Ferromagn

etism

Ferromagnetism
The atomic moments in these materials exhibit very
strong interactions, resulting in a parallel or
antiparallel alignment of atomic moments.
Exchange forces are very large, equivalent to a field
on the order of 1000 Tesla, or approximately a 100
million times the strength of the earth's field.
The exchange force is a quantum mechanical
phenomenon due to the relative orientation of the
spins of two electron.

Ferromagnetism
Ferromagnetic materials exhibit parallel
alignment of moments resulting in large
net magnetization even in the absence of a
magnetic field.
The elements Fe, Ni, and Co and many of
their alloys are typical ferromagnetic
materials.
Two
distinct
characteristics
of
ferromagnetic materials are their (1)
spontaneous magnetization and the
existence of (2) magnetic ordering
temperature

Ferromagnetism

Origin of Ferromagnetism
Hunds rule

Fe: [Ar]3d64s2

Ferromagnetism

Ferromagnetic transition metals: Fe, Co, Ni

i) Magnitude of Ms
ii) Way to reach Ms
M (ferro) >> M (para) : 1700 emu/cm3 for Fe >> 10-3 emu/cm3
Hs = 50 Oe

Weiss' Assumption
Molecular field is acting in FM not only above Tc
but also below Tc and this field is so strong that it
could magnetize the substance to saturation even in
the absence of an applied field. spontaneously
magnetized (Self-saturating)
Magnetic domain : In demagnetized state, a
ferromagnetic material is divided into a number of
small regions called domains, each of which is
spontaneously magnetized.

Magnetization process

a) Unmagnetized specimen for random orientation of domains

b) c) Single domain process (motion of domain wall)
d) Rotation of the domain along the field
Question:

Spontaneous magnetization?
Division into domains?

Magnetic Domain

Ms

(a)

Ms

(b)

Ms

(c)

(a) A single-domain sample with a large stray field. (b) A sample split into two domains in
order to reduce the magnetostatic energy. (c) A sample divided into four domains. The
closure domains at the ends of the sample make the magnetostatic energy zero.

Magnetic Domain

Domain wall motion

Barkhausen
effect

Magnetic Order

Are

ferromagnets

already in an ordered
state

before

magnetic

field

a
is

applied or is the order

by the field?

Explanation of magnetic order in ferromagnets

Weber (1852): The material could already have
small atomic magnetic moments within the solid
which are randomly aligned in the demagnetized but
which became ordered under the action of a magnetic
field.
Poisson (1983) : The atomic magnetic moments may
not exist at all in the demagnetized state but could
be induced by a mangetic field.

Explanation of magnetic order in ferromagnets

Ampre (1827): The origin of the atomic moments
was suggested that they were due to electrical
currents continually circulating within the atom.

Ewing (1893): Followed Webers idea and interested

in explaining hysteresis.

Weiss domain theory

Atomic magnetic moments

were in permanent

existence (Webers hypothesis)

Atomic magnetic moments were ordered even in the
demagnetized state. It was the domains only which
were randomly aligned in the demagnetized state.
The magnetization process consisting of reorienting
the domains so that more domains were aligned with
field.

Magnetic Domain
In order to minimize its magnetostatic energy, the
magnetic material divides up into magnetic domains.
Weiss (1907): concept of magnetic domains. A
magnetic material consisted of a number of distinct
regions termed domains each of which was saturated in
a different direction.
The concept of domains is able to explain why
ferromagnetic materials can be demagnetized even
below their Curie temperature.

Weiss Mean Field Theory

What is the origin of the alignment of the
atomic magnetic moments?
It is the Weiss mean field (later the molecular
field, further later exchange coupling from
quantum mechanics)

Curie-Weiss Law
Curie's law: Individual carrier of magnetic moment (atoms or
molecules) do not interact with one another
Curie-Weiss law:
Under the consideration of interaction between electrons
Fictitious internal field Hm (molecular field) for interaction

H m M

: molecular field constant

Ht H Hm
M
n 2
C

H 3kT T
M
C

( H M ) T
M
C
C

H T C T

CH
M
T C

Molecular field theory

Pierre Weiss introduced molecular field concept.
Interaction between magnetic moments Fictitious internal
filed

C
H m M
For > 0,

: molecular field constant

H tot H a H m H aM
Hm || M

Curie Temperature

Curie Temperature
Even though electronic exchange forces in ferromagnets
are very large, thermal energy eventually overcomes
the exchange and produces a randomizing effect.
This occurs at a particular temperature called the Curie
temperature (TC).
Below the Curie temperature, the ferromagnet is
ordered and above it, disordered.
The saturation magnetization goes to zero at the Curie
temperature.

Curie temperature

Saturation magnetization of Fe, Co, Ni

as a function of temperature

Exchange Energy
Exchange force depends on relative orientation of spins of two
electrons due to Pauli's exclusion principle
When two atoms, such as hydrogen atoms, are coming
together, there are electrostatic attractive (e-p+) and
repulsive (e-e-, p+p+) forces and exchange force.
The internal field is produced by interactions between nearestneighbor dipole moments.
The interaction arises from the electrostatic electron-electron
interaction, and is called the exchange interaction or
exchange force.

Exchange Energy: Heisenberg Model

Eex 2 J ex S i S j 2 J ex Si S j cos
SiSj: spin angular momentum
Je : a numerical quantity called exchange integral

Relative orientation of two spins determines the energy states.

(1) If Jex is positive, Eex is a minimum
when the spins are parallel, leading
to ferromagnetism
(2) If Jex is negative, Eex is a minimum
when the spins are antiparallel,
leading to antiferromagnetism.

Bethe-Slater curve

ra/r3d

Band Theory of Ferromagnetism

A simple extension of the band theory of
paramagnetism by the introduction of an
exchange coupling between the electrons.
Source of magnetic moments: unpaired electrons
In partially filled energy band, an imbalance of
spins leads to a net magnetic moment per atom.

Band Theory
When N atoms come together
to form a solid, each level of
the free atom must split into N
levels.

In transition metal elements, the

outermost electrons are the 3d
and 4s; these electron clouds
are the first to overlap as the
atoms are brought together, and
the corresponding levels are the
first to split.

Density of states

AntiFerromagn
etism

Anti-ferromagnetism
If the A and B sublattice moments are exactly equal
but opposite, the net moment is zero. This type of
magnetic ordering is called antiferromagnetism.
The clue to antiferromagnetism is the behavior of
susceptibility above a critical temperature, called the
Nel temperature (TN).
Above TN, the susceptibility obeys the Curie-Weiss
law for paramagnets but with a negative intercept
indicating negative exchange interactions.

Wess Model on Anti-ferromagnetism

Two identical sublattices A and B: While the
interaction with the moments on other sublattices
with a negative coupling coefficient, interaction
with the moments on their own sublattice with a
positive coupling coefficient

On the basis of nearest-neighbor interactions,

with a negative interaction between nearest
neighbors, this leads to simple antiferromagnetism

Anti-ferromagnetism

Electrical Insulator
(no free electron)
Molecular field theory

BCC crystal (Cr)

Anti-ferromagnetism

TN : Nel temperature
T < TN : AF state
T > TN : paramagnetic
C

T ( )

Anti-ferromagnetism

Ferrimagn
etism

Ferrimagnetism
In ferrimagnets, the magnetic moments of the A and
B sublattices are not equal and result in a net
magnetic moment.
Ferrimagnetism
is
therefore
similar
to
ferromagnetism. It exhibits all the hallmarks of
ferromagnetic behavior- spontaneous magnetization,
Curie temperatures, hysteresis, and remanence.
However, ferro- and ferrimagnets have very different
magnetic ordering.

Ferrimagnetism
Two groups of ferrites depending on their structure
1. Cubic :
General formula : MOFe2O3 where M is a divalent

metal ion (Mn, Ni, Fe, Co, Mg, ...)

CoOFe2O3 is magnetically hard, but all the other cubic
ferrites are magnetically soft.
magnetite : Fe3O4 = FeOFe2O3 : oldest ferrite
(lodestone, iron ferrite)
2. Hexagonal :
Barium ferrite (BaO6Fe2O3) is magnetically hard

Cubic ferrites (Spinel

structure)

MOFe2O3: M = Mn, Ni, Fe, Co, Mg, etc.

In the unit cell, total 56 ions (8 M2+ ions, 16 Fe3+ ions, 32
O2- ions)
64 tetrahedral A site / 8 = 8
32 octahedral B site / 2 = 16
Normal Spinel : 8 M2+ in A, 16 Fe3+ in B
Inverse Spinel : 8 Fe3+ in A, 8 M2+ + 8 Fe3+ in B
Intermediate structure : Nor perfectly normal or inverse
structure
MnO Fe2O3 (80% on A, 20% on B)
MgO Fe2O3 (10% on A, 90% on B)
Most commercial ferrites : a mixed ferrite like (Ni, Zn)O
Fe2O3

Hexagonal Ferrites
MO6Fe2O3(= BaFe12O19) where M = Ba, Sr
Calculated saturation magnetization
= 20B/molecule (experimental)
Other oxides
BaO2MO8Fe2O3

2(BaO2MO3Fe2O3)

3BaO2MO12Fe2O3)

where, M is a divalent ion

Other Ferrites
-Fe2O3 : tetragonal
(calculated net moment/molecule = 2.5B
2.39B experimental)
Garnets : 3M2O3 5Fe2O3 (M = Y or RE)
Alloys : Mn2Sb, Mn3Ga, Mn3Ge2, Mn3In, FeGe2, FeSe,
Cr3As2, CrPt3,
RECo5 (RE: Gd, Tb, Dy, Ho, Eu, or Tm)

Crystal structure

FeOFe2O3 (Iron ferrite)

Magnetite is a well known ferrimagnetic material. Indeed, magnetite

was considered a ferromagnet until Nel in the 1940's, provided the
theoretical framework for understanding ferrimagnetism.

Tetrahedral site:Fe ion is surrounded by four oxygens

Octahedral site:Fe ion is surrounded by six oxygens

Magnetite Fe3O4

Magnetite (Fe3O4) has a very high Curie temperature (850 C), but
shows complex magnetic behavior. For this reason it seems to be a
promising candidate for a high spin polarization degree near
100% even at room temperature.

Magnetite Fe3O4

Differences with Ferromagnetism

Smaller s/0 than that for Fe

Curie-Weiss behavior above Tc is not obeyed (Non-linear)
NiO Fe2O3 :
Expected to have 12 B if ferromagnetic
Experiment: 2.3 B (56 emu/g) at 0 K

Spontaneous magnetizations

Spontaneous magnetizations of the A and B sublattices and the resultant s

Kinds of Magnetism
Diamagnetism
Paramagnetism
Non-cooperative
(statistical) behavior

Ferromagnetism
Antiferromagnetism
Ferrimagnetism
Cooperative behavior

Classification of magnetic materials