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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
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It is the magnetization by an electric field or Where α is the magnetoelectric tensor, non-
the induction of electric polarization by a zero only in the absence of space and time-
magnetic field. The study of the magnetic and inversion [2].
ferroelectric materials has led to some of the
most important technological advances to date. The ME effects are limited by the following
relation.
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 From this expression it is clear that in order to
as the expansion of the free energy of a obtain the largest ME effects in single phase of
material as follows. 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.
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The term (magnetoelectric) multiferroics giving a net magnetic moment), ferrotoroidic
comprises not only ferroelectromagnetism but (spontaneous magnetic vortex), or helimagnetic
also Antiferromagnetism, Antiferroelectricity ordering (Magnetic spin moments arrange
and ferroelasticity, eg- BFO in Fig-2 [7, 8 & 9]. themselves in a spiral or helical pattern due to
exchange interaction between Ferromagnetic and
2.20 Requirements for Multiferroics Antiferromagnetic ordering) are also accepted as
The requirements for multiferroics are detailed multiferroics (Fig-3).
in 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].
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mechanics pioneered in explaining the atoms steel in 1850, which enabled the railroads and
and then solids starting from 1930s. The the building of the modern infrastructure of the
combination of physics, chemistry, and the industrial world.
focus on the relationship between the properties
of a material and its microstructure is the Structural materials
domain of Materials Science. The development Used for construction purposes. Includes
of this science allowed the designing of construction materials (steel beams, concrete,
materials and provided a strong knowledge base wood, bricks, glass etc.), materials for
for engineering applications termed as Materials machines, cars, aircraft, ships, railways, roads,
Engineering [13-16]. bridges, pipelines, containers etc.
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Fig: 4 – Classification of Materials [10-16]
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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 A mole is the amount of matter that has a mass
from the superposition of charge densities of in grams equal to the atomic mass in amu of
all atoms in the system. the atoms. Thus, a mole of carbon has a mass
of 12 grams. The number of atoms in a mole is
When an infinite number of atoms come called the Avogadro number, Nav = 6.023 ×
together to form solids they would form 1023. Note that Nav = 1 gram/1 amu. Where, M
bonding, non-bonding and antibonding is the atomic mass in amu (grams per mol).
molecular orbitals of different energies so
close together that they blur into one another Most solids have atomic densities around 6 ×
forming a band. These molecular orbitals are 1022 atoms/cm3. The cube root of that number
described by wave functions. The most gives the number of atoms per cubic
important point to come out of the theory is centimeter is about 39 million. The mean
that for N atomic orbitals in a molecule, N distance between atoms is the inverse of that,
molecular orbitals are the outcome. or 0.25 nm. This is an important number that
gives the scale of atomic structures in solids
4.10 Atomic Structure and Bonding (Fig- 5) [12].
Atoms are composed of electrons, protons, and
neutrons. Electrons and protons are negative
and positive charges of the same magnitude,
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4.20 Electrons in Atoms similar properties. The noble gases have
The forces in the atom are repulsions between closed shells, and so they do not gain or lose
electrons and attraction between electrons and electrons near another atom. Alkalis can easily
protons. The neutrons play no significant role. lose an electron and become a closed shell;
Protons (Z) is what characterizes the atom, halogens can easily gain one to form a
electrons form a cloud around the neutron, of negative ion, again with a closed shell.
radius of 0.05 to 2 nm. Electrons move in The propensity to form closed shells occurs in
‘fuzzy’ orbits called shells (Fig-5) [12]. molecules, when they share electrons to close
a molecular shell. Examples are H2, N2, and
According to quantum mechanics, the orbits NaCl. The ability to gain or lose electrons is
are identified by a principal quantum number termed electronegativity or electropositivity,
n, which is related to the size, n = 0 is the an important factor in ionic bonds.
smallest; n = 1, 2 are larger. (They are
"quantized" or discrete, being specified by The vertical columns in the periodic table of
integers). The angular momentum l is the chemical elements are referred to as groups
quantized, and the projection in a specific (Fig-6). There are 18 groups in the standard
direction m. Two electrons can be placed in an periodic table. The modern explanation of the
orbit with opposite spins in a given n, l, m pattern of the periodic table is that the elements
shell [12]. in a group have similar configurations of the
outermost electron shells of their atoms, as
In 1925, Wolfgang Pauli explained the most chemical properties are determined by the
arrangement of electrons in an atom by his orbital location of the outermost electron. The
exclusion principle. His hypothesis was that international way of numbering the groups of
only one electron can occupy a given quantum the periodic table is using Hindu-Arabic
state. Each electron in an atom has a unique numerals / Indian numerals.
set of quantum numbers (the principle
quantum number gives its energy level, the The type of orbital in which the atom's
magnetic quantum number gives the direction outermost electrons reside determines the
of orbital angular momentum, and the spin "block" to which it belongs and the number of
quantum number gives the direction of its valence shell electrons determines the group.
spin). The total number of electron shells an atom has
determines the period to which it belongs.
In fact, we now know that that the Pauli Each shell is divided into different subshells
Exclusion Principle holds for not just and as atomic number increases, they are filled
electrons but for any fermions (half-integer in roughly in this order (the Aufbau principle)
spin particles like electrons, protons, neutrons, as shown in Fig-6.
muons.)
Progressing through a group from the lightest
4.30 The Periodic Table element to heaviest element, the outer-shell
Elements are categorized by placing them in electrons (those most readily accessible for
the periodic table. Elements in a column share 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].
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For example, the outer-shell (or "valence") the atomic number (i.e. charge on the atomic
electrons of the first group, headed by nucleus) leads to greater spin-orbit coupling
hydrogen, all have one electron in an s orbital. between the nucleus and the electrons. Because
In hydrogen, that s orbital is in the lowest of the importance of the outermost shell, the
possible energy state of any atom, the first- different regions of the periodic table are
shell orbital (and represented by hydrogen's sometimes referred to as periodic table blocks,
position in the first period of the table). In named according to the sub-shell in which the
francium, the heaviest element of the group, "last" electron resides, e.g. the s-block, the p-
the outer-shell electron is in the seventh-shell block, the d-block, etc (Fig-7). The elements
orbital, significantly further out on average Ununbium, ununtrium, ununquadium, etc.,
from the nucleus than those electrons filling all have been discovered, but so far have not been
the shells below it in energy. The increase in 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].
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4.50 Atomic Bonds where the electrons spend more time in
Atomic Bonds are classified as primary and between the nuclei than outside, thus
Secondary Atomic bonds. The primary atomic producing bonding (Fig- 12).
bonds are further classified as Ionic Bonds,
Covalent Bonds, and Metallic Bonds.
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]
.
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) Permanent Dipole Bonds
Secondary Atomic and Molecular Bonds are This is the case of the hydrogen bond in ice.
classified as Permanent Dipole Bonds and The H end of the molecule is positively
Fluctuating Dipole Bonds. charged and can bond to the negative side of
another dipolar molecule, like the O side of the
Fluctuating Induced Dipole Bonds H2O dipole (Fig-15) [18].
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.
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VSEPR diffraction of the quantum mechanical electron
Valence shell electron pair repulsion (VSEPR) waves in the periodic crystal lattice [18].
theory describes molecular geometry through
the repulsion of electron fields which include When several atoms are brought together to
bonds and lone pairs and does not require any form a molecule, their atomic orbitals split, as
application of orbital shape [18]. in a coupled oscillation. This produces a
number of molecular orbitals proportional to
Crystal Field Theory (CFT) the number of atoms. When a large number of
CFT is an approximation that begins with the atoms (of order 1020 or more) are brought
geometries of the d orbitals derived from together to form a solid, the number of orbitals
quantum mechanics. Ligands (an atom, ion, or becomes exceedingly large, and the difference
molecule) with their electron density are in energy between them becomes very small,
assumed to destabilize the metal d- orbitals and so the levels may be considered to form
they interact with raising their energy while the continuous bands of energy rather than the
remaining d-orbitals drop in energy to balance discrete energy levels of the atoms in isolation.
the overall change in energy [18]. However, some intervals of energy contain no
orbitals forming band gaps [18].
Ligand Field Theory (LFT)
LFT is a hybrid of CFT and MO Theory. It is a This band gap is one of the most useful aspects
simple application of MO Theory to transition of the band structure, as it strongly influences
metal compounds [18]. the electrical and optical properties of the
material. Electrons can transfer from one band
Molecular Orbital (MO) to the other by means of carrier generation and
Molecular Orbital (MO) theory is a current and recombination process. The band gap and
often applied model of molecular bonding. MO defect states created in the band gap by doping
Theory assumes that bonds are derived from a can be used to create semiconductor devices
linear combination of atomic orbitals and each such as solar cells, diodes, transistors, laser
pair of atomic orbitals involved in bonding diodes, and others [18].
results in a bonding and anti-bonding orbital.
Basic concepts
The destabilized orbitals of CFT are now seen Theoretically, a solid has a large number of
as anti-bonding component of orbitals that bands but a few lie at energies so high that any
have overall been stabilized through bonding electron that reaches those energies escapes
interactions [18]. from the solid. These bands are usually
disregarded. Bands have different widths,
4.70 Electronic band structure based upon the properties of the atomic
The band structure of a material determines a orbitals from which they arise. Allowed bands
number of characteristics such as electronic, may overlap, producing a single large band.
optical properties etc. The band structure of a
solid describes ranges of energy that an Metals contain a band that is partly empty and
electron is limited to have due to the partly filled regardless of temperature;
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therefore, they have very high conductivity. The band appearing in the bonding region is
The lowermost, almost fully occupied band in called valence band. The antibonding region is
an insulator or semiconductor is called the called conduction band. In the case of metals
valence band by the valence electrons of the valence and conduction bands are
individual atoms. The uppermost, almost immediately adjacent (Fig-16).
unoccupied band is called the conduction band
because only when electrons are excited to the If an electrostatic potential is applied to a
conduction band current flows in these conductor, the energy levels will tend to
materials. The difference between insulators change the electrons and they will be able to
and semiconductors is only that the forbidden flow using empty adjacent conduction band
band gap between the valence band and (Fig-17) [18-26].
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.
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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:
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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.
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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.
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The Bravais Lattices o Consistency with past convention to
In 1848 the French crystallographer Bravais minimize unit cell volume
demonstrated that there are fourteen possible
lattice points by arranging the points in 3D. It o Satisfaction of minimal symmetry
was so arranged that each point has requirements
[statistically] identical surroundings [20]. The Which limits the maximum of 14 lattices and
14 Bravais lattices are detailed in Fig-27 several of these criteria are used to define the
below. cell structure of a crystal.
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covalent, metallic, molecular and hydrogen Hydrogen Bonded Crystals
bonded. Crystals with hydrogen bonds are a special
type of dipole-dipole force that exists between
Ionic Crystals an electronegative atom and a hydrogen atom
These types of crystals are usually formed bonded to another electronegative atom. This
between highly electro-positive and highly type of force always involves a hydrogen atom
electro-negative elements which favor electron and the energy of this attraction is close to that
transfer. The atoms themselves are ionized of weak covalent bonds (155 KJ/mol). These
because the elements with higher electro- attractions can occur between molecules
negativity obtain the valence electrons of the (intermolecular), or within different parts of a
element with the low electro-negativity. single molecule (intramolecular).
The different types of atoms become The hydrogen bond is a very strong fixed
oppositely charged and, are held together by dipole-dipole van der Waals-Keesom force, but
electrostatic forces. Ionic crystals such as NaCl weaker than covalent, ionic and metallic
have relatively high melting points and are bonds. In many Oxide Hydrates or Hydrogen
hard. The cohesive energy calculations can not oxides, hydrogen bonding contributes to the
be used to predict the structure of an ionic cohesive energy.
solid.
5.30 Defects in Crystals
Covalent Crystals A perfect crystal, with every atom of the same
These crystals have covalent bonding between type in the correct position, does not exist. All
all the atoms present in the crystal. These crystals have some defects. Defects contribute
crystals generally have high melting points and to the mechanical properties of metals. Defect
are non-conductors. Diamond and zinc sulfide is intentionally used to manipulate the
are examples of covalent crystals. mechanical properties of a material. Adding
alloying elements to a metal is one ways of
Metallic Crystals introducing a crystal defect.
In metallic crystals individual metal atoms sit
on lattice sites, while the valence electrons The basic classes of crystal defects are as
from each atom flow freely around the lattice. follows:
Metallic crystals have high densities along
with high melting points. Point defects are places where an atom is
missing or irregularly placed in the lattice
Molecular Crystals structure. Point defects include lattice
In this type of crystal, molecules within the vacancies, self-interstitial atoms, substitution
crystal are held together by secondary bonds impurity atoms, and interstitial impurity atoms.
such as van der Waals forces or hydrogen
bonding (Eg- Sugar). Molecular crystals are Linear defects are groups of atoms in irregular
generally soft and have low melting points. positions. Linear defects are commonly called
dislocations.
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Planar defects are interfaces between metallic (e.g. TiO). Other properties, especially
homogeneous regions of the material. Planar the "high-temperature" superconductivity of
defects include grain boundaries, stacking mixed oxides (cuprates) have been recently
faults and external surfaces. discovered. The typical examples of these
complex oxides crystal structure for cubic and
Plastic deformation in a material occurs due to layered perovskites are given in Fig-29.
the movement of dislocations (linear
defects).Any defect in the regular lattice In Transition Metals (TM) the valence
structure disrupts the motion of dislocation, electrons may be present in more than one
which makes slip or plastic deformation more shell, making most TM to have more than one
difficult. The defects of Oxides are explained oxidation state. The oxides of TM show a rich
in detail in the Transition Metal Oxide section variety of electronic properties, ranging from
[20]
. insulating to metallic and even
6.0 Metal Oxides superconducting behavior. The same applies to
Multiferroic materials are poly crystals, which their magnetic properties, where every- thing is
belong to the family of “Transition Metal found from Pauli paramagnetism to local
oxides”. Metal Oxides are formed when metals moment behavior including the occurrence of
are oxidized by oxygen. Metal oxides can be ferromagnetism and antiferromagnetism.
classified into two classes Non Transition
Metal Oxides and Transition Metal Oxides.
6.12 Transition metal oxides Fig – 29, Crystal structure of functional oxides
Transition metal oxides (TMO) are a series of
compounds with a uniquely wide range of Additionally, these materials can often be
electronic properties from insulating (e.g. tuned from one electronic or magnetic phase to
Cr2O3), semi-insulating (e.g.BaBiO3) and
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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 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
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6.21 Rock Salt 6.22 Rutile
Rock salt crystal structure is highly ionically TiO2 (titanium dioxide) is a nominal rutile
bonded. Large anions are arranged in cubic structure. It can be thought of as infinite
close packing and all the octahedral interstitial columns of edge sharing TiO6 octahedra. In
positions are filled with cations in this addition, it has its each edge-shared oxygen,
structure. This structure has an octahedral corner-shared with an adjacent infinite chain.
coordination (CN = 6). This type of Each Ti is coordinated to 6 oxygen atoms (by
coordination predicted from the radius ratio definition for octahedral coordination) and
calculation of cation to anion should be 0.732- each oxygen atom is coordinated to 3 titanium
0.414. atoms, 2 within a column, and 1 within the
adjacent column [28].
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Rutile Derivative: ABO4, ordered and Skew-edge sharing, alpha PbO2 / columbite
disordered structures
Two different metals can replace Ti in the In some situations, the MO6 octahedra will
rutile structure giving a new formula of ABO4, share skew edges and the infinite edge-sharing
keeping the metal-oxygen ratio. If the metals columns become zigzagged instead of straight.
are disordered on the site, then the However, the edge-shared oxygen atoms still
crystallographic description remains the same, share 1 corner with an adjacent chain and in
with 50% of each metal on the Ti site. While that sense the structure is the same as rutile. In
this is most often the case, the metals can also the Fig-36 below, FeWO4 is used as an
be ordered. Fig-34 shows structure of CoReO4. 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].
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6.23 Corundum magnetic properties have been extensively
The corundum structure is a general structure studied.
of a class of minerals consisting of hexagonal Multiferroics are perovskites with general
close packed O atoms with cations filling up formulas of ABO3 and A2BBO68 with units of
2/3 of the central octahedral sites. The cations cubic cell type (eg-LaxTiO3), tetragonal type
occur two in a row and they skip a site. This (eg-BaTiO3) and orthorhombic type (eg-
pattern is staggered for adjacent rows. An GdFeO3) structures (Fig-38) [28].
example is given in Fig-37.
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perovskite materials. Some examples of This structure can be visualized in terms of the
Pervoskites are given and discussed below. BO6 octahedra which share corners infinitely
in all 3 dimensions, making a symmetric
Cubic Perovskite structure. The A cations occupy every hole
The principle perovskite structure found in which is created by 8BO6 octahedra, giving the
ferroelectric materials is a simple cubic A cation a 12-fold oxygen coordination, and
structure containing three different ions of the the B-cation a 6-fold oxygen coordination.
form ABO3. The A and B atoms represent +2
and +4 ions, respectively, while the O atom is In (SrTiO3) the Sr atoms sit in the 12
the Oxygen-2 ion. coordinate A-site, while the Ti atoms occupy
the 6 coordinate B site. There are many ABO3
This ABO3 structure is a face centered cubic compounds for which the ideal cubic structure
(FCC) lattice with A-atoms at the corners and is distorted to a lower symmetry (e.g.
O atoms on the faces. The B atom completes tetragonal, orthorhombic, etc.) [28].
the picture and is located at the center of the
lattice. This A-atom is the largest of the atoms Sr2FeMoO6 - Double Perovskites
and consequently increases the overall size of The double perovskite structure is named
the ABO3 (fcc) structure. As a result, there are because the unit cell of it is twice that of the
minimum energy positions off centered from perovskite. It has the same architecture of 12
the original octahedron that can be occupied by coordinate A- sites and 6 coordinate B sites,
the B atom. Shifting of this atom due to but two cations are ordered on the B site.
applied electric fields causes the structure to be
altered, creating electric dipoles Eg SrTiO3
(Fig-39) [28].
Fig: - 39. SrTiO3 - Cubic Perovskites Fig: - 40, Sr2FeMoO6 - Double Perovskites
Page 25 of 154
The example shown here is Sr2FeMoO6. The For these phases, Sr is the A cation, and Ru is
Fe and Mo atoms have ordered in a 3D the B cation. The separating motif is a layer of
chessboard type fashion (Fig-40) [28]. Sr2, and the perovskite slabs are offset by a
(1/2, 1/2) translation. Ruddleson Popper phases
Layered Perovskites has the general formula as A(n+1)BnO(3n+1),
Layered Perovskites can be identified as indicating that the outer A atoms are part of the
Ruddleson-Popper, Aurivillius and Dion- 2D perovskite slabs.
Jacobson phases. Layered perovskites consist
of infinite 2D slabs of the ABO3 structure Aurivillius phases
which are separated by some motif. The The n=2 phase Bi3TiNbO9 is representative of
general formula for the layered perovskite is: the Aurivillius phases, for which the general
A(n-1)B(n)O(3n+1). The differentiating formula is {Bi2O2}-{A(n-1) B2O7}.
characteristics for the layered perovskites are
For this phase, Ti and Nb are statistically
o The motif which separates the layers, and dispersed on the B site. The formula can be re-
o The offsetting of the layers from each written as: {Bi2O2}-Bi (Ti, Nb)2 O7. The
other. separating motif for all Aurivillius phases is a
rock-salt Bi2O2 layer. Bi is also the A cation,
In this formula, "n" indicates the size of the 2D but that need not be the case. The displacement
slabs. n=1 means the slab is one BO6 of the perovskite slabs is a (1/2, 1/2)
octahedron thick. n=2 means two BO6 translation (Fig-42) [28].
octahedra thick, etc. The clearest examples of
this are the n=1 and n=2 Ruddleson-Popper
phases Sr2RuO4 and Sr3Ru2O7 (Fig-41) [28].
Page 26 of 154
Dion-Jacobson phases vandate spinels, AV23+O4, the d electrons are
The Dion-Jacobson phases have the general localized when 2.88A < Rv-v< 2.97Α. Fe3O4 is
formula M+1A(n-1)BnO(3n+1). They differ from an inverse spinel. The spinels Li1-xM2+xTi2O4
the other layered phases by having a layer of where (M=Mg, Mn) and Li1+xTi2O4 shows
alkali metal as the separating motif. Below is a superconductivity.
picture of KLaNb2O7 and CsLaNb2O7. The
displacement of the perovskite slabs is either Some of these hydrogen bronzes, Di- and
(1/2, 0) or nothing at all depending upon which monophosphate tungsten bronzes of the type
alkali metal is used as the separating motif. Ax(PO2)4(WO3)2m (A = Na, K, Rb, or Ba)
The crystal structures of d0 metal oxides possess hexagonal tunnels. The tunnels may be
consist of distorted metal–oxygen (MO6) empty, as in the monophosphate bronze
octahedra where the cation is displaced from P4W8O32 (m=4), or occupied, as in the
the centre of the octahedron, creating several diphosphate tungsten bronzes. CsP8W9O40, has
of the interesting features of these oxides (Fig- a unique anisotropic structure [20-28].
43) [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.
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 Fig- 44 Spinel structure of MgAl2O4
Page 27 of 154
The image above shows Al atoms sitting on the conduction. When the conduction band is
corners of tetrahedral and the Mg atoms sitting broad, the material (e.g., NaxWO3) exhibits
in tetrahedral holes (Fig-44) [28]. metallic properties.
6.3 Properties of Transition Metal Oxide Transition metal oxides with partially filled d
Physical properties of metal oxides arise as bands can be metallic or insulating. Some of
responses to external stimuli like mechanical them exhibit temperature-induced non metal-
stress, electrical field, magnetic field and to-metal transitions. Magnetic properties vary
temperature. The important properties TMO anywhere from Curie-Weiss paramagnetism to
are Electronic, magnetic, dielectric, optical and Pauli paramagnetism (through spontaneous
catalytic properties. Also the metal to Non magnetism). Rare earth metal oxides
metal transition Phenomenon and Super containing localized 4fn electrons are generally
conductivity is of notable importance [28]. insulators or hopping semiconductors and
exhibit paramagnetism [28].
6.31 Electronic Properties of TM Oxides
Transition metal oxides can be classified into Transition metal oxides with the dn
two classes based on its electronic configuration exhibit metallic properties when
configuration those in which the metal ion has the overlap between orbitals of the valence
d0 electronic configuration (empty d shell) and shells of constituent atoms is large. Two kinds
those in which d shell is partially filled (Fig- of metallic behavior can be distinguished: one
45). The d0 class of oxides has a filled oxygen due to strong cation-cation interaction arising
2p valence band and an empty metal d from a small cation-cation separation, and the
conduction band; the energy gap is around 3- other due to strong cation-anion-cation
5eV. High purity oxides of this class exhibit interaction arising from a large covalent
intrinsic electronic conduction only at high mixing of oxygen 2p orbitals with cation d
temperatures. orbitals. Iso-structural series of transition metal
oxides, possessing rock salt, corundum, rutile,
With the d0 cations at octahedral sites, the and perovskite structures, exhibit systematic
oxides exhibit spontaneous ferroelectric changes in electronic properties, wherein at
distortions (e.g., WO3). Many lose oxygen at least one member of the series shows
high temperatures, becoming properties of itinerant electrons while others
nonstoichiometric. Oxygen loss or insertion of exhibit properties due to localized electrons [20-
28]
electropositive metal atoms into these oxides .
promotes electrons to the conduction band. 0
d (Empty d shell)
The nature of electronic conduction in these The d0 class of oxides has a filled oxygen 2p
materials depends on the strength of electron- valence band and an empty metal d conduction
phonon coupling and the width of the band; the energy gap is around 3-5eV. High
conduction band derived from metal d states. purity oxides of this class exhibit intrinsic
When the coupling is large and the band is electronic conduction only at high
narrow, small polarons are formed and such temperatures. With the d0 cations at octahedral
materials (e.g., NaxV2O5) exhibit hopping 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].
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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
Where M is the magnetization, H is the to be free and under an applied field an
magnetic field, XM the molar susceptibility and imbalance between electrons with opposite
C is the Curie constant. Because of the spin is set up, leading to a low magnetization
interaction between atomic moments giving in the same direction as the applied field. The
rise to an internal field in the oxide, the susceptibility is independent of temperature,
susceptibility is described by Curie- Weiss although the electronic band structure may be
Law affected, which will then have an effect on the
susceptibility.
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].
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 Fig-47, Saturation polarization (PS) and Curie
within the compound. The packing density of temperature (TC) of a range of magnetic materials
the atomic moments will be determined by the
crystal structure (i.e. the spacing of the Magnetic Anisotropy
moments) and the presence of any non- Magnetic anisotropy is a phenomenon of
magnetic elements within the structure. aligning the magnetic moment in an easy axis
in zero fields. Magnetic anisotropy is the
For ferromagnetic materials, at finite direction dependence of a material's magnetic
temperatures, MS will also depend on how well properties. A magnetically isotropic material
these moments are aligned, as thermal has no preferential direction for its magnetic
vibration of the atoms causes misalignment of moment in zero fields, while a magnetically
the moments and a reduction in MS. For anisotropic material will align its moment to an
ferrimagnetic materials not all of the moments easy axis.
align parallel, even at zero Kelvin and hence,
MS will depend on the relative alignment of the In a crystalline magnetic material the magnetic
moments as well as the temperature. The properties will vary depending on the
saturation magnetization is also referred to as crystallographic direction in which the
Page 32 of 154
magnetic dipoles are aligned. (Fig-48) has uniaxial anisotropy means that it is
demonstrates this effect for a single crystal of difficult to demagnetize as it is resistant to
cobalt. The hexagonal crystal structure of Co rotation of the direction of magnetization [29-31].
can be magnetized easily in the [0001]
direction (i.e. along the center-axis), but has Magnetic Domains
hard directions of magnetization in the <1010> A magnetic domain describes a region within a
type directions, which lie in the basal plane material which has uniform magnetization.
(90° from the easy direction). This means that the individual moments of the
A measure of the magneto crystalline atoms are aligned with one another. The
anisotropy in the easy direction of regions separating magnetic domains are called
magnetization is the anisotropy field, Ha (Fig- domain walls, where the magnetization rotates
48), which is the field required to rotate all the coherently from the direction in one domain to
moments by 90° as one unit in a saturated that in the next domain. The concept of
single crystal. The anisotropy is caused by a magnetic domains was proposed by Weiss to
coupling of the electron orbital to the lattice, explain that ferromagnetic materials with
and in the easy direction of magnetization this spontaneous magnetization could exist in the
coupling is such that these orbital are in the demagnetized state. The findings of his work
lowest energy state. 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
Fig-48, Magneto crystalline anisotropy of cobalt of the presence of magnetic free poles at the
surface of the specimen generating a
The easy direction of magnetization for a demagnetizing field, Hd. From the convention
permanent magnet, based on ferrite or the rare adopted for the definition of the magnetic
earth alloys, must be uniaxial, however, it is moment for a magnetic dipole the
also possible to have materials with multiple magnetization within the specimen points from
easy axes or where the easy direction can lie the South Pole to the North Pole, while the
anywhere on a certain plane or on the surface direction of the magnetic field points from
of a cone. The fact that a permanent magnet 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.
Page 34 of 154
Magnetic Hysteresis (H) and magnetic flux density (B) is not linear
Hysteresis is well known in ferromagnetic in such materials.
materials. When an external magnetic field is
applied to a ferromagnet, the atomic dipoles If the relationship between the two is plotted
align themselves with the external field. Even for increasing levels of field strength, it will
when the external field is removed, part of the follow a curve up to a point where further
atomic dipole alignment will be retained and increases in magnetic field strength will result
the material will become magnetized. The in no further change in flux density. This
relationship between magnetic field strength condition is called magnetic saturation.
Page 35 of 154
If the magnetic field is now reduced linearly, When all of the domains are fully aligned with
the plotted relationship will follow a different the applied field, the saturation is reached and
curve back towards zero field strength at which the polarization can increase no further. If the
point it will be offset from the original curve field is removed the polarization returns along
by an amount called the remnant flux density the solid red line to the y-axis (i.e. H=0), and
or remanence. the domains will return to their easy direction
of magnetization, resulting in a decrease in
If this relationship is plotted for all strengths of polarization.
applied magnetic field the result is a sort of S-
shaped loop. The 'thickness' of the middle bit In Fig-51, the line from the saturation point to
of S describes the amount of hysteresis, related the y-axis is horizontal, which is representative
to the coercivity of the material. of a well aligned material, where the domains
are magnetized in the easy direction of the
Ferromagnetic and ferrimagnetic materials crystal at the saturation point.
have non-linear initial magnetization curves
(dotted lines in Fig-51), as the changing When the direction of applied field is reversed
magnetization with applied field is due to a then the polarization will follow the red line
change in the magnetic domain structure. into the second quadrant. The hysteresis means
that the polarization lags behind the applied
These materials also show hysteresis and the field and will not immediately switch direction
magnetization do not return to zero after the into the third quadrant (negative polarization).
application of a magnetic field. Fig- 51 shows The polarization will only decrease after a
a typical hysteresis loop; the two loops sufficiently high field is applied to nucleate
represent the same data, however, the red loop and grow domains favorably oriented with
is the polarization (P = µoM = B - µoH) and the respect to the applied field or rotate the
blue loop the induction, both plotted against direction of magnetization of the domains
the applied field. towards the applied field. After applying high
enough field saturation, polarization will be
The first quadrant of the loop is the initial achieved in the negative direction. If the
magnetization curve (dotted line), showing the applied field is then decreased and again
increase in positive polarization (and applied in the positive direction then the full
induction) on the application of a field to a hysteresis loop is plotted.
demagnetized sample, and are both in the same
direction. The polarization increases initially If the field is repeatedly switched from positive
by the growth of favorably oriented domains, to negative directions and is of sufficient
which will be magnetized in the easy direction magnitude then the polarization and induction
of the crystal. When the polarization can will cycle around the hysteresis loop in a
increase no further by the growth of domains, counter-clockwise direction. The area
the direction of magnetization of the domains contained within the loop indicates the amount
then rotates away from the easy axis to align of energy absorbed by the material during each
with the field. cycle of the hysteresis loop [29-31].
Page 36 of 154
Magnetic parameters Coercivity-mechanisms
The hysteresis loop is used to measure the There are various methods of increasing or
various parameters to characterize magnetic decreasing the coercivity of magnetic
materials. The Saturation polarization, PS and materials, all of which involve the controlling
Saturation magnetization, MS can be measured of the magnetic domains within the material.
from the first quadrant. Most of the useful For a hard magnetic material it is desirable that
information is derived from the second the domains cannot easily rotate on its
quadrant of the loop [29-31]. direction of magnetization and the domain
walls do not move easily and nucleation of
Remanence domains is difficult. However to prevent easy
The field that is produced by the magnet after rotation of domains the material could have a
the magnetizing field has been removed is strong uniaxial magneto crystalline anisotropy.
called the remanence, Br or Pr [29-31]. If the size of a magnetic particle / grain
decreases then there is a critical size below
Inductive coercivity which the decrease in magnetostatic energy by
The reverse field required to bring the splitting into two domains is less than the
induction to zero is called the inductive increase in energy due to the introduction of
coercivity, bHc, whereas the reverse field the domain wall. Particles that are below this
required to bring the magnetization to zero is critical size are known as “single domain
called the intrinsic coercivity, MHc. The particles”, and if they have sufficiently high
maximum value of the product of B and H is anisotropy to prevent the easy rotation of the
called the maximum energy product, (BH)MAX direction of magnetization then the particles
and is a measure of the maximum amount of will be permanently magnetic and difficult to
useful work that can be performed by the demagnetize. This type of coercivity
magnet. (BH)MAX is used as a figure of merit mechanism can be observed in melt-spun
for permanent magnet materials. NdFeB magnets where the crystal size is
~50nm, compared to the critical size for single
In addition, the shape of the initial domain particles of ~300nm [29-31].
magnetization curve and the hysteresis loop
can provide information about the magnetic Magnetoelasticity
domain behavior within the material. The Magnetoelasticity refers to the coupling of the
squareness factor is a measure of how square magnetic and elastic fields in a material.
the loop is and is a dimensionless quantity Magnetostriction is the result of the
between 0 and 1, defined by the ratio of the magnetoelastic coupling and refers to the
reverse field required to reduce P by 10% from dimensional change undergone by a material in
the remanence to Hcp. A squareness factor of the presence of a magnetic field. Most
one therefore corresponds to a perfectly square ferromagnetic materials, such as iron and
loop. There are several other methods to nickel, show some measurable shape change
quantify the squareness of the loop, such as the when subject to a magnetic field. The highest
ratio of Pr to Ps [29-31]. room temperature magnetostriction of a pure
element is Co - 60 microstrains [29-31].
Page 37 of 154
However, alloying elements can produce much shown in Fig-52a. Furthermore, the
larger magnetostriction even under a small reorientation of the domains due to the two
field; examples are: DyFe2, and TbFe2. There mechanisms mentioned above is shown in Fig-
are two processes that contribute to 53c.
magnetostriction on a macroscopic level. The
one is migration of domain walls in the Ferroelasticity
materials in response to the applied field and Ferroelasticity is a phenomenon in which a
second is the rotation of the domains. These material may exhibit a spontaneous strain
two mechanisms cause the dimensional change when a stress is applied. The applied stress will
in the material which in turn raises the strain cause a phase change to occur in the material
energy of the system (elastic properties of from one phase to an equally stable phase
materials are discussed later). When strain either of different crystal structure (e.g. cubic
energy increases the material tries to elongate to tetragonal) or of different orientation (a
in both horizontal and vertical directions when 'twin' phase). The shape memory effect and
a field is applied, but this is not possible super elasticity are manifestation of
because ferromagnetic material usually possess ferroelasticity. Nitinol (nickel titanium), a
triangular domains for closure and this common ferroelastic alloy, can display either
orientation does not enable the material to superelasticity or the shape-memory effect at
elongate in both directions simultaneously room temperature, depending on the
(Fig- 52b). 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
Fig-52, (a) Domain Structure after strain energy and lattice.
exchange energy compromise, (b) Triangular domain
structure for most ferromagnetics, (c) elongation due to
reorientation and rotation
Even if the domain boundaries do become
pinned, they may be reversed through heating.
However, the strain energy is reduced by Thus, a pseudoelastic material may return to its
decreasing the volume of the domains, which previous shape (hence, shape memory) after
means additional domain walls will be needed. the removal of even relatively high applied
This would in turn increase the exchange strains. One special case of pseudoelasticity is
energy; therefore, the final domain structure is called the Bain Correspondence. This involves
usually a compromise between the two, as the austenite/martensite phase transformation
Page 38 of 154
between a face centered crystal lattice and a based shape memory alloys are considered to
body centered tetragonal crystal structure [32- be engineering materials. These compositions
33]
. can be manufactured to almost any shape and
size. The yield strength of shape memory
Superelastic alloys belong to the larger family alloys is relatively low compared to
of shape memory alloys. When mechanically conventional steel, but some compositions
loaded, a superelastic alloy deforms reversibly have a higher yield strength than plastic or
to very high strains - up to 10% - by the aluminum. The yield stress for NiTi can reach
creation of a stress-induced phase. When the 500 [MPa]. The high cost of the metal and the
load is removed, the new phase becomes processing requirements make it difficult and
unstable and the material regains its original expensive to implement SMA's into design. As
shape. Unlike shape-memory alloys, no change a result, these materials are used in
in temperature is needed for the alloy to applications where the superelastic properties
recover its initial shape. Superelastic devices or the shape memory effect can be exploited.
take advantage of their large, reversible The range of applications for SMAs, are
deformation and include antennas, eyeglass increasing in recent years in the fields of
frames, and biomedical stents. Nickel Titanium consumer/commercial applications, industrial
is an example of an alloy exhibiting applications, medical applications. Nitinol wire
superelasticity [32-33]. is also used in robotics, Aerospace to reduce
aircraft Engine noise by Boeing, General
Shape memory alloys Electric Aircraft Engines, Goodrich
Shape memory alloy (SMA) / smart alloy is an Corporation, NASA, and All Nippon Airways
[35]
alloy that "remembers" its shape. After a .
sample of SMA has been deformed from its
original crystallographic configuration, it 6.33 Electrical Properties
regains its original geometry by itself during Electrical conductivity or specific conductivity
heating (one-way effect) or, at higher ambient is a measure of a material's ability to conduct
temperatures, simply during unloading an electric current. The conductivity σ is
(pseudo-elasticity or superelasticity). These defined as the ratio of the current density to
extraordinary properties are due to a the electric field strength :
temperature-dependent martensitic phase
transformation from a low-symmetry to a
highly symmetric crystallographic structure.
Those crystal structures are known as On the basis of the electrical properties solid
martensite (at lower temperatures) and materials can be classified into metals,
austenite (at higher temperatures) [34]. semiconductors and insulators, where the
charge carriers move in band states. In certain
The three main types of SMA are the copper- semiconductors and insulators, charge carriers
zinc-aluminum-nickel, copper-aluminum- are localized and their motion involves
nickel, and nickel-titanium (NiTi) alloys. The diffusive process. The expression for electrical
Copper based and NiTi (Nickel and Titanium) conductivity σ of a metal is given by
Page 39 of 154
the Seebeck effect, the Peltier effect, and the
Thomson effect.
σ = ni e (un + up)
Page 40 of 154
conduction. So the above equation can be Hall Effect in semiconductors
expressed as follows. When a current carrying semiconductor is kept
in a magnetic field, the carriers of the
Extrinsic semiconductors semiconductor experience a force in a direction
In extrinsic semiconductors is α generally perpendicular to the magnetic field and current
large (0.1 – 1 mV/K) and decreases with field, this is called Hall Effect in
increasing temperature [20-21]. semiconductors.
Hall Coefficient
The Hall Effect refers to the potential Where Eh is the Hall field
difference (Hall voltage) on the opposite sides The simple formula for the Hall coefficient
of an electrical conductor through which an given above becomes more complex in
electric current is flowing, created by a semiconductors where the carriers are
magnetic field applied perpendicular to the generally both electrons and holes which may
current. The ratio of the voltage created to the be present in different concentrations and have
power of the product of the amount of current different mobilities. For moderate magnetic
and the magnetic field (I*B), divided by the fields the Hall coefficient is
element thickness, is known as the Hall
coefficient RH.
6.34 Superconductivity
Superconductivity is a transition phenomenon
occurring in certain materials at extremely low
temperatures, characterized by exactly zero
Where Cr ~ 1, e is the electron charge, and n is electrical resistance and the exclusion of the
the charge carrier density of the carrier interior magnetic field (the Meissner effect).
electrons.
Page 41 of 154
The electrical resistivity of a metallic 6.35 Dielectric Properties
conductor decreases gradually as the Dielectric materials are substances that are
temperature is lowered. However, in ordinary poor conductors of electricity, but efficient
conductors such as copper and silver, supporters of electrostatic fields. If the flow of
impurities and other defects impose a lower current between opposite electric charge poles
limit. Even near absolute zero a real sample of is kept to a minimum while the electrostatic
copper shows a non-zero resistance. The lines of flux are not impeded, an electrostatic
resistance of a superconductor, on the other field can store energy. This property is useful
hand, drops abruptly to zero when the material in capacitors, especially at radio frequencies.
is cooled below its "critical temperature". Dielectric materials are also used in the
construction of radio-frequency transmission
The Meissner effect is the expulsion of a lines. Most dielectric materials are solids and
magnetic field from a superconductor and it is some examples are ceramic, mica, glass,
a fundamental property of the superconducting plastics, and the oxides of various metals.
state. It is used as a means of detecting Some liquids and gases can serve as good
superconducting transitions. There are two dielectric materials. Dry air is an excellent
kinds of superconductors depending on their dielectric, and is used in variable capacitors
magnetic behavior [20-21]. and some types of transmission lines. Distilled
water is a fair dielectric. A vacuum is an
Type - 1 Superconductors exceptionally efficient dielectric.
Materials in which superconductivity is
destroyed abruptly at a critical field Hc An important property of a dielectric is its
(function of temperature) called type-1 ability to support an electrostatic field while
superconductors. dissipating minimal energy in the form of heat.
The lower the dielectric loss (the proportion of
Type - 2 Superconductors energy lost as heat), the more effective is a
In type 2 superconductors the magnetic flux dielectric material [20, 21, 26].
starts to penetrate the material at a field of Hc1
lower than the thermodynamic critical field Hc. Capacitance
When two parallel plates of area A, separated
The magnetization gradually decreases with by a small distance l, are charged by +Q, –Q,
increasing field strength until H = Hc2, the an electric field develops between the plates
superconducting state is completely destroyed. can be expressed as follows
Between Hc1 and Hc2 the material is in vortex
state consisting of rod-shaped regions of
normal conductivity within the
superconducting bulk substance.
Where D = Q/A. e0 is called the vacuum
Oxides are some of the most important permittivity and e the relative permittivity, or
superconducting materials showing the highest dielectric constant (e = 1 for vacuum). In terms
Tc values [20, 21-30]. of the voltage between the plates, V = E l,
Page 42 of 154
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
The constant C= Aee0/l is called the an ionic crystal are displaced with respect
capacitance of the plates [20, 21]. to each other.
o Orientation polarization→ permanent
Field Vectors and Polarization dipoles (like H2O) are aligned.
The dipole moment of a pair of positive and
negative charges (+q and –q) separated at a The molar polarization of a solid is given by
distance d is p = qd. If an electric field is the Clausius – Mossotti equation
applied, the dipole tends to align the positive
charge points in the field direction.
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
Where, Q0 is the charge of a vacuum capacitor. Polarizability.
With Q' = PA, the charge density becomes 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
Where the polarization is given as follows, 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 voltage across a dielectric material becomes
specific polarization to occur is called the too great -- that is, if the electrostatic field
relaxation time [20, 21 and 36]. becomes too intense -- the material will
suddenly begin to conduct current. This
Dielectric constant phenomenon is called dielectric breakdown.
Another consideration is the dielectric
constant, the extent to which a substance Dielectric Strength
concentrates the electrostatic lines of flux. In Very high electric fields (>108 V/m) can free
Dielectric materials the randomizing effect of electrons from atoms, and accelerate them to
temperature is balanced by orienting effect of such high energies that they can, in turn, free
the internal field. The dielectric constant is other electrons, in an avalanche process (or
derived as follows. electrical discharge). This is called dielectric
breakdown, and the field necessary to start the
breakdown is called the dielectric strength or
breakdown strength.
Page 44 of 154
addition, the energetic shift of these transitions prisms and other purposes. Oxides absorb
due to the pressure dependence of the crystal- electromagnetic radiation by different modes
field splitting is used in sensors for very high depending on the nature of bonding.
pressures of up to more than 109 Pa.
Tightly bound electrons and ions in oxides
Electromagnetic Radiation & Light Interaction give rise to narrow resonance absorption,
The optical behavior of a solid material is a electrons in the ultraviolet region, and ions in
function of its interactions with the infrared region (restrahlen absorption).
electromagnetic radiation [Fig-53] having Absorption of radiation due to loosely bound
wavelengths within the visible region of the electrons is generally attributable to inter-band
spectrum. Possible interactive phenomena transitions. Such absorption bands in
include refraction, reflection, absorption, and semiconductors are broad and featureless, but
transmission of incident light [36, 37]. 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.
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Refraction
Light radiation experiences refraction in ---------------------- (3)
transparent materials and its velocity is
retarded and the light beam is bent at the Where κ is the extinction coefficient,
interface. Index of refraction is the ratio of the The index of refraction n and the extinction
velocity of light in a vacuum to the velocity in coefficient κ represent the real and imaginary
a particular medium. The phenomenon of parts, respectively, of a single complex
refraction is a consequence of electronic quantity, namely the complex index of
polarization of the atoms or ions, which is refraction
induced by the electric field component of the
light wave. The optical coefficient is the index
of refraction n. The index of refraction relates ------- (4)
to the ratio of the velocity of propagation of an Knowledge of ˜n allows derivation of
electromagnetic wave in vacuum c to the additional optical coefficients more useful in
velocity v in a medium comparing with predictions from theoretical
models, e.g., the complex dielectric constant
------------- (1) or the complex optical conductivity . The
complex dielectric constant obtained from
The refractive index similarly varies with the Maxwell’s equations is related to by
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 ----- (5)
purposes [20, 36 and 37]. The complex optical conductivity
relates to giving
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 -------- (6)
may undergo absorption. The intensity a Here is defined by the relation of the
distance x in the medium from the boundary is electric displacement to the electric field, D
given by = . Conventionally represents the
response of bound charges, though may in
principle be redefined providing that Eq. (6) is
--------------- (2) maintained. Rearranging Eq. (6) gives the real
Where I0 is the incident intensity and the σ1 and imaginary σ2 parts of the complex
absorption coefficient α is the fraction of optical conductivity
power absorbed in the medium per unit length.
Page 46 of 154
--- (8)
Page 47 of 154
Opacity and Translucency in Insulators ranges in the transmitted beam [20, 36 and 37] (Fig-
Normally transparent materials may be made 54).
translucent or even opaque if the incident light
beam experiences interior reflection and/or Optical phenomena
refraction. Translucency and opacity as a result Three other important optical phenomena are
of internal scattering may occur, (1) in luminescence, photoconductivity, and light
polycrystalline materials that have an amplification by stimulated emission of
anisotropic index of refraction, (2) in two- radiation (lasers).
phase materials, (3) in materials containing
small pores, and (4) in highly crystalline Luminescence
polymers [20, 36 and 37]. 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.
Page 48 of 154
Lasers the other due to localized electrons. Further
Coherent and high-intensity light beams are TMO based on oxygen bonding is discussed
produced in lasers by stimulated electron below.
transitions.
Laser (light amplification through stimulated 6.371 Monoxides
emission of radiation) action is seen in Monoxides of 3d transition metals, TiO to
materials such as ruby (0.01 atom%Cr3+ in NiO, possess the rock salt structure and exhibit
Al2O3). This occurs because of population interesting properties (Fig-55). TiO and VO
inversion, achieved by optical pumping to exhibit properties characteristic of itinerant d
higher energy levels (4F1 and 4F2) from which electrons. MnO, FeO, CoO, and NiO show
de-excitation occurs through a non-radiative localized electron properties.
process to an intermediate level (2E), from
which lasing occurs to the ground state (4A2),
giving 6943 Ȧ radiation.
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.
6.372 Dioxides
Dioxides of many of the transition metals Fig-56, Transition metal Di-oxides with Rutile structure
crystallize in the rutile structure, and their
electronic properties are shown in (Fig-56). The rutile structure therefore enables the oxide
The rutile structure provides the possibility of to become metallic through cation-cation
135o cation-anion-cation interaction between interaction and/or through cation-anion-cation
corner-shared octahedral and 90o cation-anion- interaction [20].
cation interaction between edge-shared
octahedral. A direct cation-cation interaction is 6.373 Sesquioxides
possible along the direction c. The important sesquioxides of the first row
transition metals crystallizing in the corundum
The octahedral crystal field of the cation and structure are Ti2O3, V2O3, Cr2O3, and α-Fe2O3.
the tetragonal structure provide an axial field, Cr2O3, and α-FeO3 are antiferromagnetic
which splits the triply degenerate metal t2g insulators. Ti2O3 and V2O3 exhibit
orbital into a non degenerate t|| orbital and a semiconductor-metal transitions at 410K and
150K, respectively.
doubly degenerate t﬩ orbital. While t﬩ can form
π∗ bands with anion pπ orbitals, t|| forms cation The transition in Ti2O3 is broad, occurring over
sub lattice d bands of the cation-cation distance a large temperature interval. In V2O3, the
along the c-axis is less than Rc. transition is accomplished by
antiferromagnetic ordering. These properties
Page 50 of 154
can be understood in terms of the cation-anion- 6.374 Properties of Pervoskites and Spinels
cation interactions (135o and 90o) and cation- The physical properties of perovskite include
cation interactions (in the basal plane and superconductivity, colossal magnetoresistance,
along the hexagonal c-axis). ionic conductivity, and a multitude of
dielectric properties, which are of great
The structure provides a trigonal component to importance in microelectronics and
the octahedral crystal field, which splits the t2g telecommunication. The great flexibility
orbitals into a1g (directed along cH) and eg(π) inherent in the perovskite structure enables
directed in the basal plane. In Ti2O3, with one many different types of distortions, which can
d electron per atom and a small hexagonal c/a occur from the ideal structure.
ratio, both the cation-cation distances are
smaller than the critical value (Rcc < Rbb < Rc). These include tilting of the octahedra,
The a1g band is therefore filled and separated displacements of the cations out of the centers
from the empty eg(π) band by a finite gap, of their coordination polyhedra, and distortions
accounting for the semiconducting behavior at of the octahedra driven by electronic factors
low temperatures. (i.e. Jahn-Teller distortions). Many of the
physical properties of perovskites depend
In V2O3, with large c/a ratio and with two d crucially on the details of these distortions,
electrons per vanadium, Rcc < Rbb < Rc; the eg particularly the electronic, magnetic and
(π) band is more stable than the a1g band. The dielectric properties which are so important for
metallic nature of rhombohedral V2O3 many of the applications of perovskite
indicates that these bands overlap to some materials.
extent. In Cr2O3 and Fe2O3, the a1g and eg(π)
orbitals are half-filled. In Cr2O3, the eg The perovskite structure is ideally suited for
electrons are localized, but the a1g electrons are the study of 180o cation-anion-cation
likely to be intermediate, since the interaction interaction of octahedral site cations. The
distance in the c direction is less than Rc. In possibility of cation-cation interaction is
Cr2O3, with no eg(σ) electrons. Accordingly, remote because of the large interaction
TN in Fe2O3 is higher (953 K) than in Cr2O3 distance along the face diagonal. Various
(307 K). Fe2O3 exhibits weak, parasitic properties of perovskites are shown with the
ferromagnetism in the range 253 < T < 953 K. examples: BaTiO3 is ferroelectric, SrRuO3 is
In this temperature range, the atomic moments ferromagnetic, LaFeO3 is weakly
lie nearly in the basal plane. ferromagnetic, and BaPb1-xBixO3 is super-
conducting, while LaCoO3 shows a nonmetal-
Anti-symmetric spin coupling is parallel to the to-metal transition. Several perovskite oxides
c-axis, and the anisotropic super exchange exhibit metallic conductivity; some examples
cants spins in the basal plane to produce a net are ReO3, AxWO3, LaTiO3, AMoO3 (A = Ca,
moment. Upon application of a strong Sr, Ba), SrVO3, and LaNiO3. Metallic
magnetic field in the c direction, a field- conductivity in perovskites is due to the strong
induced first-order spin-flip transition (Morin cation-anion-cation interaction.
transition) is observed around 260 K [20].
Page 51 of 154
6.375 Mixed Valence 6.376 Defects in Oxides
Many transition metal oxides contain cations in Most crystalline materials are not perfect and
more than one oxidation state. Properties of their regular pattern of atomic arrangement is
these oxides are generally determined by the interrupted by crystal defects.
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).
Page 52 of 154
environment, behaving as a more. The intrinsic defect concentration in
thermodynamically bivariant system. In these solids is therefore extremely small even
stoichiometric oxides, vacancies order at high temperatures. The intrinsic defect
themselves to give rise to super structures or concentration in binary solids around 0.8Tm is
complexes [20]. ~10-5 [20].
Page 53 of 154
Crystallographic shear where the G (P, T) surfaces of the parent and
One way by which anion-deficient product phases intersect sharply, the entropy
nonstoichiometry is accommodated in some and the volume show singular behavior. In
transition metal oxides is by eliminating point second-order transitions, on the other hand, the
defects by crystallographic shear. This leads to heat capacity, compressibility, or thermal
the formation of isolated shear plane or a expansivity shows singular behavior.
random array of shear planes, known as
Wadsley defect. Many physical properties diverge near Tc; that
is, they show anomalously large values as Tc is
In close packed oxides, we also see stacking approached from either side. An important
faults such as: tilt boundary (array of aspect of phase transition in solids is the
periodically spaced edge dislocations), twist presence of two modes. Operationally, a soft
boundary (array of screw dislocations), twin mode is a collective excitation whose
boundaries (a layer with mirror plane frequency decreases anomalously as the
symmetry), and coincidence boundary (one transition point is reached. In second-order
part of a crystal rotated with respect to another) transitions, the soft-mode frequency goes to
and antiphase boundaries (across which the zero at Tc, but in first-order transitions, the
sublattice occupation is interchanged) [20]. phase change occurs before the mode
frequency goes to zero. It has been found
6.377 Phase Transitions convenient to classify phase transition in solids
When temperature rises and pressure is held on the basis of the mechanism.
constant, a typical substance changes from
solid to liquid and then to vapor. Transitions Three important kinds of transition are as
from solid to liquid, from liquid to vapor, from follows: nucleation and growth transitions, a
vapor to solid and vice versa are called phase typical example being the anatase-rutile
transformations or transitions. Since some transformation of TiO2; positional and
substances have several crystal forms, there orientational order-disorder transitions; and
can also be solid to another solid phase martensitic transitions. Orientational order-
transformation. disorder is exhibited by many solids such as
ammonium halides, plastic (orientationally
Phase transitions involve changes in atomic disordered) crystals. A martensitic transition is
configuration, electronic or the spin a structural change caused by atomic
configuration. During a phase transition, the displacements (and not by diffusion)
free energy of the solid remains continuous, corresponding to a homogenous deformation
but thermodynamic quantities such as entropy, where the parent and product phases are related
volume, and heat capacity exhibit by a substitutional lattice correspondence, an
discontinuous changes. Depending on which irrational habit plane, and a precise
derivative of the Gibbs free energy, G, shows a orientational relationship [20, 21].
discontinuous change at the transition. Phase
transitions are generally classified as first order Structural phase transitions are also classified
or second order. In a first-order transition, 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].
Page 55 of 154
experimental observation by Astrov [39] in 1960 7.20 Progress of researches in Multiferroics
and Folen in 1961 (Fig-60), the magneto The field gained interest in the past decade
electric effect was studied intensively in the (Fig-61) after the observation of gigantic
1960s and 1970s [40] attracted continuing ferroelectric polarization in one of the
interest for more than four decades. The conventional multiferroics, BiFeO3 (Bismuth
history of multiferroics research dates back to ferric Oxide) at room temperature [40], and the
1958 from the work by Smolenskii and discovery of a new class of multiferroics
coworkers (Fig-60) [40]. showing a large magnetoelectric effect.
Numerous multiferroics have been identified to In 2003, ferroelectric activity was found in
date. Examples are some boracites (Ni3B7O13I, rare-earth manganites with orthorhombically
Co3B7O13I, etc.), some fluorides [BaMF4 (M = distorted perovskite structure, TbMnO3, which
Mn, Fe, Co, and Ni)], magnetite Fe3O4, shows antiferromagnetic orders with long
hexagonal manganites (YMnO3, HoMnO3, wavelength modulation as compared to their
etc.), perovskites ABO3 having a Bi or Pb ion chemical unit cell, [44] owing to competing
on the A site and transition metal(s) on the B magnetic interactions. In this new multiferroic
site [e.g., PbFe 1−X NbxO3, BiFeO3 and compound, a large magnetoelectric effect has
BiMnO3], CdCr2S4, and hexagonal ferrites been observed at the onset field of a
(e.g., LuFe2O4). metamagnetic transition. More recently,
theoretical and experimental studies of the
Scientific communities around the world have rare-earth manganites revealed that the
made lot of contributions in publishing several ferroelectricity originates from a cycloidal
reviews in the past years which led to the spiral spin structure. These results indicate the
understanding of magnetoelectric effect, emergence of a new class of ferroelectrics in
characterization of magnetoelectric which the origin of ferroelectricity is related to
multiferroics, according to the origin of their magnetic order and is different from known
multiferroic nature [40]. 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].
Page 56 of 154
order is much larger than for magnetic order, properties of BFO thin films, Nano structures
and the origins of these orders have no relation and Nanopillar forms are quite promising and
to each other, which leads to only weak encouraging for further research to use the
coupling between magnetism and BFO thin films in industrial applications,
ferroelectricity. Single-phase multiferroics especially in the new and novel device
show spontaneous magnetization and applications.
polarization simultaneously at ambient
conditions, remains elusive as most systems 7.40 Structures of Multiferroics
(Eg: manganites) exhibit multiferroicity only at Multiferroics are perovskites with general
low temperatures [40]. 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.
Page 57 of 154
system in which magnetic and electric ordering high temperature mirror plane, while keeping
have been found to coexist. The Mg and W the distance to OT constant [45].
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].
a vertical shift of the Y ions away from the one intermediate situation among them which
Page 58 of 154
can produce multiferroics [46]. Charge ordering Among the few room temperature single-phase
in the sites leads to a checker board ordering magnetoelectric multiferroics reported so far,
pattern as shown in Fig-64(a) and is known as BiFeO3 shows the highest ferroelectric
Site-Centered ordering (SCO). When the polarization, with a ferroelectric Curie
charge ordering occurs in the bonds instead of temperature (TC) of ~1,100 K and an
in the sites, as depicted in Fig-64(b), it is called antiferromagnetic N´eel temperature (TN) of
a Bond-Centered Ordering (BCO). ~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.
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].
Fig.65 Schematic of the crystal structure of BFO and the ferroelectric polarization (arrow) and antiferromagnetic plane
(shaded planes).
Page 60 of 154
Advanced, high- performance computers, high- 8.20 Materials for Thin Films
definition TV, digital camcorders, sensitive Electronic materials are mainly used to
broadband imaging systems, flat-panel fabricate or grow thin films and they can be
displays, robotic systems, and medical classified in to insulating, semi-insulating and
electronics and diagnostics are but a few metallic. Thin films can be classified in to
examples of miniaturized device technologies Ferro / Ferrimagnetic thin films, Ferro / Ferri
that depend on the utilization of thin film electric thin films and Magnetoelectric /
materials [20, 53]. Multiferroic thin films.
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.
Page 62 of 154
Deposition Directionality Uniform Coating
o Directional: good for lift-off, trench Uniform Coating for spherical surfaces with
filling source on its edge (Fig-69) is given by
o Non-directional: good for step coverage
Cost of ownership and operation
Page 63 of 154
Fig-71 Graph showing Sample size Vs Source –Sample
distance in Uniform Coating requirements for flat
surface
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].
Page 65 of 154
These processes create the solid thin films 8.32 Vacuum Systems
directly from the material without any Many prevalent deposition techniques used in
chemical reaction. The deposited material is modern thin film technology requires the
physically moved on to the substrate (Fig-74). creation of vacuum condition for the
deposition to occur. The quality and
Types of PVD consistency in quality of final products (thin
o vacuum evaporation film) depends on these vacuum systems [62].
o sputtering
o Molecular beam epitaxy (MBE) Basic Vacuum Concept
Vacuum is the absence of gases, moisture and
Chemical Vapor Deposition particles which normally fill our environment.
In CVD, the deposition happens because of a In a deposition system a container is provided
chemical reaction. This process creates the and the majority of these elements are removed
solid thin films directly from chemical to create a vacuum. The vacuum condition is
reactions in gas and/or liquid compositions or an important factor to get suitable vacuum
with the substrate material. The solid material environment to produce quality thin films.
is usually not the only product formed by the Vacuum condition, accelerates the mean free
reaction. By products can include gases, path for atoms by eliminating the presence of
liquids and even other solids. gases that could react with the materials to be
deposited; It could reduce the vapor pressure
Types of CVD and lower the evaporation temperature of the
target material and provides the ultimate clean
o Atmospheric pressure chemical vapor vacuum environment.
deposition (APCVD)
o Low pressure chemical vapor deposition Measure of vacuum
(LPCVD) In vacuum measurements, pressures are mostly
o Plasma assisted (enhanced) chemical vapor measured in millimeters of mercury or torr.
deposition (PACVD, PECVD) One torr is the pressure necessary to support a
o Photochemical vapor deposition (PCVD) column of mercury with a height of one
o Laser chemical vapor deposition (LCVD) millimeter.
o Metal-organic chemical vapor deposition
(MOCVD) 1 atmosphere = 101 KPa = 760 torr.
o chemical beam epitaxy (CBE)
Vacuum conditions are classified as low
vacuum of pressure range 105 to 103 Pa (760-
Other thin film growth techniques - from liquid 25 torr), Medium vacuum 103 to 10-1 Pa (25
and solution phase are: torr to 0.75 milli torr), High vacuum 10-1 to10-4
o spray coating Pa (~ 10-3 to 10-7 torr) and Very high vacuum
o spin coating 10-4 to 10-7 Pa ( ~ 10-7 to 10-12 torr). Most
o electroplating practical deposition processes occur in the
o liquid phase epitaxy medium to high vacuum ranges [62].
Page 66 of 154
There are two pressure regimes in vacuum Where D is the diameter of the tube in
systems, and gases behave differently in each centimeters, and L is its length, also in
regime. centimeters.
o In the viscous flow regime, gas flows as a
fluid, where the mean free path of the gas Pumping speed is expressed in liters per
molecules is much smaller than the second. The amount of mass going through the
dimensions of the apparatus. Pump is given by
o In the molecular flow regime, the mean
free path is much longer than the
characteristic dimensions of the apparatus. Where P is the pressure at the inlet of the
In this regime, gas molecules interact pump, and Sp is the pump speed. The net speed
almost entirely with the walls of the of a pump connected to a vacuum chamber by
chamber, acting independent of each other. a tube is
Where Q is the mass flow, P1 is the pressure at Where, V is the volume of the chamber.
the input of the tube, and P2 is the pressure at
the output and C is the conductance of the Vacuum Chambers
tube. Generally vacuum chambers are made out of
stainless steel or glass chambers because they
Conductance in the viscous flow regime is do not corrode, are easily cleaned, non
proportional to the average pressure in the tube magnetic and have good out-gassing
and is high, compared to the molecular-flow characteristics. Stainless is used for large
regime, because the gas molecules push each vacuum systems because of its relatively high
other along. In the molecular-flow regime, strength, ease of welding and machinability.
conductance through a tube is independent of The vacuum system consists of a vacuum
pressure and is given by 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
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.
Page 68 of 154
Contamination Deposition (CVD), Sputtering and Molecular
Contamination in the vacuum system is the Beam Epitaxy (MBE) are discussed below.
result of leaks from the vacuum container and
evaporation of moisture and other materials 8.34 Pulsed Laser Deposition (PLD)
from the inside walls of the container known as Pulsed laser deposition (PLD) is an efficient
out-gassing. The rate of out-gassing from a method to produce thin films by utilizing a
surface can be expressed as technique called laser ablation. PLD gained
tremendous interest after T.Venketesan in 1987
first applied this method to create high
temperature superconductive (HTSC) films.
Where Or is the rate of out-gassing, q is the
specific out-gassing rate for the material and A PLD is applicable to almost any material, in
is the surface area. particular to compounds that are difficult to
produce in thin-film form by other techniques.
The specific out-gassing rate is unique for a Examples of such materials include complex
given material as in Fig-76. The types of ceramic materials such as high-temperature
materials used in vacuum system, the quality superconductors and certain magnetic
of seals (rubber seals, metallic seals etc) and materials (e.g., yttrium iron garnet (YIG) and
the general clean environment can limit the ferromagnetic shape-memory (FSM) alloy Ni-
maximum obtainable vacuum [62, 63]. Mn-Ga.
Page 69 of 154
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.
Excimer Lasers
The term “excimer” is an abbreviation of
Fig-78 Principal components of the vacuum system “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
Page 71 of 154
o Cost-effective: one laser can serve many
vacuum systems. Sputtering has proven to be a successful
o Fast: high quality samples can be grown method of coating a variety of substrates with
reliably in 10 or 15 minutes. thin films of electrically conductive or non-
o Scalable: as complex oxides move toward conductive materials. One of the most striking
volume production [62, 63 and 64]. characteristics of sputtering is its universality.
Since the coating material is passed into the
8.35 Sputtering vapor phase by a mechanical rather than a
Sputtering is a vacuum evaporation process chemical or thermal process, virtually any
which physically removes portions of a coating material can be deposited. Direct current is
material called the target, and deposits a thin, used to sputter conductive materials, while
firmly bonded film onto an adjacent surface radio frequency is used for non-conductive
called the substrate (Fig-79). The process materials.
occurs by bombarding the surface of the The range of sputtering application is large.
sputtering target with gaseous ions under high Current applications of great importance
voltage acceleration. As these ions collide with include thin films of:
the target, atoms or occasionally entire o Magnetic materials for data storage tapes.
molecules of the target material are ejected and Typical materials are Co-Ni, Tb-Fe and
propelled against the substrate, where they Co-Ni-Cr.
form a very tight bond. The resulting coating is o Optical materials for lens characteristics.
held firmly to the surface by mechanical Typical materials are CeO2, MgO and
forces, although, in some cases, and alloy or MgF2.
chemical bond may result [65, 66]. 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.
Fig- 79 Sputtering Vacuum Deposition Process
Page 72 of 154
Additional applications include oxide These energetic free electrons in-elastically
microcircuit insulation layers, amorphous collide with Ar atoms and excitation of Ar
optical films for integrated optics devices, occurs and the gas glows which induces the
piezoelectric transducers, photoconductors, ionization of Ar forming Ar+ + 2nd electron.
luminescent films for display devices, optically The 2nd electrons repeat the above process
addressed memory devices, video discs, solid causing the gas to breakdown and the
electrolytes and thin film lasers [65, 66]. discharge to glow (plasma) (Fig-80) [65, 66].
Page 73 of 154
dark space are accelerated toward the cathode o sputtered atoms have to go through
(target), bombarding (sputtering) the target. hundreds of collisions before reaching the
The atoms knocked out from the target substrate
transport to the substrate (momentum transfer, o significantly reduces deposition rate
not evaporation!) and generate 2nd electrons o also causes source to deposit on chamber
that sustain the discharge (plasma) [65, 66]. wall and re-deposit back to the target
Page 74 of 154
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
Fig- 83 Schematic of DC Magnetron sputtering showing commercial PVD for several reasons. The
the impact of Magnetic field on ions. major reasons are it is not economic to use
large RF power supplies due to their high cost
Hopping radius r: and the fact that you introduce high
temperatures, due to the high self-bias voltage
associated with RF power, into insulating
materials.
Where, Vd is the voltage drop across the dark DC sputtering cannot be used for depositing
space (~ 100 V), B is the magnetic field (~ 100 dielectrics because the insulating cathode will
G) for electron r ~ 0.3 cm and Ar+ ion the r ~ cause charge build up during Ar+ bombarding,
81 cm. which reduces the voltage between electrodes
and the discharge distinguishes. To eliminate
Then the current density (proportional to this problem AC power was used, that
ionization rate) increases by 100 times and developed the RF Sputtering technique.
required discharge pressure drops 100 times
and deposition rate increases 100 times~ as
shown in Fig-84 [65, 66].
Page 75 of 154
Using AC power at low frequency (<100 KHz) material is sputtered from the target, it reacts
both electrons and ions can follow the with this gas, so that the deposited film is a
switching of the voltage (Fig-85) [65, 66]. different material, i.e. an oxide or nitride of the
target material.
At high frequency (> 1 MHz) the heave ions
can no longer follow the switching and the ions Reactive sputtering Process
are accelerated by dark-space (sheath) voltage. Reactive gases like oxygen or nitrogen is
added to the chamber during deposition
The electron neutralizes the positive charge (evaporation or sputtering). Chemical reactions
buildup on both electrodes however; there are take place on substrate and target. The target
two dark spaces which sputter both target and may get unwanted impurities if chemical
substrate at different cycles as shown in Fig- reactions are faster than sputter rate. This can
86. be avoided by adjusting the reactive gas flow
to get good stoichiometry without
incorporating excess gas into film [65, 66].
Reactive sputtering
In this process, a small amount of some non-
noble gas such as oxygen or nitrogen is mixed
Fig. 87 Schematic diagram of a MBE system
with the plasma-forming gas. After the
Page 76 of 154
The solid source materials are placed in UHV is the essential environment for MBE.
evaporation cells to provide an angular Therefore, the rate of gas evolution from the
distribution of atoms or molecules in a beam. materials in the chamber has to be as low as
The substrate is heated to the necessary possible. So pyrolytic boron nitride (PBN) is
temperature and, when needed, continuously chosen for the crucibles which give low rate of
rotated to improve the growth homogeneity [64, gas evolution and chemical stability up to
66]
. 1400oC, molybdenum and tantalum are widely
used for the shutters, heaters and other
MBE operating conditions components, and only ultra pure materials are
used as source. To reach UHV, a bakeout of
o The mean free path λ of the particles the whole chamber at approximately 200oC for
should be larger than the geometrical size 24 hours is required any time after having
of the chamber. It is easily fulfilled if the vented the system for maintenance. A
total pressure does not exceed 10-5 Torr cryogenic screening around the substrate
(Fig-88). minimizes spurious fluxes of atoms and
molecules from the walls of the chamber.
o The condition for growing a sufficiently
clean epilayer must be satisfied. (Eg: For Despite this big technological problem, MBE
the monolayer deposition times of the systems permit the control of composition and
beams tb and the background residual vapor doping of the growing structure at monolayer
tres the relation is t res < 10-5 tb. This can be level by changing the nature of the incoming
fulfilled by (UHV) ultra high vacuum). 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 %.
Page 77 of 154
like the RHEED (Reflection High Energy accommodated on the surface, the complete
Electron Diffraction). The oscillation of the expression for the flux leaving the surface can
RHEED signal exactly corresponds to the time be easily found as
needed to grow a monolayer and the diffraction
pattern on the RHEED window gives direct
indication over the state of the surface as can The factor ‘a’ is dependent on the microscopic
be seen in Fig-89 [64, 66]. status of the surface and is strongly
unpredictable.
Effusion Cells
The effusion cells used in MBE systems The Knudsen evaporating method overcomes
exploit the evaporation process of condensed this problem providing a molecular beam that
materials as molecular flux source in vacuum. is independent of ‘a’. An ideal Knudsen cell is
In a closed enclosure, for pure substances, composed of a large enclosure where the
equilibrium is established between the gas and condensed material is in thermodynamic
the condensed phase. Such systems have only equilibrium with the gas phase and peq is not
one degree of freedom f, that means that the perturbed.
pressure peq is a function of the temperature T
and can be approximately expressed by the The ideal Knudsen cell (as explained in in
Clapeyron equation. Section: ) exhibits an angular distribution of
the evaporated particles that follows a cosine
law, where the angle θ is referred to the normal
Where, ∆H is the evaporation enthalpy and k B to A.
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 The beam is usually bent through an angle of
phase surface shows that the maximum value 270° in order to ensure that the gun filament is
for the evaporated flux Γm is not directly exposed to the evaporant flux.
Page 78 of 154
Compounds such as gallium arsenide are reaction that produces another compound)
usually deposited by repeatedly applying a undergoes a chemical change at a solid surface,
layer of one element (Ga), then a layer of the leaving a solid layer on the surface with little
other (As), so that the process is chemical, as regard to direction. Thin films from chemical
well as physical. deposition techniques tend to be conformal,
rather than directional. Chemical deposition is
The beam of material can be generated by further categorized by the phase of the
either physical means (that is, by a furnace) or precursor like liquid phase, Gas Phase [65, 66].
by a chemical reaction (chemical beam
epitaxy) [64, 66]. 8.37 Chemical vapor deposition (CVD)
generally uses a gas-phase precursor, often a
A typical MBE chamber is shown in Fig-90 to halide or hydride of the element to be
visualize the actual equipment. 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].
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 Fig. 91 Schematic diagram of CVD Process
compounds that participate in the chemical
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.
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) o Temperature is controlled around 600 -
Thermal energy for reaction activation 900ºC by “flat” temperature zone through
o System works at vacuum (~ 0.1 –1.0 torr), using multiple heaters
resulting in high diffusivity of reactants o Low gas pressure reduce gas-phase
reaction-rate is limited. reaction which causes particle cluster that
o Wafer can stacked closely without lose contaminants the wafer and system
uniformity as long as they have the same
temperature
Page 81 of 154
Fig-93 Comparison chart for various thin film deposition technologies
Page 82 of 154
Doping Process type impurity. Semiconductors which are
The pure semiconductor is basically neutral. It doped in this manner with either ‘N’ or ‘P’
contains no free electrons in its conduction type impurities are referred to as EXTRINSIC
bands. Even with the application of thermal semiconductors.
energy, only a few covalent bonds are broken,
yielding a relatively small current flow. A N-Type Semiconductor
much more efficient method of increasing The N-type impurity loses its extra valence
current flow in semiconductors is by adding electron easily when added to a semiconductor
very small amounts of selected additives to material, and in doing so, increases the
them, generally no more than a few parts per conductivity of the material by contributing a
million. These additives are called impurities free electron. This type of impurity has 5
and the process of adding them to crystals is valence electrons and is called a
referred to as Doping (Fig-94). 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.
P-Type Semiconductor
Fig- 94 Doping a Semi conductor
The second type of impurity, when added to a
semiconductor material, tends to compensate
The purpose of semiconductor doping is to
for its deficiency of 1 valence electron by
increase the number of free charges that can be
acquiring an electron from its neighbor.
moved by an external applied voltage. When
Impurities of this type have only 3 valence
an impurity increases the number of free
electrons and are called TRIVALENT
electrons, the doped semiconductor is
impurities. Aluminum, indium, gallium, and
NEGATIVE or N TYPE, and the impurity that
boron are trivalent impurities. Because these
is added is known as an N-type impurity.
materials accept 1 electron from the doped
However, an impurity that reduces the number
material, they are also called ACCEPTOR
of free electrons, causing more holes, creates a
impurities.
POSITIVE or P-TYPE semiconductor, and the
impurity that was added to it is known as a P-
Page 83 of 154
Methods of doping Ion implantation
The methods of doping are Diffusion, Ion The introduction of dopants in a semiconductor
implantation and doping during growth which is the most common application of ion
are explained below. implantation. Dopant ions such as boron,
phosphorus or arsenic are generally created
Diffusion from a gas source, so that the purity of the
In this method, the semiconducting material to source can be very high. These gases tend to be
be doped is placed in a furnace wherein the very hazardous.
furnace contains an atmosphere of a carrier gas
and a dopant containing gas. The doping When implanted in a semiconductor, each
containing gas is greater than about 0.1 volume dopant atom creates a charge carrier in the
percent of the total volume in the furnace semiconductor (hole or electron, depending on
chamber. The pressure of the composite gas is if it is a p-type or n-type dopant), thus
greater than about 0.1 Torr. The composite gas modifying the conductivity of the
has an oxidizing agent concentration of less semiconductor in its vicinity (Fig-96) [68-70].
than about 1 part per million (Fig-95) [68-70].
This method permits the direct doping of a Fig- 96 Doping a Semi conductor by Ion implantation
silicon surface to form a shallow n-doped
region having a high peak concentration by a Doping during growth
diffusion process thereby eliminating damage In this method the dopant is injected into the
to the silicon surface from ion implantation plasma and are based on the interactions of
which is the commonly used method to plasma or neutral gas with the surfaces of
achieve these high doping concentrations. substrate at different temperatures and varying
Since the method is non directional trench electric potentials (co-sputtering, dc-sputtering,
sidewalls can be doped at high concentrations. thermally activated injection to the neutral gas,
plasma-assisted transport) (Fig-97) [68-70].
Page 84 of 154
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.
Page 85 of 154
absorption of polarized light on passing The Cu signal is constant, reflecting its
through a material in two different directions constant 1nm thickness (Fig-99). It also gives
called dichroism. information on the chemical environment of
the atoms and their magnetic state. Core
The origin of the dichroism effect can be electrons are excited in the absorption process
anisotropies in the charge or the spin in the into empty states above the Fermi energy and
material known as magnetic dichroism. The thereby probe the electronic and magnetic
principles and applications of magnetic properties of the empty valence levels. The
dichroism techniques in the x-ray region, the magnetic properties of 3d transition metal
X-Ray Magnetic Circular Dichroism (XMCD) elements Fe, Co and Ni are largely determined
and X-Ray Magnetic Linear Dichroism by the 3d valence electrons. Since X-ray
(XMLD) techniques are discussed below [71]. absorption spectra are governed by dipole
selection rules the d-shell properties are best
8.43 X-ray absorption spectroscopy (XAS) probed by L-edge absorption studies (2p to 3d
X-ray absorption spectroscopy (XAS) utilizes transitions). The L-edge X-ray absorption
the energy dependent absorption of x-rays to spectra of the transition metals and oxides are
obtain information about the elemental dominated by two main peaks separated by
composition of the sample, as shown in Fig-98. about 15 eV as shown in Fig-99 [71, 72].
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].
Page 87 of 154
the angle between the photon spin and the
In Fig-101 the transitions occur from the spin- magnetization direction.
orbit split 2p core shell to empty conduction
band states. In conventional X-ray absorption The maximum dichroism effect (20%) is
the total transition intensity of the two peaks is observed if the photon spin direction and the
proportional to the number of d holes (first magnetization directions are parallel and anti-
sum rule). By use of circularly polarized X- parallel as shown on the left side of Fig-102.
rays the spin moment (b) and orbital moment When the photon spin and the magnetization
(c) can be determined from linear directions are perpendicular the resonance
combinations of the dichroic difference intensities at the L3 and L2 edges lie between
intensities A and B, according to other sum those obtained for parallel and anti-parallel
rules [71, 72]. alignments [71, 72].
Since spin flips are forbidden in electric dipole The L3 and L2 resonance intensities and their
transitions, spin-up (spin-down) photoelectrons differences for parallel and anti-parallel
from the p core shell can only be excited into orientation of photon spin and magnetization
spin-up (spin-down) d hole states. 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].
Page 88 of 154
cubic systems. This effect is the basis for the The resulting pd hole configuration again gives
determination of the spin axis in ferromagnetic rise to multiple splitting and the XAS spectrum
and especially antiferromagnetic systems by reflects the multiple structure. In the
means of x-ray magnetic linear dichroism paramagnetic state the absorption spectrum of
(XMLD) spectroscopy [71, 72]. NiO does not exhibit polarization dependence
because of cubic symmetry. In the
Since the electric field vector oscillates in time antiferromagnetic state the spin-orbit coupling
along an axis and the radiation may be leads to a distortion of the charge density and
absorbed at any time, linearly polarized x-rays an XMLD effect is observed [71, 72].
are only sensitive to axial not directional
properties. Because of the cubic symmetry of the NiO
lattice the charge distribution around the atoms
The orientation of the antiferromagnetic or is nearly spherical and no linear dichroism
ferromagnetic axis, but the spin direction itself effect exists above the Néel temperature (520
cannot be determined. Fig-102 shows the K), where NiO is paramagnetic. At room
origin of the XMLD effect in NiO. 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.
Page 89 of 154
In general, the XMLD effect is small in 3d of the reciprocal lattice directly with a small
metals owing to the small size of the spin orbit stationary crystal. Because of the charge,
interaction and the large band width, resulting interaction of electrons with atoms is
in small charge anisotropy when the d states considerably stronger than that of X-rays, thus
are summed over the Brillouin zone. making it possible to record electron
diffraction patterns almost simultaneously.
However, a sizeable XMLD effect (of order One can investigate defect ordering,
10-30%) may be observed in the presence of superstructures, and fine particle samples [20, 72,
and 73]
multiplet splitting. At a particular multiplet .
energy only selected d valence states are
probed through matrix element effects that Neutron diffraction
enhance the XMLD effect. Each multiplet is a Thermal neutrons with a velocity of about
strongly coupled spin-orbit state whose spatial 4000 m/s associated with a wavelength of ~ 1.0
extent is non-spherical, giving rise to the large Ǻ are used in neutron diffraction experiments.
XMLD effect. Neutron diffraction is particularly useful in
locating light atoms such as hydrogen in
In Fig-102 the XMLD effect is especially crystals.
visible at the Ni L2-edge where a sizeable
difference is observed for E parallel (green) Neutron diffraction provides an experimental
versus perpendicular (red) to the magnetic axis. means whereby the different magnetic
Since x-ray linear dichroism can arise from structures can be determined. Inelastic neutron
electric and magnetic asymmetry s, magnetic scattering by crystals is used in the study of
order effects can be distinguished from Ligand quantized vibrational modes (phonons) and
field effects through temperature dependent dynamics in solids [20, 72, and 73].
measurements.
8.46 Piezoresponse force microscopy
Circularly polarized x-rays have directionality Piezoresponse Force Microscopy (PFM) is a
and they can detect the direction of the spin scanning probe microscopy (SPM) technique
and orbital moments which is utilized in based on the reverse piezoelectric effect, where
XMCD microscopy of ferromagnets. The a (piezoelectric) material expands or contracts
dependence of the XMLD intensity on the upon applying to it an electric field [20, 72, 73].
relative orientation of the electric field vector
and the magnetic axis can be used for XMLD PFM is an Imaging Technique classified under
imaging for antiferromagnets [71, 72]. Derivative Imaging Modes. It is a derivative of
the Primary Imaging Mode called Contact
Electron diffraction Mode AFM. In PFM, the AFM probes a
Electron diffraction is a valuable technique for sample’s mechanical response to an applied
studies in solids. The differences entail the electric field. The AFM tip used in PFM is
small wavelength of electrons and the charge usually made of, or is coated with, a
carried by them. The smaller wavelength conductive material, as this conductivity
makes it possible to record extensive sections
Page 90 of 154
enhances the electrical contact between the tip In Fig-104, the PFM image (phase signal, right
and the sample. 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.
Page 91 of 154
PFM Spectroscopy is a non-imaging technique electron spin resonance (ESR) spectroscopy,
that compliments PFM imaging. In PFM and scanning tunneling microscopy (STM) [20,
72-75]
Spectroscopy, the piezoresponse of a given .
location on the sample can be mapped versus 8.50 Classification of Thin Films
the dc bias. This technique can also be used to Thin Film are classified based on their
study hysteretic characteristics of the properties as follows
piezoresponse [72-75]. o Magnetic Thin Films
o Ferro / Ferri Electric Thin Films
8.47 Transmission Electron Microscopy o Multiferroic thin films
The electron microscope is the most versatile o Magnetoelectric thin films
instrument available to study the ultrastructure o Magnetoelastic thin Films
of materials, to identify new or known phases, o Piezoelectric thin films
and to simultaneously yield information on They can be of varying thickness from 10µm
composition. Usually electron diffraction and to 1nm based on its application requirements.
imaging are employed together in transmission
electron microscopy (TEM). These capabilities 8.51 Magnetic thin films
are further enhanced in a scanning Thin magnetic films originated from the
transmission electron microscope (STEM). studies of their effects on light, today, they are
TEM generally produces a projected image being layered to make complex structures with
wherein all depths of thin specimens are in unique magnetic properties. Devices based on
focus at the same time, making it difficult to these structures are revolutionizing electronic
interpret surface features of specimens to data storage, due to growing applications in
operate at different temperatures, in different magnetic sensors and in magnetic storage
atmospheres [20, 72-75]. media like computer disks and random-access
memories. Magnetic random-access memories
8.48 Scanning Electron Microscopy (MRAMs) based on structures of magnetic
In scanning electron microscopy (SEM), a metallic films interspersed with nonmagnetic
finely focused electron beam probe moves metallic or insulating interlayer could be the
from one point on the specimen to the next to next generation in magnetic-storage
form a faster pattern, similar to television technology, replacing the semiconductor-based
imaging. The most important aspect of electron dynamic random-access memories (DRAMs)
microscopy in the study of metal oxide is its that are now the standard [76].
ability to elucidate problems that are beyond
the capability of X-ray or neutron Advantages of MRAMs,
crystallography. High resolution electron o Non-volatility (they retain information
microscope (HREM) images show local when the computer is switched off).
structures of crystal in great detail. Many other o High storage density.
techniques are employed for the study of metal o Low energy consumption.
oxides. Some of the important ones are o MRAM devices would be smaller.
extended absorption fine structure (EXAFS) o Faster.
spectroscopy, solid state NMR spectroscopy, o Cheaper.
Page 92 of 154
o More robust in extreme conditions such as
high temperature, or high-level radiation or
interference.
Page 93 of 154
n-type semiconductor regions, which are Spintronics describes technology that makes
isolated from the p-type substrate by reversed- use of the spin state of electrons. Electrons
biased p-n diodes. A metal (or poly-crystalline) exhibit the basic properties of spin, charge, and
gate covers the region between source and mass. When the intrinsic spin of an electron is
drain and the flow of electrons from the source measured, it is found in one of two spin states,
to the drain is controlled by the voltage applied known as spin up and spin down. The Pauli
to the gate and the gate voltage changes Exclusion Principle states that the quantum-
electron density (Fig-106). 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.
Page 94 of 154
and German physicists [84]. It results from the charge of electrons for increased
subtle electron-spin effects in ultra-thin functionality. Potential benefits of using spin
'multilayers' of magnetic materials, which currents include increased speed of devices and
cause huge changes in their electrical decreased power consumption. IBM identified
resistance when a magnetic field is applied. It that the read heads incorporating GMR
is a sandwich structure with alternating layers materials would be able to sense much smaller
of magnetic and nonmagnetic metal (Fig-107). 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
Fig- 107 Typical GMR sandwich structure antiparallel) as in a conventional transistor
memory device. Another application is a
Depending upon the relative orientations of the magnetic version of a random access memory
magnetizations in the magnetic layers, the (MRAM) device used in computers [86].
electrical resistance changes from small MRAM is rapidly developing as a technology
(parallel magnetizations) to large (antiparallel because it can allow quantum computing by
magnetizations). The magnitude of this change use of spin of individual particles to process
is twice the order of magnitude larger than is information, is known as a quantum bit or
possible with conventional materials, hence the qubit. It is amazing to know that only 34 qubits
name “giant magnetoresistance” [81]. are required to represent the total amount of
To make a spintronic device, the primary information stored in a 10 Gb hard rive [80].
requirement is to have a system that can With the exception of MRAM, none of the
generate a current of spin polarized electrons, spintronic devices such as spin based light
and a system that is sensitive to the spin emitting diodes (spin LEDs), resonant
polarization of the electrons. Most devices also tunneling diodes (spin RTDs), field effect
have a unit in between that change the current transistors (spin FETs), and spin based single
of electrons depending on the spin states. The electron devices based on quantum dot arrays
simplest method of generating a spin-polarized can be fabricated without the ability to
current is to inject the current through a generate, maintain, and propagate long lived
ferromagnetic material. The most common spins in a semiconductor [80]. All spintronic or
application of this effect is a giant more specifically semiconductor spintronic
magnetoresistance (GMR) device. Unlike devices act according to the simple scheme:
traditional IC’s in which signals are (1)information is stored (written) into spins as
determined by the charge of electrons, a particular spin orientation (up or down), (2)
Spintronics devices utilize both the spin and 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 .
The long coherence time of spin makes The basic idea behind semiconductor based
spintronic devices particularly attractive for spintronics is to add the characteristics of
memory storage and magnetic sensor magnetic devices to existing devices such as
applications, and, potentially for quantum light-emitting diodes and field effect
computing where electron spin would transistors [81]. This would lead to technologies
represent a bit (called qubit) of information [79]. such as memory and microprocessor functions
Page 96 of 154
integrated on the same chip, magnetic devices not found in the constituent materials. The
with gain and integrated sensors with on-chip ferroelectric order by magnetic phase transition
signal processing and off-chip optical in TbMnO3 in the absence of magnetic fields is
communications. A technology tree which discussed below [40].
summarizes the spin-based devices is shown is
shown in Fig-108. 8.521 Magnetoelectric multiferroic Thin
Films -TbMnO3 and Ni3V2O8
Recent Progress in Spintronics In these magnetoelectric multiferroics,
In the past few years, a new set of ferroelectric order develops upon a magnetic
magnetoelectric multiferroics such as TbMnO3 phase transition into a spiral magnetic ordered
and Ni3V2O8 has been discovered and it is phase. In addition, these systems show large
under intense research in the field of magnetoelectric effects accompanied by
spintronics for the potential novel applications metamagnetic transitions. Non-collinear spiral
as discussed below [40]. Researchers are now magnetism is the key to understand the
trying to use non-equilibrium thin film growth magnetoelectric properties in these systems.
techniques to develop new materials for The reported studies [40] presented here indicate
Spintronics applications and to perform that spiral magnets are promising candidates
detailed characterization to understand the for magnetoelectrics showing large magneto
correlation between the structural, magnetic, electric effects at low magnetic fields.
and electronic properties of materials such as
complex oxides and diluted magnetic Magnetic and ferroelectric properties of
semiconductors. TbMnO3
TbMnO3 is an example of magnetoelectric
The complex oxides (e.g. perovskites) have multiferroics that exhibit large magnetoelectric
received renewed interest due to their novel response [88].
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, Fig- 109 Structure of TbMnO3
magnetostriction, and piezoelectricity).
Considerable research is being done to study The crystal structure of TbMnO3 is the
the interactions between layers with different orthorhombically distorted perovskite structure
ferroic properties and to explore the existence (the space group Pbnm and crystal symmetry
of new phenomena at surfaces and interfaces mmm) at room temperature, as illustrated in
Page 97 of 154
(Fig-109). The crystal symmetry has an For the magnetic structure below TN, the Mn
inversion center, and the system is nonpolar at moments are aligned along the b axis and show
room temperature, but at lower temperatures, sinusoidal order with a propagation wave
the system shows successive magnetic phase vector (0, kMn, 1) in the Pbnm orthorhombic
transitions. unit cell (Fig-111). The kMn (~0.29) is
insufficient at TN and decreases with
decreasing temperature [89, 90].
Page 98 of 154
temperature, the electric polarization also structure or elliptically modulated cycloidal
exhibits a small anomaly. spiral magnetic structure (Fig-112).
These results suggest an intimate connection
between magnetism and ferroelectricity in This spiral spin structure has also been
TbMnO3. confirmed in a similar rare-earth manganite,
Tb1−x DyxMnO3, for which the commensurate
At the lowest temperature, the magnitude of propagation wave vector (kMn = 1/3) is
electric polarization is ~ 6 to 8 × 10−4C m−2. observed at ferroelectric phase by a model-free
The spontaneous polarization of TbMnO3 is analysis via the use of single-crystal neutron
rather small as compared with that of diffraction data.
conventional perovskite ferroelectrics.
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.
Page 99 of 154
electric polarization along the c-axis (Pc) and direction of the spontaneous polarization in
the a-axis (Pa) is at 9 K and 15 K for a ferroelectric TbMnO3 can be switched by 90◦
TbMnO3 single crystal Fig- 113a and 113b. 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 application of a magnetic field along the c the application of sufficiently large magnetic
axis causes a single metamagnetic transition fields along the c axis.
above 5 T, as shown in Fig-114c. Comparison
of the M–H curves with the P–H curves (Fig- A recent neutron diffraction measurement
114f) reveals that the metamagnetic transition revealed that the suppression of ferroelectricity
gives rise to the suppression of Pc. The in a magnetic field along the c axis is related to
observed feature in the H // c configuration is the disappearance of the incommensurate
similar to that in H // ‘a’ and H // b, the effect antiferromagnetic ordering of Mn spins and the
of magnetic fields along the c axis is distinct appearance of a simple commensurate
from that along the ‘a’ and ‘b’ axes. The antiferromagnetic ordering with the (0, 1, 0)
electric polarization vanishes for all magnetic Bragg reflection. These results
crystallographic directions by the application clearly demonstrate the strong interplay
of a high magnetic field along the c axis. This between long-wavelength magnetic order and
means thatTbMnO3 loses its ferroelectricity by ferroelectricity in TbMnO3. The possible
Fig- 116 Schematic illustrations of types of magnetic structure with a long wavelength
If the spin rotation axis is perpendicular to the screw (Fig-116d) or cycloidal (Fig-116e)
propagation vector of spiral, the resulting component. These conical structures are
arrangement is termed a cycloidal spiral generally obtained by the application of weak
structure (Fig-116c). A rather more magnetic fields to screw or cycloidal spiral
complicated system is conical spiral, in which structures [40].
a ferromagnetic component coexists with a
In recent years there has been an extensive A ZnO based DMS would be very promising
research towards introducing ferromagnetic because of its widespread applications in
property at room temperature in electronic devices, such as transparent
semiconductors to realize new class of conductors, gas sensors, varistors, surface
spintronic devices such as spin valves, acoustic wave devices, optical wave guides,
transistors, spin light emitting diodes, magnetic acousto-optic modulators/deflectors, ultra
sensors, non-volatile memory, logic devices, violet laser source, and detectors [114]. Out of
optical isolators and ultra-fast optical switches. all the transition metals (TM), the doping of
The potential advantages of spintronic devices Mn in ZnO is most favorable because Mn has
will be higher speed, greater efficiency, and the highest possible magnetic moment [115] and
better stability, in addition to the low energy also the first half of the d-band is full, creating
required to flip a spin [105]. a stable fully polarized state.
Most of the past work on DMS has focused on The theoretical studies on Mn doped ZnO also
(Ga,Mn)As and (In,Mn)As. But the highest proved its novelties in the fabrication of room
reported Curie Temperature (Tc) in the single temperature spintronic devices. A Tc higher
phase samples grown by MBE range from ~ 35 than 300 K for p-type ZnO has been predicted
to 172 K [108, 109]. theoretically, but this has not been
experimented. Moreover, Mn is known to be
This search for a room temperature antiferromagnetic [116], which makes this
ferromagnetic Semiconductor, gained system more clean in terms of metal precipitate
momentum, following a theoretical prediction induced ferromagnetism, which is the subject
by Dietl et al., that ZnO and GaN would of great controversies in DMS.
exhibit ferromagnetism above room
temperature on doping with Mn, provided that Despite uncertainty in the mechanism of
the hole density is sufficiently high [110]. ferromagnetism in doped semiconductors, and
Where S(r) and s(r) are respectively the Mn SnO2 based DMS
and hole spin densities. The coupling J(r) SnO2 is ‘n-type’ semiconductor with a wide
between Mn local moments and hole spins can, band gap of ~3.6 eV which has its application
in principle, be ferromagnetic (J < 0) or as a transparent conducting electrode in solar
antiferromagnetic (J > 0), but the effective cells [129] and gas sensors. It has a rutile
interaction between the Mn local moments structure with octahedral coordination similar
mediated by the holes (through HM) is always to anatase TiO2. Large n-type carrier
ferromagnetic. The magnitude of J must come concentration up to 1021 cm-3 can be achieved
from a first principles band structure by antimony doping. The effective electron
calculation or from experiments. mass is quite large ~0.3me. These
characteristics are important for strong
Oxide based DMS magnetic exchange interactions in terms of
Compared to non-oxide semiconductors, the carrier induced magnetism. Epitaxial films of
oxide semiconductors have many advantages. Mn doped rutile-SnO2 were fabricated by PLD.
Their wide band gap makes them transparent
and also suitable for applications with short Co doped ZnO
wavelength. They can be easily grown at low ZnO based DMS have wide band (3.3eV) gap,
temperature even on a plastic substrate and are and large excitation energy (60meV) [131, 132]. It
ecologically safe and durable besides being is a well-known piezoelectric and electro-optic
low in cost. In addition, strong material, and can be easily deposited in thin
electronegativity of oxygen is expected to film form. It has wide applications in
produce strong p-d exchange coupling between electronic devices such as transparent
band carriers and localized spins, a prerequisite conductors, thin film gas sensors, varistors,
for DMS [128]. Summarized below are some of surface acoustic wave (SAW) devices, optical
the reports on oxide semiconductor based wave-guides, acousto-optic modulators /
DMS. deflectors, ultraviolet LASER sources, and
ultraviolet detectors [113]. It is n-type
TiO2 based DMS semiconductor with the room temperature hall
mobility in ZnO single crystals in the order of
TiO2 has been widely studied for its unique
200cm2V-1s-1.
physical and chemical properties like high
refractive index, optical transmittance in the
Electron doping via defects originates from Zn
visible and near-infrared region, high dielectric
interstitials in the ZnO lattice. The intrinsic
constant and photo catalysis for water
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]
.
Electrostrictive effect –
Quadratic effect, present for all materials
Piezoelectric coefficient
8.63 Ferroelectrics
d33=2ε33Q33P3
d31=2ε33Q13P3
d15=2ε11Q44P3
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 ↓
Fig-134 OP- and IP-PFM images of (001) BFO/SRO/STO films after switching with schematics showing the three
possible switching mechanisms.
o Detailed transmission electron microscopy to analyze the cation composition and see a
studies of both planar and cross sections of Bi:Fe ratio of 1:1 in the films.
the samples of thickness from 30nm, 90nm,
100nm and 120nm of BFO thin films However, the oxygen stoichiometry is difficult
grown on 001 STO substrates, did not to determine exactly so they have assumed the
reveal any second phases. nominal oxygen composition to describe the
film (ie- BiFeO3). Such notation does not
o Piezo imaging with an atomic force imply that the films are free of point defects,
microscope (AFM) has clearly shown the including vacancies, interstitials, or anti-site
existence of piezoelectricity down to at defects.
least 30-nm thickness, although the degree
of leakage goes up with decreasing They have been using X-ray absorption
thickness. spectroscopy (XAS) and X-ray magnetic
circular dichroism (XMCD) to understand the
o X-ray diffraction studies have revealed no origin of higher moments in the thin films.
secondary phases.
The measurements shown in Fig-138(a) was
o They have used Rutherford backscattering derived with a magnetic field of 800 Oe.
and energy dispersive x-ray spectroscopy XMCD results from the same series of films
that were used to obtain the structural and
In Fig-138(b), the normalized XMCD The presence of Fe2+ in the films suggests the
spectrum of the 30-nm BFO film to that of a origination as discussed below
Fe3O4 film is compared and several key points One possibility is a ferrimagnetic arrangement
that emerge from this comparison are in which the moments of the Fe2+ ions are
discussed below. aligned oppositely to those of the Fe3+ ions,
o First, using the Fe3O4 spectrum as a leading to a net magnetic moment. Eerenstein
fingerprint, it is clearly identified that the et al. [163] suggest that an oxygen count of 2.75
peak at 709.5 eV as the Fe2+ peak, is (instead of 3) would be required to produce our
consistent with our X-ray photoelectron experimentally observed moment of 0.5µB/Fe.
spectroscopy results. This would be the case for high-spin Fe2+, but
o Second, this peak progressively vanishes as the oxygen deficiency required to produce the
the thickness is increased (Fig-138a). observed moment would be much lower if
o Third, the total intensity of the spectrum low-spin Fe2+ were present.
from the 30nm BFO film is approximately
15% of the Fe3O4 film, which suggests that But on the contrary, Wang et al suggests that
such a ferrimagnetic arrangement may be
The out-of-plane lattice parameter for the BFO prior studies, the recently grown epitaxial BFO
layer progressively increases as the thickness is thin films showed a large spontaneous
decreased, consistent with the expected effect polarization.
of epitaxial constraint. In contrast to all their
o The second coupling mechanism of interest Recent report of experimental work carried out
is based on a classic exchange coupling by the researchers to explore the multiferroic
interaction [167] that arises at the interface nature of epitaxially strained BFO thin films
between a ferromagnet and an are discussed below. High-quality epitaxial
antiferromagnet (Fig- 140b). BFO films have been prepared by pulsed laser
Researchers have used such heterostructures to deposition (PLD) [168, 169], radiofrequency
tune the properties of ferromagnets for over sputtering [160] metal-organic chemical vapor
five decades. With the addition of a deposition [160], and chemical solution
multiferroic antiferromagnet, we can control deposition on various substrates [167], including
the state of the antiferromagnet electrically and STO, DSO, and LaAlO3, with various
thereby indirectly control the state of the conducting-oxide electrodes such as SRO, (La,
ferromagnet by completing the bottom leg of Sr) MnO3, and LaNiO3.
the coupling triangle in (Fig-140a). Thus the
combination of magnetoelectric coupling in a Transmission electron microscopy (TEM) was
multiferroic and exchange coupling between used to identify the presence of a highly
magnetic materials offers a new approach for coherent and smooth interface between BFO
the electrical control of magnetism. and the electrode layer and the relevant TEM
image is shown in Fig-141(a). Substrate and
9.18 Epitaxial Strain - RSM film thickness can be varied to study epitaxial
Epitaxial Strain induces modification of strain effects in BFO. The out-of-plane lattice
various physical properties in BFO thin films, parameter is shown in Fig-141(b) as a function
when compared to the bulk. Recently Wang et of BFO film thickness on both STO and DSO
al. [157] reported an enhancement of the room- substrates.
temperature spontaneous polarization in
epitaxially compressed strained thin films of It has been observed that because of the lattice
the ferroelectric compound BiFeO3. mismatch between BFO and STO, the BFO
lattice is compressed in the in-plane direction
The crystal structure of these films was found and elongated in the out-of-plane direction;
to be monoclinic, in contrast to that of the bulk this strain gradually decreases with increasing
material which is rhombohedral. The effect of film thickness. Films thinner than ~30 nm, the
Fig-144 Schematic of vicinal STO substrates and the corresponding BFO domain structure and polarization variants
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.