Ferroelectricity

Introduction:
Ferroelectric, Peizoelectric and Pyroelectric ceramics are new class of dielectric materials.

Ferroelectric effect was first observed by Roger Valasek in the year 1921, and they constitute
a very important group of dielectrics.

For many years the discovery was not raised to an excitement and has no applications. After
few decades, technological interest led to much more extensive studies for better
understanding.

Materials that exhibit dielectric polarization, even in the absence of electric field are known
as Ferroelectric materials. They are anisotropic crystals that exhibit spontaneous polarization.

Spontaneous Polarization: It is the dielectric polarization, which occurs under the action of
the internal processes without application of an electric field.

Minor deviation from crystallographic symmetry or some inherent asymmetry in the crystal
structure itself is the origin for existence of spontaneous polarization.

In absence of an electric field, the centre of positive charge and the centre of negative charge
do not coincide. This results a net dipole moment which is the cause of spontaneous
polarization. In other words these polarizations do exist, because they have a pre-existing
dipoles in this material even in the absence of external electric field.

The materials are electrical analogue of ferromagnetic materials.

Ferro electricity refers to the creation of enormous value of induced dipole moment in a weak
electric field as well as existence of electric polarization even in absence of applied electric
field.

Properties of Ferroelectric materials:

Ferro electric materials can be easily polarized in weak electric field.
 They exhibit dielectric hysteresis – lagging of polarization behind the applied electric
field is called dielectric hysteresis.
 Materials possess spontaneous polarization – polarization that persists in zero electric
field.
 They possess permanent electric dipoles and internal electric field which develop
spontaneous polarization at Ferro electric Curie temperature.
 Exhibit Ferro electricity at temperature less than Curie Temperature ( T < T C ) and Para
electricity at temperature above Curie Temperature ( T > T C ).
 They exhibit domain structure as in the case of ferromagnetic materials.
 Ferroelectric materials exhibit Peizo and Pyro electricity.
 They possess very high values of dielectric constant of the order 1000 to 10,000.
𝐶
 The dielectric constant varies with temperature according to the relation 𝜖 = 𝑇−𝑇 (𝑇 >
𝐶
𝑇𝐶 ) known as Curie Weiss Law, where C is called Curie Constant and T C is known as
Curie temperature.
Dependence of Dielectric polarization on Electric field:

Generally Ferro electric materials are known as non – linear dielectrics.

When a ferro electric material is subjected to an alternating electric field,
dielectric polarization varies non linearly following hysteresis.

A ferroelectric material contains large number of domains within which all

the dipoles are in parallel orientation. In absence of electric field the net
polarization is zero due to random orientation of domains.

When an applied electric field is increased slowly the favourably oriented

domain grow in size and unfavourable oriented domain sinks in size.
Ultimately at the end of the process all the domains will have parallel
orientation or whole material can be imagined to be a single domain. The direction of the dipole
moment in that domain may or may not be in the direction of applied field. In such case if the
field is increased slightly then the direction of dipole moment gets oriented in to the direction of
applied field. The polarization reaches maximum value called saturation polarization. There will
be no further change in polarization even the field is increased further.
Thus the polarization first rises rapidly with applied field to a value above which the dependence
is linear and reaches saturation Ps.
On subsequently reducing the field to zero, remanent (residual) polarization Pr remains. The
negative field to reduce the polarization to zero is called the coercive field and represented E c.
When cycle completes an hysteresis loop is formed, the area of which gives the loss of energy.

The hysteresis loop of a ferroelectric material changes its shape as the temperature is increased.
The height and width decrease with increase of temperature. At a certain temperature known as
ferroelectric curie temperature, the loop merges into a straight line and the ferroelectric behaviour
disappears.

Curie – Weiss Law:

The relation between electrical susceptibility and the absolute temperature of a non polar
ferroelectric material can be explained with the help of Curie – Weiss Law. It is expressed as
𝑁𝛼
𝜀𝑜 3𝑇𝐶
𝜒= 𝑁𝛼 = Here N is the number of dipoles per unit volume, 𝛼 is dipolar
1− 𝑇−𝑇𝐶
3𝜀𝑜
polarizability, TC Ferro electric transition temperature or Curie temperature

In a Ferro electric material, spontaneous alignment of electric dipoles takes place due to
mutual interaction. This is due to a local field E’ which is increased by dipole alignment in
the direction of the field. The local field E’ dominates only at temperature less than TC.
Thermal energy cannot randomize the electric dipoles due to dipole – dipole interaction and
local field.
Following the basic principles, polarization P can be expressed as
𝑃 = (𝜀𝑟′ − 1)𝜀𝑜 𝐸 ′ = 𝑁𝛼𝐸 ′
𝑃 𝛾𝑃
𝐸 ′ = 𝐸 + 3𝜀 (in case of cubic and isotropic materials ), otherwise 𝐸 ′ = 𝐸 + 3𝜀 𝛾is internal
𝑜 𝑜
𝑃 𝑃
field constant. 𝑃 = 𝑁𝛼 [𝐸 + 3𝜀 ] = 𝑁𝛼𝐸 + 𝑁𝛼 3𝜀
𝑜 𝑜
𝑁𝛼 𝑃 𝑁𝛼
𝑃 [1 − 3𝜀 ] = 𝑁𝛼𝐸 = 𝑁𝛼
𝑜 𝐸 [1− ]
3𝜀𝑜
 𝑁𝛼
𝑃 𝜀𝑜
𝜒 = 𝜀′ − 1 = =
𝜀𝑜 𝐸 [1 − 𝑁𝛼 ]
3𝜀 𝑜
𝑁𝛼
Both 𝜒 and 𝜀 ′ must approach infinity when 3𝜀 approaches 1.
𝑜
This is the condition for spontaneous polarization. At this point dipolar Polarizability is too high
𝐶
such that 𝛼 = 𝛼𝑑 = where C is Curie Constant. 𝐶 = 𝐾𝑇𝛼𝑑
𝐾𝑇
𝐶
𝑁𝛼 𝑁𝐾𝑇 𝑁𝐶 𝑁𝛼𝑑 𝑇 𝑇𝑐 𝑁𝛼𝑑
𝐶
Now at T = TC = =1 𝑇𝐶 = = → =
3𝜀𝑜 3𝜀𝑜 3𝐾𝜀𝑜 3𝜀𝑜 𝑇 3𝜀𝑜
Below TC spontaneous polarization is prevalent and dipoles tend to align.
𝑁𝛼 3𝑇𝐶
𝜀𝑜 3𝑇𝐶
𝜒= = 𝑇 =
𝑁𝛼 𝑇 𝑇 − 𝑇𝐶
1− 1− 𝐶
3𝜀𝑜 𝑇
This is known as Curie – Weiss Law:
Thus as T tends to TC susceptibility, dielectric constant and polarization tends to infinity.

Structure of BaTiO3:
The phase transitions in BaTiO3 single crystal are very interesting.
However, so far the driving force for the phase transitions is
physically unclear.
The experimental observations have demonstrated sequence
of phase transitions as follows: cubic → tetragonal →
orthorhombic → rhombohedral. For these ferroelectric phases, the
spontaneous polar directions are also accordingly changing from
the <100> axes ( along cubic edge ), to the <110> axes ( face
diagonal ), and to the <111> axes ( body diagonal ) as the
temperature decreases.

A unit cell of Bariuum titanate, shown in figure takes the shape of cubic crystal at temperature >
120oC ( Curie Temperature ). Above 120oC it
behaves like a non – ferro electric material with
zero spontaneous polarization.

Explaination:

It has centre of symmetry with Ba2+ ions located at

the corners of unit cell, the O2- ions at face centred
positions and Ti4+ ion nearly at the centre of unit
cell. The centre of positive charge and negative
charge coincides as a result no dipole moment and
also no spontaneous polarization. Material behaves
like a non – ferro electric material.
Once the temperature is reduced to a value below curie
temperature then positive and negative ions get
displaced – Ti4+ ion shifts upwards and oxygen O2- ions
shifts downwards. Consequently, a permanent ionic
dipole moment arises in each unit cell.
Strong interactions between the adjacent permanent dipoles cause all the dipoles to mutually align
in the direction within some volume of the solid. Such regions of spontaneous polarization are
known as ferro electric domains.
 Now the cubic structure changes to tetragonal with polarization in the direction <001> - c
– axis (along cubic edge ). This structure is stable in temperature range 5<T<120oC.
 When temperature is reduced below 5oC then structure now
changes to orthorhombic with polarization along the face
diagonal <110>. This structure is stable in temperature
range -90oC < T < 5oC.
 When temperature falls below -90oC the structure becomes
rhombohedral and the direction of polarization changes to
body diagonal <111>.
A sharp rise of dielectric constant can be seen at 120oC, 5oC
and -90oC

Classification of ferroelectric materials:

Ferroelectric materials may be classified into the following three groups depending
on their chemical composition and structure
a) Tartrate group - Sodium potassium Tatrate (NakC4H44H2O) - Rochella Salt
b) Dihydrogen phosphates and arsenates alkali metals - potassium di-hydrogen
phosphate - KH2PO4
c) Oxygen octahedron group- Barium Titanate BaTiO3

Tartrate group: A typical example of ferroelectric material of this group is Rochella salt
(Sodium potassium Tatrate (NakC4H44H2O). This material was the first solid known to
exhibit ferroelectric properties ( during 1920’s) . This material has unique property that it is
ferroelectric only in the temperature range extending from -18oC to 23 oC. It has two
transition regions instead of one. Spontaneous polarisation is in the order of 0.25 x 10-2 C/m2
The variation of spontaneous polarization Ps of Rochella salt with temperature is shown in the
figure 1.
Dihydrogen Phosphates and Arsenates of Alkali Metals: A typical example
of this category is potassium di – hydrogen phosphate – KH2PO4. The variation
of spontaneous polarization Ps of this material with temperature is shown in the
figure 2. Spontaneous polarisation is in the order of 4.95 x 10-2 C/m2

Oxygen Octahedron Group: The best known ferroelectric material is

barium titanate BaTiO3; The ferroelectric curie temperature is 120oC.
When the temperature is lowered through the critical temperature of
120oC, the material becomes spontaneously polarized and at the same
times the structure changes. It has two more transition temperatures one
at 5oC and -80oC where the spontaneous polarization changes its
directions. These three transition temperatures are reflected in the dielectric constant and in the
spontaneous polarization of the material, as shown in figure3. Spontaneous polarisation is in
the order of 26 x 10-2 C/m2
Few important Pervoskite Ferro electric materials:

Some of the pervoskite ferro electric materials which are very important from application point of
view are listed
Barium Titanate: It is one of the important ferro electric material which finds very good
number of industrial applications. It was the first ferro electric material developed commercially
for various applications.
In general many ferro electric materials are developed by taking Barium titanate as base or
reference. Many doped materials are added to stabilize, the capacitance value, or to enhance the
capacitance, or to reduce the temperature dependence of dielectric constant.

Barium Strontium Titanate; Ba ( Sr Ti ) O3: BST

Barium site was replaced with Strontium.
The purity of this material is very high and also very stable.
It can be obtained in thin film form, submicron and nano powder form.
They are widely used in the field of electronics and batteries.

Lead Zirconate Titanate – PZT – It is one of the world’s most widely used ceramic material,
especially in peizo electric applications.
Each unit consists of a small tetravalent metal ion (Zirconium in a lattice of large divalent metal
ions ( Lead ).
They are physically strong , chemically inert and relatively inexpensive.
They can be easily tailored to meet the requirements of a specific purpose.
It has greater sensitivity and higher operating temperature.

Niobates:
These are another group of pervoskite ferro electric materials. KNbO3 and LINbO3 are two
important niobates.
Titanium is replaced with niobium.
These materials are important for optical waveguides mobile phones, piezoelectric sensors,
optical modulators and various other linear and non – linear optical applications.

Applications:
• Ferroelectric thin films have attracted attention for applications in many electronic and
electro – optical devices
• Applications of ferro electric thin film utilizes the unique dielectric, peizo electric, pyro
electric and electro – optical properties of ferro electric materials
• Some of the most important electronic applications of ferro electric thinfilms includes,
non volataile memories, thin film capacitors, surface acoustic wave (SAW ) substrate
• SRAM and DRAM are volatile. EEPROM and CMOS require a battery backup and are
very costly. Ferroelectric Random Access Memory is non-volatile as well as cheaper.
FRAM is reliable as well.
• A waveguide is a device which controls the propagation of light within the device. It
carries the electromagnetic wave. The material used inside a waveguide is
a Ferroelectric Material
• Latest optical memory displays technologies are devised using the Ferroelectric
Material. PLZT is most preferred Ferroelectric Material for this purpose.
• The Ferroelectric Material is used in pressure sensors. These pressure sensors are also
termed as displacement transducers.