SOLID STATE PHYSICS

MODULE – 4 (PART – 2)
DIELECTRIC, FERROELECTRIC AND MAGNETIC PROPERTIES
Theory of Dielectrics
Polarization, Dielectric constant, Local Electric field, Dielectric polarizability, Polarisation from Dipole orientation,
Ferroelectric crystals, Order-disorder type of ferroelectrics, Properties of BaTiO3, Polarisation catastrophe, Displacive type
ferroelectrics, Landau theory of ferroelectric phase transitions, Ferroelectric domain, Antiferroelectricity, Piezoelectricity,
Applications of Piezoelectric Crystals,
LOCAL ELECTRIC FIELD AT A
N
 LOCAL ELECTRIC FIELD AT AN ATOM
• In dielectric solids, the atoms or molecules experience not only the external applied electric
field but also the electric field produced by the dipoles. The resultant electric field acting on
the atoms or molecules of dielectric substance is called the local field (internal field)
• Macroscopic field in (average field) in a sphere is,
4𝜋
𝑬 = 𝑬0 + 𝑬1 = 𝑬0 − 𝑷
3
Eo = field produced by fxed charges external to the body
E1= field of the surface charge denisty P on the boundary

Consider the field that acts on the atom at the center of the sphere.
• If all dipoles are parallel to the z axis and have magnitude p, the z component of the field at
the center due to all other dipoles is,

If all dipoles are equal to the dipole field at the center of the sphere is

≠𝑬
Cubic symmetry → → →

Evaluation of internal field

• Consider a dielectric be placed between the plates of a parallel plate capacitor and let there be
an imaginary spherical cavity around the atom A inside the dielectric.
• The internal field at the atom site 'A' can be made up of four components E0,E1,E2 and E3
Here
➢ E0 = field produced by fixed charges external to the body
➢ E1 = depolarization field, from a surface charge density ii . P on the outer surface of the
specimen
➢ E2 = Lorentz cavity field: field from polarization charges on inside of a spherical cavity cut
(as a mathematical fiction) out of the specimen with the reference atom as center
➢ E3 = field of atoms inside cavity

For an abitrary symmetry E2 = Lorentz cavity field (due to

charges on surface of cavity)

E3 = field of atoms inside cavity

E1 + E2 = field of body with hole.

E1 + E2 + E3= field of all other atoms at one atom.

E1 + E2 = field of body with hole.

Lorentz Field, E2

Field of Dipoles inside Cavity, E3

E3 is only field that depends on crystal structure.

For cubic crystals

Lorentz relation

Dipoles at distances greater than perhaps ten lattice constants from

the reference site make a smoothly varying contribution to this sum, a contribution which may be
replaced by two surface integrals.

➢ One surface integral is taken over the outer surface of the ellipsoidal specimen and defines E1
➢ The second surface integral defines E2 and may be taken over any interior surface that is a suitable
distance (say 50 A) from the reference site.
➢ Count in E3 any dipoles not included in the volume bounded by the inner and outer surfaces.
 FERROELECTRICS

General properties of ferroelectric materials

➢ The dielectrics show a linear relationship between polarization and applied electric field.
➢ This topic deal with dielectrics for which this relationship exhibits hysteresis effects.
➢ The dielectric behavior of these materials is in many respects analogous to the magnetic
behavior of ferromagnetic materials, they are called ferroelectric solids, or simply
ferroelectrics.
FERROELECTRIC MATERIALS ARE DIELECTRIC MATERIALS THAT ARE
SPONTANEOUSLY POLARIZED, ie , It is polarized in the absence of an external field

➢ All the dipoles are oriented in same direction in one domain

➢ But all the dipoles are randomly oriented
➢ Consider a crystal which initially has an over-all polarization equal to zero, i.e., the sum of
the vectors representing the dipole moments of the individual domains vanishes.
➢ There are favourable and unfavourable domains
➢ Favourable domains are those aligned in one direction, when field is applied. So their walls
merge into each other.
➢ If we further increase E, the unfavourable domains also starts to align in same direction .
STRUCTURAL PHASE TRANSITIONS:
• Crystals transform from one crystal structure to another as the temperature or pressure is
varied.
• For example, Hydrogen and xenon, become metallic under extreme pressure.
• Ferroelectric transitions are a subgroup of structural phase transitions, a subgroup marked by
the appearance of a spontaneous dielectric polarization in the crystal. Ferroelectrics are of
theoretical and technical interest because they often have unusually high and unusually
temperature-dependent values of the dielectric constant, the piezoelectric effect, the
pyroelectric effect, and electro-optical effects, including optical frequency doubling
FERROELECTRIC CRYSTALS :
➢ A ferroelectric crystal exhibits an electric dipole moment even in the absence of an external
electric field.
➢ Ferroelectricity usually disappears above a certain temperature called the transition
temperature. Above the transition the crystal is said to be in a para- electric state.
➢ In some crystals the ferroelectric dipole moment is not changed by an electric field of the
maximum intensity which it is possible to apply before causing electrical breakdown. In these
crystals we are often able to observe a change in the spontaneous moment when the
temperature is changed . Such crystals are called pyroelectric. Lithium niobate, LiNbO3, is
pyroelectric at room temperature.
Classification of Ferroelectric Crystals :
In Table, some of the crystals commonly
considered to be ferroelectric, along with the
transition temperature or Curie point T, at which
the crystal changes from the low-temperature
polarized state to the high-temperature
unpolarized state. Thermal motion tends to
destroy the ferroelectric order. Some ferroelectric
crystals have no Curie point because they melt
before leaving the ferroelectric phase. The table
also includes values of the spontaneous
polarization Ps.

• Ferroelectric crystals may be classified into two main groups:

➢ order- disorder or displacive
➢ The order-disorder class of ferroelectrics includes crystals with hydrogen bonds in which the
motion of the protons is related to the ferroelectric properties, as in potassium dihydrogen
phosphate and isomorphous salts. The substitution of deuterons for protons nearly doubles Tc,
although the fractional change in the molecular
weight of the compound is less than 2 percent.
➢ The displacive class of ferroelectrics includes
ionic crystal structures closely related to the
perovskite and ilmenite structures. The
simplest ferro- electric crystal is GeTe with the
sodium chloride structure. We shall devote
ourselves primarily to crystals with the
perovskite structure
 Consider the order of magnitude of the ferroelectric
effects in barium titanate: the observed saturation
polarization P, at room temperature is 8 X 104esu cm-
2
. The volume of a cell is (4 X 10-4 )3= 64 X 10-24 cm3,
so that the dipole moment of a cell is (CGS)

p =(8 X104 esu cm-2)(64 X10-24cm-3) =5x10-18 esu cm

If the positive ions Ba2+ and Ti4+ were

moved by δ = 0.1 Å with respect to the
negative 0-2 ions, the dipole moment of
a cell would be 6eδ =3 X 10-18 esu cm.
In LiNbO3 the displacements are
considerably larger, being 0.9 Å and
0.5 Å for the lithium and niobum ions respectively, giving the
larger Ps.
DISPLACIVE TRANSITIONS:

POLARIZATION CATASTROPHE:
• Polarization catastrophe occurs if an ion displaced from its equilibrium position by an
external force.
• This leads to an asymmetrical shift from the equilibrium of ion positions resulting in
permanent ion movement.
• Here the local electric field caused by the ion movement is greater than the elastic restoring
forces. Higher order restoring forces limit the shift to a finite displacement.

CONDENSATION OF TRANSVERSE OPTICAL ( TO ) PHONON:

• It happens when TO phonon frequency vanishes at some point in the Brillouin zones.
• LO phonon frequency is always greater than the TO phonon frequency.
• So, we are not concerned with LO condensation.

4𝜋𝑃
▪ In simple catastrophe theory, the local electric field at all atoms is equal to 𝐸 + in CGS
3
𝑃
unit and 𝐸 + in SI units.
3𝜀

▪ The theory now leads to second order transitions and physical idea leads to first order
transitions.
Difference between first order and second order transitions:
▪ First order: there is latent heat, order parameter is discontinuous at transition temperature.
▪ Second order: there is no latent heat, order parameter is not discontinuous at transition
temperature.
Polarization catastrophe condition:
▪ Here we have to consider the equation of dielectric constant in the CGS form,
8𝜋
1 + 3 ∑𝑗 𝑁𝑗  𝛼𝑗
𝜀=
4𝜋
1 − 3 ∑𝑗 𝑁𝑗  𝛼𝑗

Where the 𝛼𝑖 is the electronic plus ionic probability of an ion type i,Ni is the no. of ions i per unit
volume.
▪ When the applied field is zero,𝜖 tends to infinity and permits a finite polarization.
▪ From the above equation, to get dielectric constant infinity the denominator should be equal
to zero. So,
4𝜋
1− ∑ 𝑁𝑖 𝛼𝑖 = 0
3
4𝜋
∑ 𝑁𝑖 𝛼𝑖 = 1
3
 3
∑ 𝑁𝑖 𝛼𝑖 =
4𝜋
this is the condition for catastrophe.
▪ The value of 𝜀 is very sensitive to the small deviation of ∑ 𝑁𝑖 𝛼𝑖 from the critical value 3/4𝜋.
4𝜋
▪ If we write 3
∑ 𝑁𝑖 𝛼𝑖 = 1 − 3𝑠,and s<<1 then the equation of dilelectric constant ,

→
for s → 0

→
(
p
▪ Near the transition temperature, s varies linearly with temperature.

▪ So,

1
We know 𝜀 = 𝑠 , then

Here T is closer to Tc ,so it is closely approaches to paraelectric state

(where T>Tc).this is the theory of polarization catastrophe and displacive transition.