeO3 and CoFe2O4 phases form facets.
BiFeO3 mostly forms hut-shaped islands with
the (110) end facet and the (001), (010), (00 ),
and (100) side facets. The facets of the
CoFe2O4 phase are {111} type; however, they
are not clearly identified from Fig-149c.
BiFeO3 has a higher geometry than CoFe2O4,
which is probably because of the slight
difference in their wetting properties on the
(110) substrate. The observed topographic
Fig-150 AFM images of BiFeO3 -CoFe2O4 nanostructures
shape and facets of the BiFeO3–CoFe2O4
nanostructures agree very well with the
Winterbottom construction based on the
surface energy isotropy. It is further found that
the volume fraction of the two phases did not
introduce distinct changes in the morphologies
of the BiFeO3–CoFe2O4 nanostructures. For
example, irrespective of the volume fraction,
CoFe2O4 forms nanopillars in a BiFeO3 matrix
on a (001)-oriented substrate, BiFeO3 forms
nanopillars in a CoFe2O4 matrix on a (111)-
oriented substrate, and BiFeO3 and CoFe2O4
form a maze pattern on a (110)-oriented
substrate (Fig-150). So, it is clear that
differences in anisotropic strain, surface stress,
and surface diffusivity [192] can result in
differences in the morphologies of the
nanostructures with different compositions.
Page 145 of 154
Size and Spacing of nanostructures CoFe2O4 nanopillar size from a BaTiO3–
The size and spacing of nanostructures are CoFe2O4 system. [193]
controlled by their growth kinetics (e.g.,
growth rate, temperature), which will be
discussed below.

From Fig-150 the differences in the details of

the morphologies are observed in the
nanostructures with different volume fractions.
The fact that the volume fraction of the two
phases does not change their growth modes
there by validating the growth model based on
surface energy anisotropy using the
Winterbottom construction.

At growth temperatures in the range of 550–

700°C and growth rates of 0.5–8 nm / min, the
dimensions of the BiFeO3–CoFe2O4 nano-
structural features increase as the growth
temperature increases and decrease as the
growth rate increases. A lower growth
temperature and/or a higher growth rate induce
supersaturated perovskite type phases which
are metastable. These trends are applicable to Fig-151 Temperature dependence of BiFeO3 - CoFe2O4
all BiFeO3–CoFe2O4 nanostructures with
different volume fractions on differently It is interesting that a similar trend and fitting
oriented substrates. We focus on the kinetics of has been observed in both cases. Fig-151b
BiFeO3–CoFe2O4 nanostructures with a plots the lateral size of the CoFe2O4 pillars
volume fraction of 1:1 grown on (001) versus the growth rates at a constant growth
substrates. temperature of 700 °C. The lateral size of the
pillars (d) decreases as the growth rate
At a constant growth rate of 4 nm min–1, the increases, which can be fitted into a second
lateral size of the CoFe2O4 pillars versus the
order plot, d2∞1/v.
growth temperatures is plotted in Fig-151a.
Diffusion process model
The lateral size of the pillars (ln(d)) decreases
The growth of the BiFeO3–CoFe2O4
as the growth , which can be fitted into a linear
nanostructures can be modeled as a diffusion
plot, ln(d) ∞ 1/T. For comparison, we also
process. In a steady-state growth of the
plotted the temperature dependence of
nanostructures, the multi-component species
come to the film surface and phase-separate

Page 146 of 154

into nanostructures. The nanostructures are
formed at the film surface and subsequently
incorporated into the bulk film. Transport is
limited to the advancing solid–vapor interface,
and diffusion within the bulk film is negligible.
This has been confirmed by the result that no
obvious changes were observed after the
nanostructures were annealed at the film
growth temperatures for 10 hours. For the 2D
diffusion, we simply use the standard equation
This analysis based on diffusion agrees well
with the experimental observations in Fig-151.
The temperature dependence of the CoFe2O4
nanopillars for the BiFeO3– CoFe2O4 system
gives activation energy of 0.83 eV, yielding
activation energy for diffusion of 1.66 eV.
Such activation energy for diffusion is close to
the value (1.56 eV) calculated for the BaTiO3–
CoFe2O4 nanostructures.
They further calculated the activation energy
from the temperature dependence of the size of
the BiFeO3 nanopillars (also a linear plot) in
the BiFeO3–CoFe2O4 nanostructures grown on
(111) substrates.
A smaller activation energy value (0.58 eV) for
diffusion was been obtained. The calculated
activation energy corresponds to the diffusion
barrier for the formation of nanopillars. For
example, the relatively high volatility of Bi
may induce lower activation energy of the
BiFeO3 nanopillars.
Step growth is unlikely to be the limiting factor
for the growth of BiFeO3–CoFe2O4
nanostructures. This is based on the fact that
the activation energy for CoFe2O4 nanopillars
are similar for both BiFeO3–CoFe2O4 and
BaTiO3–CoFe2O4 nanostructures but the facets
of the CoFe2O4 nanopillars are very different
(CoFe2O4 islands are in a dome shape in
BaTiO3–CoFe2O4 nanostructures[191-193] and
they have distinct {111} facets in BiFeO3–
CoFe2O4 nanostructures).
A similar diffusion mechanism was used to
understand the phase separation in Al–Ge films
by Atzmon and co-workers, [194, 195] from
which the calculated activation energy is
consistent with the surface diffusion barrier of
Al and Ge. The activation energies for
CoFe2O4 were relatively high (above 1 eV) and
only a slight difference was observed in the
Page 147 of 154
values for BaTiO3– CoFe2O4 and BiFeO3–
CoFe2O4 nanostructures, although there is
about 200 °C difference in the growth
temperature. For the growth of nanostructures
with different structures and multiple
components, the surface steps, exchange
mechanisms, [196] and other factors may have to
be considered as diffusion barriers.
In summary, they have reported that the
BiFeO3– CoFe2O4 nanostructures with volume
fractions of 65:35, 1:1, and 33:67 grown on
SrTiO3 substrates with (100), (111), and (110)
orientations. Unique morphologies, obtained
irrespective of the volume fraction, was
observed on each substrate. The dependence of
the morphologies of the BiFeO3–CoFe2O4
nanostructures on the substrate orientations is
attributed to the different growth modes of the
two phases.
They also studied the growth kinetics of the
BiFeO3–CoFe2O4 nanostructures. A higher
growth temperature and/or a slower growth
rate induce larger-sized nanopillars. The
BiFeO3–CoFe2O4 is a model system for the
growth and control of two-phase
nanostructures.
The BiFeO3–CoFe2O4 nanostructures are ideal
for the future study on the morphological
dependence of magnetoelectric coupling.
Conclusion
Multiferroic material offers a great prospect for
the development of next generation
multifunctional devices to meet the growing
demand of Microelectronics and
Nanotechnology. The contributions of
scientific communities positively ascertain the
industrial application of Multiferroic BFO thin
films in the very near future by the following
findings.
o Heteroepitaxial growth of these materials
in to thin films allows, controlling and
engineering the properties and
functionalities.
o Growth and investigation of vertical
nanostructures confirm the strong epitaxy
mediated coupling, but emphasizes the
need to break time reversal symmetry to
switch magnetism.
o Strong exchange coupled heterostructures
have been created.
o Promising indication for the possibility of
controlling ferromagnetism with an electric
field using BFO thin films through
switching and reduction of leakage
currents.
o BiFeO3 is a green material (lead-free)
ferroelectric / piezoelectric, very promising
for memory / piezo / multifunctional
applications, and a potential candidate to
replace the hazardous PZT.
o Role of defects has to be investigated
further to understand their contribution.
Acknowledgement
It is indeed a great pleasure in thanking
professor Ramesh Ramamoorthy for guiding
me to this valuable gold mine of knowledge
about Multiferroics and its allied subjects.
Page 148 of 154
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