Materials Science UNIT 5

Materials
Science
UNIT 5
N. LAKSHMI
SYLLABUS
MAGNETIC MATERIALS (8L):
•Soft magnetic materials

•Hard magnetic materials
•Thin films- ferrites- weakly Ferrimagnetic crystals (canted
antiferromagnetics)
•Reorientation transition layered Magnetic nanoparticles
•Magnetic thin films- multilayer- DMS,GMR,CMR.
•Measurement of Particle size, density- porosity- lattice constant using X-
ray.
•Magnetic characterization using Mössbauer spectroscopy and Neutron
diffraction,
•NMR, FMR, MOKE, MCD,
•Hall Effect field measurement,
•VSM (Low and high field magnetic field and temperature).
MAGNETIC MATERIALS: Basic Concepts
Magnetic field strength H
The externally applied magnetic field, sometimes called the magnetic

field strength, is designated by H.
If the magnetic field is generated by means of a cylindrical coil (or

solenoid) consisting of N closely spaced turns, having a length l, and
carrying a current of magnitude I, then
-----------------20.1
Figure 20.3 (a) The magnetic field H as generated

by a cylindrical coil is dependent on the current I,
the number of turns N, and the coil length l,
according to Equation 20.1.
Magnetic magnetic induction (or magnetic flux density ) B
The magnetic induction, or magnetic flux density, denoted by B,

represents the magnitude of the internal field strength within a substance
that is subjected to a field of magnitude H.
The units for B are teslas [or webers per square meter, Wb/m2 ]
Figure 20.3 (b) The magnetic flux density B

within a solid material is equal to µH, where µ is
the permeability of the solid material
The magnetic field strength H and flux density B are related as:
------------------------------------------ (20.2)
Definition of relative permeability

Definition Magnetization M
SOFT MAGNETIC MATERIALS
The size and shape of the hysteresis
curve for ferromagnetic and
ferrimagnetic materials is of considerable
practical importance.
The area within a loop represents a

magnetic energy loss per unit volume of
material per magnetization–
demagnetization cycle;
This energy loss is manifested as heat

that is generated within the magnetic
specimen and is capable of raising its
temperature.
Figure 20.19 Schematic magnetization curves

for soft and hard magnetic materials.
Both ferromagnetic and ferrimagnetic materials are classified as either soft or
hard on the basis of their hysteresis characteristics.
Soft magnetic materials are used in devices that are subjected to alternating
magnetic fields and in which energy losses must be low;
One familiar example consists of transformer cores.
For this reason the relative area within the hysteresis loop must be small; it is
characteristically thin and narrow, as represented in Figure 20.19.
Consequently, a soft magnetic material must have a high initial permeability

and a low coercivity.
A material possessing these properties may reach its saturation magnetization

with a relatively low applied field
i.e., it is easily magnetized and demagnetized and still has low hysteresis energy
losses.
HARD MAGNETIC MATERIALS
THIN FILMS
When the measured value of some physical or mechanical property is

found to depend on the size of the specimen, that property is said to
exhibit a size effect.
Thus the yield stress in tension of an iron whisker 50 µm in diameter is

more than a thousand times that of the same iron in the form of a single-
crystal rod 1 cm in diameter.
On the other hand, both specimens have the same density.
In general, only structure-sensitive properties show a size effect.
INTRODUCTION TO MAGNETIC MATERIALS 2nd Ed.

Cullity and Graham, pg 359
THIN FILMS
Among magnetic properties, the saturation magnetization Ms, for
example, is independent of specimen size (upto such sizes where surface
effects can be neglected in comparison to volume).
On the other hand, the coercivity Hc shows a marked size effect.
The coercivity of elongated iron particles 150Å in diameter is some 104

times that of iron in bulk.
Size effects are seen in thin films, fine wires, and small particles.
Of these, thin films are important in computer applications, and fine

particles in permanent magnets.
INTRODUCTION TO MAGNETIC MATERIALS 2nd Ed.

Cullity and Graham, pg 359
THIN FILMS
There are two principal types of magnetic media—particulate and thin
film.
Particulate media consist of very small needle-like or acicular particles,

normally of - Fe2O3 ferrite or CrO2;
these are applied and bonded to a polymeric film (for magnetic tapes)
or to a metal or polymer disk.
During manufacture, these particles are aligned with their long axes in
a direction that parallels the direction of motion past the head (see
Figures 20.23 and 20.24).
Each particle is single domain that may be magnetized only with its
magnetic moment lying along this axis.
MSE, Callister, pg 790

THIN FILMS
Two magnetic states are possible, corresponding to the saturation

magnetization in one axial direction, and its opposite.
These two states make possible the storage of information in digital

form, as 1’s and 0’s.
In one system, a 1 is represented by a reversal in the magnetic field

direction from one small area of the storage medium to another as the
numerous acicular particles of each such region pass by the head.
A lack of reversal between adjacent regions is indicated by a 0.
MSE, Callister
THIN FILMS
Figure 20.23
Schematic representation showing
how information is stored and
retrieved using a magnetic storage
medium.
Figure 20.24
A scanning electron micrograph
showing the microstructure of a
magnetic storage disk. Needle-
shaped particles of -Fe2O3 are
oriented and embedded within an
epoxy phenolic resin.
MSE, Callister
Thin-film heterostructures : Multilayers
Magnetic multilayers are formed of alternating layers of magnetic and
nonmagnetic metal.
Heterostructures can also be made of magnetic layers in direct contact

one with another; there will be direct exchange coupling at the interface.
Indirect exchange coupling in multilayers is mediated by spin

polarization in the nonmagnetic layers, provided they are thin enough.
Dipolar interactions also play a role in coupling ferromagnetic thin

films which are not perfectly smooth.
These structures can show a variety of magnetic properties which are

not otherwise attainable.
For example, we can synthesize artificial structures for use in

electronic devices with special directional properties,
anisotropies etc.
MAGNETORESISTANCE JMD Coey
Magnetoresistance may be defined as:
Where, ρ(B) and ρ(0) are resistances in the presence and absence of
applied field B.
•The ↑ or ↓ electrons in a ferromagnet may undergo spin-flip scattering
events
•However, these spin flipping events are relatively rare compared with
normal momentum scattering events.
•An electron in a ferromagnetic 3d metal may undergo 100 or more

scattering events, before it experiences a spin flip.
•This led Mott to propose his two-current model in 1936, whereby the ↑
and ↓ conduction channels are regarded as independent, and conduct in
parallel.
•Hence σ = σ ↑ + σ↓, or in terms of resistivity

21
Multilayers: Giant magnetoresistance (GMR)
The most important property of magnetic Albert Fert, 1938–
multilayers from a practical viewpoint is
magnetoresistance.
The unexpectedly large effect dubbed giant

magnetoresistance (GMR) was discovered in an
epitaxially grown, antiferromagnetically coupled
Fe–Cr multilayer by Albert Fert and coworkers, and
independently by Peter Grünberg and coworkers in
1988.
Their discovery, which led to the development of

Peter Grünberg ,1939–
the spin-valve sensor, was recognized by the award
of the 2007 Nobel Prize in physics.
The magnitude of the GMR effect, given by the

ratio R/R, where R is the resistance change in the
field, and R is the zero-field resistance, can be some
tens of per cent. Hence the effect is ‘giant’
The decrease of resistance on
applying the field can be understood in
terms of electron scattering from
parallel and antiparallel layers
The ↑ and ↓ electron channels

conduct in parallel, but the scattering is
different for parallel and antiparallel
magnetic alignment of the layers.
If we consider only bulk scattering in

the ferromagnetic layers, the quantities
R↑ and R↓ are the resistances of the
stack for the ↑ and ↓ electrons.
When the layer-averaged mean free path for electrons of one spin direction
exceeds the multilayer period, and differs from that of the other spin
direction, GMR is observed.
Adding the contributions of the two spin channels, the net resistance in
the parallel state is given by
whereas, in the antiparallel state, each channel has the same resistance
(R↑ + R↓)/2, so
The magnetoresistance is defined as:
can be expressed in terms of the resistivity ratio α = ρ↓/ρ↑ as

Double Exchange: results in ferromagnetic interaction
Two electrons are transferred simultaneously.
one from a bridging O2− anion to the Mn IV centre and
one from a Mn III centre to the O2− anion.
The transferred electron that originates from Mn III replaces that which
was located on the O2− anion, such that their spins are identical, in
accordance with the Pauli principle.
For the ground state, the spins of all unpaired electrons at the metal
centres will then align parallel to the spin of the transferred electrons in
accordance with Hund's rules.
in double-exchange, the
interaction occurs only
when one atom has an
extra electron compared to
the other
Colossal magnetoresistance (CMR)
Colossal magnetoresistance CMR is the substantial fall in resistance
observed in the vicinity of the Curie temperature of double-exchange
materials such as La0.7Ca0.3MnO3 when they are subjected to a large
applied magnetic field.
The field aligns the partly disordered manganese moments, which

promotes electron hopping, and in turn enhances the exchange.
Such ferromagnetic mixed valence oxides, where double exchange is the

dominant ferromagnetic coupling mechanism, show enhanced negative
magnetoresistance in the vicinity of TC.
Despite the impressive magnitude of the resistance change, CMR is of

limited use because of the huge fields needed to create it.
The temperature dependence of resistivity near TC in CMR materials is

used in bolometers.
Dilute Magnetic Semiconductors (DMS)
Magnetic semiconductors are semiconductor materials that exhibit
both ferromagnetism (or a similar response) and
useful semiconductor properties.
If implemented in devices, these materials could provide a new type of

control of conduction.
Whereas traditional electronics are based on control of charge

carriers (n- or p-type), practical magnetic semiconductors would also
allow control of quantum spin state (up or down).
This would theoretically provide near-total spin polarization which is

an important property for spintronics applications, e.g. spin transistors.
These are based on traditional semiconductors, but

are doped with transition metalsi nstead of, or in addition to,
electronically active elements.
Dilute Magnetic Semiconductors (DMS)
Example : (MnxGa1−x)As
The GaAs is a p-type semiconductor with a gap εg = 1.43 eV.
Each Mn dopant introduces a hole in the As 4p band.
With substitutional Mn, the ferromagnetic semiconductor is hole-doped,

and the ↓ polarized holes in the As 4p valence band mediate a
ferromagnetic interaction among Mn ions.
Ferromagnet TC = 170K for optimal Mn-doping, i.e., x = 0.08, the

solubility limit of Mn in GaAs.
It is used with GaAs-based heterostructures (quantum wells) for spin-

electronic demonstrators.
Other possible dilute magnetic semiconductors (DMS) are GaN:Mn and

TiO2:Co.
The beginnings
Rudolf Ludwig Mössbauer

born in Munich and obtained a Ph.D. degree in physics from
the Technical Institute in Munich in 1958 (at age 29) After his
discovery he gained world recognition and moved to the United States
in 1960. He went to the California Institute of Technology. In 1961, he
was awarded the Nobel prize in physics for his 1958 discovery.
Rudolf Mössbauer, in 1958, discovered the recoil-free emission and

absorption of gamma rays by nuclei.
At the time it was thought impossible for nuclei to absorb and
emit gamma rays resonantly.
The beginnings
It was believed that due to conservation of momentum, the

emitting and absorbing nuclei would lose some of the gamma ray
energy by recoiling
Since in general the Γ line-widths are very narrow, the chance of
the Γ ray being absorbed again by another nucleus becomes almost
zero
In 1958, however, Mössbauer showed that if the absorber and
emitting atoms are embedded in a lattice the recoil due to the Γ ray
may is taken up by the entire solid, making the energy loss
negligible.
This is in fact the very essence of Mössbauer Spectroscopy: the
discovery of recoil-free nuclear resonance emission and
absorption.
Recoil
A boat in a frozen lake:

No recoil
A boat in water: when the man

tries to jump, the boat recoils :
so he cannot reach the ladder
The nature width of absorption/emission line
Heisenberg uncertainty principle:
- inaccuracy in measuring energy,

- time interval disposed to the measurement of one energy value,
- modified Planck´s constant.
Nuclear Ground state:
Nuclear Excited state:
Γ – natural width of absorption/emission line

Comparison of the atomic & nucleus fluorescence parameters: why
is it difficult to observe nuclear resonance (emission & re-absorption)
Atomic Nucleus
Selected action
fluorescence fluorescence
parameter
(in general) (57Fe isotope)
W0 [eV] ~ 10 14,4·103
τex [ns] ~ 4,5 97,0

absorbing/emitting
Γ [eV] ~ 10-7 4,5·10-9 nucleus atom ejected from
lattice (WB binding
Γ / W0 ~ 10-8 3,1·10-13  energy of atom in lattice)
WR [eV] ~ 5·10-10 1,9·10-3
WR / Γ ~ 5·10-3 4·105 momentum accepted from

absorbed/emitted photon &
transferred to crystal by
nucleus
Observation good difficult
Why has the Mössbauer effect become so
important?
the resolution possible, i.e, 1 part in 1013!

Makes this technique one of the most sensitive -
capable of detecting very small shifts in energy
this is equivalent to a
small speck of dust on the back
of an elephant or one sheet of
paper in the distance between
the Sun and the Earth
Emission-Absorption-Re-emission

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Materials

•Soft magnetic materials

The externally applied magnetic field, sometimes called the magnetic

If the magnetic field is generated by means of a cylindrical coil (or

Figure 20.3 (a) The magnetic field H as generated

The magnetic induction, or magnetic flux density, denoted by B,

Figure 20.3 (b) The magnetic flux density B

Definition of relative permeability

The area within a loop represents a

This energy loss is manifested as heat

Figure 20.19 Schematic magnetization curves

One familiar example consists of transformer cores.

Consequently, a soft magnetic material must have a high initial permeability

A material possessing these properties may reach its saturation magnetization

When the measured value of some physical or mechanical property is

Thus the yield stress in tension of an iron whisker 50 µm in diameter is

On the other hand, both specimens have the same density.

In general, only structure-sensitive properties show a size effect.

INTRODUCTION TO MAGNETIC MATERIALS 2nd Ed.

On the other hand, the coercivity Hc shows a marked size effect.

The coercivity of elongated iron particles 150Å in diameter is some 104

Of these, thin films are important in computer applications, and fine

INTRODUCTION TO MAGNETIC MATERIALS 2nd Ed.

Particulate media consist of very small needle-like or acicular particles,

MSE, Callister, pg 790

Two magnetic states are possible, corresponding to the saturation

These two states make possible the storage of information in digital

In one system, a 1 is represented by a reversal in the magnetic field

A lack of reversal between adjacent regions is indicated by a 0.

Heterostructures can also be made of magnetic layers in direct contact

Indirect exchange coupling in multilayers is mediated by spin

Dipolar interactions also play a role in coupling ferromagnetic thin

These structures can show a variety of magnetic properties which are

For example, we can synthesize artificial structures for use in

Magnetoresistance may be defined as:

•An electron in a ferromagnetic 3d metal may undergo 100 or more

•Hence σ = σ ↑ + σ↓, or in terms of resistivity

The unexpectedly large effect dubbed giant

Their discovery, which led to the development of

The magnitude of the GMR effect, given by the

The ↑ and ↓ electron channels

If we consider only bulk scattering in

The magnetoresistance is defined as:

can be expressed in terms of the resistivity ratio α = ρ↓/ρ↑ as

one from a bridging O2− anion to the Mn IV centre and

one from a Mn III centre to the O2− anion.

The field aligns the partly disordered manganese moments, which

Such ferromagnetic mixed valence oxides, where double exchange is the

Despite the impressive magnitude of the resistance change, CMR is of

The temperature dependence of resistivity near TC in CMR materials is

If implemented in devices, these materials could provide a new type of

Whereas traditional electronics are based on control of charge

This would theoretically provide near-total spin polarization which is

These are based on traditional semiconductors, but

The GaAs is a p-type semiconductor with a gap εg = 1.43 eV.

Each Mn dopant introduces a hole in the As 4p band.

With substitutional Mn, the ferromagnetic semiconductor is hole-doped,

Ferromagnet TC = 170K for optimal Mn-doping, i.e., x = 0.08, the

It is used with GaAs-based heterostructures (quantum wells) for spin-

Other possible dilute magnetic semiconductors (DMS) are GaN:Mn and

Rudolf Ludwig Mössbauer

Rudolf Mössbauer, in 1958, discovered the recoil-free emission and

It was believed that due to conservation of momentum, the