Ferroelectrics 1

Symmetry classes of Piezoelectric/Ferroelectric Materials

In general, all materials undergo a small change in dimension when subjected to an

external force, such as an applied electric field, a mechanical stress, or a change in
temperature (heat). Depending on the material structure, such a small change in
dimension may result in a change in electric polarization and hence give rise to the
occurrence of the ferroelectric, piezoelectric, or pyroelectric effects. It can be
imagined that materials exhibiting these effects must be polar and have an electrical
order, implying that they must be crystals or polycrystalline materials composed of
crystallites. A crystal or a crystallite must have a definite chemical composition, with
the molecules made up of positive ions (atoms sharing part of their valence electrons
with others) and negative ions (atoms receiving part of electrons from others)
occupying lattice sites to constitute a crystal structure lattice. The smallest repeating
unit of the lattice is called the unit cell, and the specific symmetry of the unit cell
determines whether the crystal exhibits ferroelectric, piezoelectric, pyroelectric, or
electro-optic effects. On the basis of the symmetry elements of translational position
and orientation, there are 230 space groups. Ignoring translational repetition, these
230 groups break down into 32 classes, known as the 32 point groups. Point groups
are based on orientation only. Of the 32 classes (or point groups), 11 classes are
centrosymmetric and 21 classes are noncentrosymmetric, possessing no center of
symmetry. The latter is the necessary requirement for the occurrence of
piezoelectricity. However, one of the 21 classes, though classified as the
noncentrosymmetric class, possesses other combined symmetry elements, thus
rendering no piezoelectricity. So, only 20 classes of noncentrosymmetric crystals
would exhibit piezoelectric effects. In 10 of these 20 classes, polarization can be
induced by a mechanical stress, while the other 10 classes possess spontaneous
polarization, so they are permanently polar and thus can have piezo piezoelectric as
well as pyroelectric effects. There is a subgroup within these 10 classes that possesses
spontaneous polarization and reversible polarization; this subgroup can exhibit all
three effects—ferroelectric, piezoelectric, and pyroelectric. In fact, the ferroelectric
effect is an empirical phenomenon distinct from piezoelectric and pyroelectric effects
in that it exists with a reversible polarization.

M Chaitanya Varma
Dept. of Engineering Physics,
GITAM University
Ferroelectrics 2

Ferroelectric Phenomena
Ferroelectricity is one of the most fascinating properties of dielectric solids. Materials
exhibiting ferroelectric properties must be either single crystals or polycrystalline
solids composed of crystallites; they must also possess reversible spontaneous
polarization. In this section, we shall discuss the various features of ferroelectrics, the
mechanisms responsible for the appearance of these features, and ferroelectric
materials and their applications.

General Features
The polarization induced by an externally applied field in normal dielectric materials
is very small, with the dielectric constant usually less than 100, and its effects on
other physical properties are also very small. However, there are a number of crystals
with a nonsymmetrical structure that exhibit a large polarization, with the dielectric
constant up to 105, under certain conditions. Obviously, such a large magnitude of
polarization has attracted many researchers to study it theoretically and to develop
various practical applications.

The ferroelectric effect was first observed by Valasek in 1921, in the Rochelle salt.
This has molecular formula KNaC4H4O6·4H2O. The effect was then not considered
for some time, and it wasn't until a few decades ago that they came into great use. To
be ferroelectric, a material must possess a spontaneous dipole moment that can be
switched in an applied electric field, i.e. spontaneous switchable polarisation. In a
M Chaitanya Varma
Dept. of Engineering Physics,
GITAM University
Ferroelectrics 3

ferroelectric material, there is a net permanent dipole moment, which comes from the
vector sum of dipole moments in each unit cell, Σµ. This means that it cannot exist in
a structure that has a centre of symmetry, as any dipole moment generated in one
direction would be forced by symmetry to be zero. Therefore, ferroelectrics must be
non-centrosymmetric. This is not the only requirement however. There must also be a
spontaneous local dipole moment (which typically leads to a macroscopic
polarisation, but not necessarily if there are domains that cancel completely). This
means that the central atom must be in a non-equilibrium position. Materials are
polarised along a unique crystallographic direction, in that certain atoms are displaced
along this axis, leading to a dipole moment along it. Depending on the crystal system,
there may be few or many possible axes. In a crystal, it is likely that dipole moments
of the unit cells in one region lie along a different one of the directions to the dipole
moments in another region. Each of these regions is called a domain. A domain is a
homogenous region of a ferroelectric, in which all of the dipole moments in adjacent
unit cells have the same orientation. In a newly-grown single crystal, there will be
many domains, with individual polarisations such that there is no overall polarisation.

In an electric field, E, a polarised material lowers its energy by –P.E, (where P is the
polarisation). Any dipole moments which lie parallel to the electric field are lowered
in energy, while moments that lie perpendicular to the field are higher in energy and
moments that lie anti-parallel are even higher in energy, (+P.E).

This introduces a driving force to minimise the free energy, such that all dipole
moments align with the electric field. Now consider a material which is fully
polarised, so that all of the dipole moments are aligned in the same direction. Then
apply a reversed electric field over it. New domains with a reversed polarisation
nucleate inhomogenously. The removal of the field will leave some polarisation
behind, and only when the field is reversed does the polarisation start to lessen as
new, oppositely poled domains form. The polarisation which remains after a material
has been fully polarised and then had the field removed is called the remanent
polarisation (Pr). Only after a field is applied in the opposite direction to the original
polarising field does the polarisation diminish significantly. There is a specific field
which results in zero net polarisation (d). This is called the coercive field (EC).They
grow quickly however, giving a large change of polarisation for very little electric
field. But to form an entirely reversed material, a large switching field is required.
Finally, if a sufficiently strong electric field is applied in the reverse direction, the
polarisation will reach its maximum value in the opposite direction

M Chaitanya Varma
Dept. of Engineering Physics,
GITAM University
Ferroelectrics 4

In a ferroelectric crystal the hysteresis also depends on temperature, delimited by a

transition point called the Curie temperature, Tc. At temperatures above Tc, the
crystal is no longer ferroelectric and exhibits normal dielectric behavior. Ferroelectric
materials usually, but not always, exist in a nonpolar state at temperatures above Tc,
and have anomalously high dielectric constants, especially near the Curie temperature.
Typical dielectric constant–temperature and polarization–temperature characteristics
are shown in below figure. The dielectric constant increases very rapidly to a very
high peak value at Tc. The anomalously high value of er in the neighborhood of Tc is
generally referred to as the anomalous value. At T > Tc, anomalous behavior follows
closely the Curie–Weissrelation

Typically, materials demonstrate ferroelectricity only below a certain phase transition

temperature, called the Curie temperature, Tc, and are paraelectric above this
temperature.

BaTiO3-Type Ferroelectrics

BaTiO3 belongs to the family of ABO3 Perovskite mineral (CaTiO3) structures, in

which A and B are metals. The total charge of the A and B positive ions must be +6,
and A and B must be of quite different sizes; the smaller ion, with a larger charge,
must be a transition metal. For BaTiO3, Ti is a 3d transition element and has the d
orbital for electrons to form covalent bonds with its neighbors. The radius of Ti4+ ion
is about 0.68 Å, and that of Ba2+ is about 1.35 Å. These ions form nice octahedral
cages, with the O2- ions held apart. At temperatures higher than the Curie temperature

M Chaitanya Varma
Dept. of Engineering Physics,
GITAM University
Ferroelectrics 5

(>120°C), Ti4+ stays in the cage, rattling around it to make the unit cell maintain a
symmetrical cubic structure, as shown in below figure.

However, the structure of the unit cell is temperature dependent. At a certain

transition temperature, the particular structure of the unit cell becomes unstable and
must transform to a more stable one. So, at the Curie temperature Tc, the octahedral
cages distort and the positive ions move to off-center positions. The crystal takes a
tetragonal form, resulting from the stretching of the cubic unit cells along one edge, as
shown in below figure. In fact, the Ba2+ ions shift 0.05 Å upward from their original
position in the cubic structure; Ti4+ ions shift upward by 0.1 Å, and the O2- ions
downward by 0.04 Å to form the tetragonal structure. As a result of the ion shifts, the
centroid of the positive charges no longer coincides with the centroid of the negative
charges; therefore, the unit cells become permanently polarized and behave as
permanent dipoles, leading to spontaneous polarization. The direction of the
displacement can be reversed by a sufficiently high electric field of opposite polarity.
This possibility of dipole reversal distinguishes ferroelectric materials from
nonferroelectric ones. At temperatures below Tc and between 120°C and 5°C, the
structure is tetragonal and the polar axis (i.e., the direction of the spontaneous
polarization) is along the c-axis of the unit cells, in which c > a. At about 5°C, the
tetragonal unit cells undergo a transition for a higher stability to the orthorhombic
structure, which is formed by stretching the cell along the face-diagonal direction with
the polar axis also along the same direction. This structure will remain stable for
temperatures between 5°C and -90°C. Similarly, at around -90°C, a rhombohedral
M Chaitanya Varma
Dept. of Engineering Physics,
GITAM University
Ferroelectrics 6

structure, formed by stretching the unit cell along the body-diagonal direction,
becomes preferred, as shown in below figure. The direction of spontaneous
polarization is always along the direction of the unit cell’s elongation, that is, the
stretching direction. This is also referred to as the ferroelectric polar axis. Above
120°C, barium titanate has a cubic structure. This means it is centro-symmetric and
possesses no spontaneous dipole. With no dipole the material behaves like a simple
dielectric, giving a linear polarisation.

M Chaitanya Varma
Dept. of Engineering Physics,
GITAM University