FERROELECTRICS

FERROELECTRICS

Basic principles
Outline

What is the origin of electrostatic effects from crystalline materials?

How might one classify ferroelectrics?
A tour of some examples of ferroelectric materials
An overview

Non-conducting materials may have a net electrostatic polarisation

induced by an external electric field.
Where the affects upon observable properties such as elastic, optical and
thermal behaviour is large, these materials are termed ferroelectrics.
To gain some understanding, well start with a simple model
A nave picture
A nave picture
A nave picture
A nave picture
A nave picture

The local alignment of dipoles can

exist over any length scale.
Different regions may exist with
different polarisation orientations:
Call these domains in line with
magnetic materials.
In contrast with magnetism, domain
walls are abrupt.
Applied field

Suppose we now apply an electric field, horizontal in the figure.

If it is of sufficient strength, the small ions will be able to overcome the barrier and
dipoles will switch direction
The dipoles are polarised by the applied field.
Domain walls move.
Polarisation vs. E-field

Suppose we start with a material where there are many domains which are aligned
randomly.
What is the initial polarisation?
Polarisation vs. E-field

If we apply a small electric field, such that it is not able to switch domain
alignments, then the material will behave as a normal dielectric:
P E
As E is increased, we start to flip domains and rapidly increase P.
When all domains are switched, we reach saturation.
What happens if the E-field is now removed?
Polarisation vs. E-field
The value at zero field is termed the remnant polarisation (Pr).
The value of P extrapolated back from the saturation limit is the spontaneous
polarisation. It is defined to be the magnitude of the dipole moment per unit
volume or the magnitude of the electrical charge per unit area on the surface
perpendicular to the axis of spontaneous polarisation.
Reversal of the field will eventually remove all polarisation
-The field required is the coercive field (Ec).
For a ferroelectric material coercive field is the electric field required to switch its
polarisation from its remnant polarisation (Pr) to zero polarisation [P = 0].
Further increasing the reverse field will completely reverse the polarisation, and
so a hysteresis loop is formed
Polarisation hysteresis

E
Polarisation hysteresis

E
Polarisation hysteresis

The essential feature of a ferroelectric is not that there is a

spontaneous polarisation, but that the spontaneous polarisation can
be reversed by the application of an electric field.
Curie temperature
Above a critical temperature the
spontaneous polarisation will be lost due
to one of two effects:
A change of structure such that there
is a single minimum in the energy
mid-way between sites
The rate that the small ions hop is so
high that on average there is no net
polarisation
Curie temperature

This temperature is termed the Curie temperature, Tc, in light of the analogy with the
transition temperature between ferromagnetism and paramagnetism.
Above the Curie temperature, ferroelectrics behave as non-polar dielectrics,
sometimes termed a paraelectric phase.
Some ferroelectrics do not have a Curie temperature why might this be?
Other temperature effects

In addition to the change in spontaneous polarisation, temperature affects the

dielectric constant of the material, normally defined as the rate of change of
dielectric displacement with electric field.
For ferroelectrics where there is a non-linear relationship between D and P, we use
=(D/ E)E=0
Other temperature effects

In some ferroelectrics, the temperature dependence of can be reasonably

accurately represented by the Curie-Weiss law:
= 0+C/(T-T0)
C is the Curie constant
T0 is the Curie-Weiss temperature, which in general differs from the Curie
temperature (Tc)
Close to T0 becomes very large.
In some ferroelectrics, TcT0, and the phase transition is of second order.
In others Tc is far from T0 and the phase transition is first order.
Beyond the nave model
In the model, we have picked out pairs of atoms, and attributed point
dipoles associated with the combination of their charges and
separations.
More realistically, each unit cell carries a dipole moment:
The definition allows the polarisation to be as influenced by
distortions in the electron density as it is by displacements in the
point-like ion sites.
A necessary condition for the piezoelectric effect to occur is that there
has to be a lack of a center of symmetry in the materials crystalline structure.
There are 32 classes or point groups of crystals, of which 11 have
a center of symmetry (centrosymmetric) and 21 do not have a center of
symmetry (see Fig. 9.1). When there is a lack of symmetry, the net movement
of positive and negative ions with respect to each other as a result of
stress will produce an electric dipole. When there is a centrosymmetry, the
centers of the positive and negative charges will still coincide, even after
deformation of the crystal due to stress. Of the 21 non-centrosymmetric
crystal classes, 20 are piezoelectric.
Of the 20 classes of crystals that are piezoelectric, 10 have a unique
polar axis and are called polar crystals. Even when no external stress is
being applied, those 10 classes of crystals with unique polar axes have a
permanent electric dipole moment within their unit cells and are, thus, said
to be spontaneously polarised. Spontaneous polarisation (PS) is defined to
be the magnitude of the dipole moment per unit volume or the magnitude
of the electrical charge per unit area on the surface perpendicular to the axis
of spontaneous polarisation. The magnitude of the spontaneous polarisation
depends on temperature (). The temperature dependence of spontaneous
polarisation is called the pyroelectric effect and crystals that exhibit this
property are called pyroelectrics. The pyroelectric effect is mathematically
described by the formula
PS = p
where p is the pyroelectric coefficient. Changing the temperature of a pyroelectric
changes the value of its electric dipole moment.
A subgroup of the pyroelectric classes of crystals is the ferroelectrics.
Crystal classifications
Crystallography and ferroelectrics

The crystal classification of a T Th O Td Oh

material has immediate
implications for ferroelectric C4 S4 C4h D4 C4v D2d D4h
effects D2 C2v D2h
There are 32 crystal classes
11 of them have a centre of symmetry
C2 Cs C2h
(centrosymmetric) and cannot support C1 Ci
ferroelectricity
Of the remaining 21, the O-point group C3 S6 D3 C3v D3d
(432) also excludes ferroelectricity.
The remaining 20 classes all exhibit C6 C3h C6h D6 C6v D3h D6h
the piezoelectric effect
Crystallography and ferroelectrics

The crystal classification of a T Th O Td Oh

material has immediate
implications for ferroelectric effects C4 S4 C4h D4 C4v D2d D4h
There are 32 crystal classes D2 C2v D2h
11 of them have a centre of C2 Cs C2h
symmetry (centrosymmetric) and
cannot support ferroelectricity C1 Ci
Of the remaining 21, the O-point group
(432) also excludes ferroelectricity. C3 S6 D3 C3v D3d
The remaining 20 classes all exhibit the
piezoelectric effect
C6 C3h C6h D6 C6v D3h D6h
Crystallography and ferroelectrics

The crystal classification of a

material has immediate T Th O Td Oh
implications for ferroelectric effects
There are 32 crystal classes C4 S4 C4h D4 C4v D2d D4h
11 of them have a centre of D2 C2v D2h
symmetry (centrosymmetric) and
cannot support ferroelectricity C2 Cs C2h
Of the remaining 21, the O-point C1 Ci
group (432) also excludes
ferroelectricity. C3 S6 D3 C3v D3d
The remaining 20 classes all exhibit
the piezoelectric effect C6 C3h C6h D6 C6v D3h D6h
Piezoelectric effect

The application of an electric field

induces a geometrical change.
Alternatively, a distortion of the
material induces a potential
difference.
Used in many electrical devices, e.g.
sound-to-electricity
Crystallography and ferroelectrics
The crystal classification of a
material has immediate
implications for ferroelectric
effects T Th O Td Oh
There are 32 crystal classes C4 S4 C4h D4 C4v D2d D4h
11 of them have a centre of
symmetry (centrosymmetric) D2 C2v D2h
and cannot support
ferroelectricity C2 Cs C2h
Of the remaining 21, the O- C1 Ci
point group (432) also
excludes ferroelectricity. C3 S6 D3 C3v D3d
The remaining 20 classes all
exhibit the piezoelectric effect C6 C3h C6h D6 C6v D3h D6h
Of these, 10 have a unique
polar direction.
Crystallography and ferroelectrics
Crystal classes with a unique polar axis are called polar.
The spontaneous polarisation can be seen in terms of its change with
temperature: the pyroelectric effect.
The 10 polar classes are therefore sometimes referred to as the
pyroelectric classes.
http://www.staff.ncl.ac.uk/j.p.goss/symmetry/PP_classes.html

Ferroelectric crystals must belong to the pyroelectric classes.

But Ferroelectrics must exhibit the hysteresis, so we define ferroelectric
crystals as pyroelectric crystals that exhibit reversible polarisation.
Ferroelectric Materials
A group of dielectric materials that
display spontaneous polarization. In
other words, they possess polarization
due to their crystalline structure in the
absence of an electric field.

According to M. Budimir, a crystal is

defined to be ferroelectric when it has at
least two orientation states of spontaneous
polarization in the absence of an external
electric field and can be shifted from one to
another of these states by an electric field.
 When a ferroelectric material is heated above its Curie Temp. then the
unit cell becomes cubic, all the ions assume symmetric positions
within the cubic unit cell and ferroelectric behavior ceases.

Spontaneous polarization is a result of interactions between adjacent

permanent dipoles which mutually align, all in the same direction.
Examples of Ferroelectrics
Barium Titanate, Rochelle salt, potassium dihydrogen phosphate,
potassium niobate, and lead zirconate-titanate (PZT)
Outstanding Properties
The reversibility of the permanent polarization by an electric field.
Reversibility is a result of the fact that the polar structure of a ferroelectric is a
slightly distorted nonpolar structure. The distortion gives rise to nonlinear
dielectric behavior.
Ferroelectrics have very high dielectric constants at relatively low applied
field frequencies. Capacitors made from these materials can be significantly
smaller than capacitors made out of other dielectric materials.
Classification of ferroelectrics
i. Crystal-chemical: hydrogen-bonded (e.g. KH2PO4) or otherwise (e.g.
double oxides).
ii. No. of polarisation directions: single direction (e.g. PbTa2O6), several
equivalent directions (e.g. BaTiO3).
iii. Centrosymmetric non-polar phase: E.g. Rochelle salts exhibit
piezoelectric phase above Tc, whereas BaTiO3 is centrosymmetric.
iv. First vs. second order phase change at Tc. It turns out this
corresponds to the value of the Curie constant (C), one group being of
the order of 103K, and the other 105K.

These four classifications do not necessarily coincide.

Antiferroelectrics

If the free energy of an antipolar phase is

comparable to the polar state then the
material is termed antiferroelectric.

If a material exhibits ferroelectric effects

Antipolar
in one polar direction, and
antiferroelectric effects perpendicular, it
may be termed ferrielectric.

Polar
Figure: Double hysteresis curve of an anti-ferroelectric
material.
The black curve represents the case where the electric
fields are not high enough to switch the material from
the anti-ferroelectric state to the ferroelectric state;
The red curve represents the case where the
composition of the material is closer to the phase
boundary so that the anti-ferroelectric -to- ferroelectric
switching field is lower and has a butterfly loop; and
The green curve is for the case where the composition
of the ferroelectric material is on the ferroelectric side of
the phase transition and has a typical ferroelectric loop.
(Courtesy of W. Hackenberger and E. Alberta, TRS
Technologies.)
Antiferrolectric Materials

Crystals that are isomorphous to ferroelectrics, undergo with

decreasing temperature phase transitions from a state of higher
symmetry to a state of lower symmetry which are connected with
slight distortions of the crystal lattice. This leads to twinning. However,
the twins have no net electric dipole moment. In most cases the
crystal structure of the low symmetry phase can be described in terms
of equivalent sublattices with equal but opposite polarization.
Materials in Actuators

Anti-ferroelectric films can be used for high strain microactuators

Ferroelectric liquid crystalline elastomers (FLCE) can be used for soft
actuators
Composite Polyurethane-Ferroelectric Ceramics made of PZT
Twinned lithium tetraborate is used in monomorph actuators
Many Ferroelectric thin films
Perovskites

Perovskite is a naturally occurring mineral with chemical formula

CaTiO3.
This is a prototype for many ABO3 materials which are very important
in ferroelectrics.
These materials may be envisaged by consideration of a non-polar,
cubic basic building block
Perovskites

A
Perovskites
Below the Curie temperature, these crystals undergo symmetry
lowering distortions. Well initially focus up the distortions of BaTiO3.
There are three phase transitions in order of decreasing temperature:
120oC, 5oC, and -90oC.
 Barium Titanate (BaTiO3)
A major turning point in ferroelectricity came in 1941, when it was discovered
that a number of mixed oxides, such as TiO2 and BaO, which forms barium
titanate, crystallised with a perovskite structure and exhibited unusual
dielectric properties i.e. permittivities 1000 times higher than those of any
other known ceramics at the time.
The Ba2+ ions are in the corners, they have a tetragonal symmetry. The O2-
ions are displaced below the centers of each of the six faces and the Ti4+ ion
is displaced upward from the unit cell center by the same amount.
The permanent ionic dipole moment comes from the relative displacements
of the oxygen and titanium ions from their symmetrical positions.
BaTiO3

Above 120oC BaTiO3 is cubic (non-polar)

Ti
O

Ba
BaTiO3

From 120oC down to ~5oC, there is a

distortion to a tetragonal phase.
All of the cube directions can
undergo this type of distortion: this
leads to complexity in domain
formation.
BaTiO3

From 5oC down to around -90oC the

structure is orthorhombic by dilation
along [110] directions and
contraction along [1-10].
There are 12 possible orientations.
BaTiO3

Finally the lowest temperatures yield

rhombohedra (distortions along the
body diagonal).
There are therefore 8 equivalent
distortion directions
Thank You