Ferroelectric Materials

Ferroelectrics are an important device in todays world. They are useful both as
capacitors, for example in camera flashes, or as non-volatile memory storage. The
memory use of which you are most likely to be aware is in the Playstation 2.

Aims
After completing this tutorial, you should:

Be aware of the atomic requirements for ferroelectricity.

Understand how this atomic structure leads to spontaneous polarisation, and how
this polarisation can be switched.
Understand how this polarisation leads to the interesting electrical properties
displayed by ferroelectrics.
Understand how these properties are made use of in today's technologies.

Before you start

This TLP should be fairly self-contained, but some knowledge of crystal structures is
assumed. It may be helpful to read the teaching and learning package on Atomic Scale
Structure Of Materials first.

Introduction
The ferroelectric effect was first observed by Valasek in 1921, in the Rochelle salt. This
has molecular formula KNaC4H4O64H2O. The effect was then not considered for some
time, and it wasn't until a few decades ago that they came into great use. Nowadays,
ferroelectric materials are used widely, mainly in memory applications. This TLP will
show how the ferroelectric effect arises, and how it is usefully used.

The dipole moment

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. This is
found when two particles of charge q are separated by some distance r, i.e.:

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The dipole moment, is:

= q.r

In a ferroelectric material, there is a net permanent dipole moment, which comes from
the vector sum of dipole moments in each unit cell, . 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. For example, consider an atom in a
tetrahedral interstice.

In (A) the structure is said to be non-polar. There is no displacement of the central atom,
and no net dipole moment. In (B) however, the central atom is displaced and the
structure is polar. There is now an inherent dipole moment in the structure. This results
in a polarisation.

Polarisation
Polarisation may be defined as the total dipole moment per unit volume, i.e.

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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. As it is the most common and
easy to see, let us examine a tetragonal system that forms when cooled from the high
temperature cubic phase, through the Curie temperature, of e.g. Tc=120C in BaTiO3.

In this system, the dipole moment can lie in 6 possible directions corresponding to the
original cubic axes:

In a crystal, it is likely that dipole moments of the unit cells in one region lie along a
different one of the six directions to the dipole moments in another region. Each of
these regions is called a domain, and a cross section through a crystal can look like this:

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. They often appear:

The polarisation of individual domains is organised such that +ve heads are held near -
ve tails. This leads to a reduction in stray field energy, because there are fewer isolated
heads and tails of domains. This is analogous to the strain energy reduction found in
dislocation stacking.

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Domain boundaries are arranged so that the dipole moments of individual domains meet
at either 90 or 180. In a polycrystal (one with more than one crystallographic grain),
the arrangement of domains depends on grain size. If the grains are fine (<< 1 micron),
then there is usually found to be one domain per grain. In larger grains there can be
more than one domain in each grain.

This is a micrograph showing the domains in a single grain.

This micrograph is reproduced from the DoITPoMS Micrograph Library.

In this grain, the domains are twinned in such a way as to reduce the overall stray
electric field energy. As each domain possesses its own dipole moment, we may switch
dipole moments in order to encode information.

Switching polarisation (1)

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

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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.

Let us start by considering how dipole moments may align in zero applied field:

These two moments are stable, because they sit in potential energy wells. The potential
barrier between them can be represented on a free energy diagram:

This material is considered to be homogenous. If the polarisation points left then we

have:

The electric field alters the energy profile, resulting in a tilting of the potential well:

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An increase in the electric field will result in a greater tilt, and lead to the dipole
moments switching, leading to:

Next we must look at the more realistic scenario in which domains form.

Switching polarisation (2)

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. This requires a certain amount of
time, in the same manner as any nucleation process. When the fluctuating nuclei reach a
certain critical radius, they grow outwards, forming needle-like structures. When they
reach the other side of the ferroelectric, they begin to grow outwards.

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+

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This shows the origin of the hysteresis loop. 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. 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. This is because of both defects in the crystal
structure, in a manner similar to Zener drag, and also to do with stray field energy. The
polarisation of the material goes from a coupled pattern, with 180 boundaries, to a state
in which many heads and tails are separated. This leads to the increase in stray field
energy. Therefore, to attain this state, lot of energy has to be put in by a larger field.

Here we show a how a minor hysteresis loop fits into the major loop above.

The part of curve shown fits into the major hysteresis curve.

There are three sections to this curve.

1) Reversible domain wall motion.
2) Linear growth of new domains.
3) New domains reaching the limit of their growth.

Measurement of polarisation
Polarisation may be defined as:

where Q is the charge developed on the plates (Coulombs) and A is the area of the plates
(m2).

A good ferroelectric has 10 C cm-2 < P < 100 C cm-2.

We can measure the polarisation by using the classic Sawyer-Tower circuit:

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In this experiment, the voltage is cycled by the signal generator. Its direction is reversed
at high frequency, and the voltage across the reference capacitor is measured. The
charge on the capacitor must be the same as the charge over the ferroelectric capacitor,
as they are in series. This means the charge on the ferroelectric can be found by:

where C is the capacitance of the reference capacitor, and V is the voltage measured
over this capacitor. We can therefore represent the polarisation of a material in an
oscillating electric field, by plotting the voltage applied to the material on the x-axis of
the oscilloscope, and the surface charge on the y-axis. This can be done because the
capacitance of the reference capacitor is much higher than the capacitance of the
ferroelectric, so most of the voltage lies over the ferroelectric. It is only possible to
measure P by cycling the polarisation through cycling the voltage across the
ferroelectric. We cannot measure absolute values instantaneously, but can deduce
absolute values from the changes measured when cycling the polarisation.

Fabrication of a KNO3 ferroelectric capacitor

A capacitor can be made from potassium nitrate (KNO3), which is ferroelectric below
120C. (The temperature dependence of ferroelectrics will be explained later.) The
following video clip shows the construction of a KNO3 capacitor, and the hysteresis
loop it displays. The circuit used is the standard Sawyer-Tower circuit.

The result is a hysteresis loop. This arises from the fact that a system does not respond
immediately to a given set of external conditions. Rather, there is a history dependence
and this is the basis for memory (two states are possible in E=0).

The final hysteresis loop appears like this:

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When the field is removed, the polarisation does not disappear like a dielectric. (a c).
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).
Finally, if a sufficiently strong electric field is applied in the reverse direction, the
polarisation will reach its maximum value in the opposite direction (e).
To understand how the polarisation switches we must consider domains more fully.

Temperature dependence of the Hysteresis loop

We have now seen the way in which the hysteresis loop arises. However, there are more
aspects to the hysteresis loop.

We have only observed it at one particular temperature, one at which the material is
ferroelectric. What happens if the temperature is raised? The hysteresis loop changes
with temperature, becoming sharper and thinner, and eventually disappearing, i.e.:

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As you can see, the polarisation increases at 90C, as a result of a phase transition.
Between this temperature and room temperature, the polarisation increases steadily, as a
direct relation with temperature, such that:

where p = pyroelectric coefficient (C m-2 T-1).

Why should this be?

This is a general behaviour (that does not apply to KNO3) that can arise for two reasons
depending on the material.

i. Disorder. Each unit cell has its own dipole moment, which, when there is a net
polarisation, are described as ordered. At high T, the direction of the dipole
moments randomises, giving a disordered material with no net polarisation.
ii. Phase transitions that can open up new possibilities for dipole moments to form.
In this case, there is a jump at 0C, and at 90C, where the loop becomes taller.

Barium titanate
Let us consider one of the most well-known ferroelectrics, barium titanate, (BaTiO3).

It has this perovskite structure:

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Barium titanate and phase changes
The temperature at which the spontaneous polarisation disappears is called the Curie
temperature, TC.

Above 120C, 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. TC for barium titanate is 120C.

Below 120C, it changes to a tetragonal phase, with an accompanying movement of the

atoms. The movement of Ti atoms inside the O6 octahedra may be considered to be
significantly responsible for the dipole moment:

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The cubic phase of barium titanate changes to a tetragonal phase with the lengthening of
the c lattice parameter. This is mainly associated with a movement of the Ti atom inside
O octahedra, although apical O atoms and the Ba atoms move too.

This shows the BaTiO3 structure with an O6 octahedron surrounding the important Ti
atom.

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The switching to a cubic structure is the reason for the polarisation spontaneously
disappearing above 120C. Barium titanate has two other phase transitions on cooling
further, each of which enhances the dipole moment:

The phase which is reached after cooling to ~ 0C from tetragonal is orthorhombic.

And then rhombohedral below -90C:

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All of these ferroelectric phases have a spontaneous polarisation based to a significant
extent on movement of the Ti atom in the O6 octahedra in the following way (using
pseudo-cubic notation):

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Order of phase transitions
Two common types of phase transition may be identified. These are named depending
on how the order changes during the transition. In ferroelectrics this is the polarisation,
which is called the order parameter. A first order transition is one which has a
discontinuity in the order parameter itself, while a second order transition is one which
has a discontinuity in the first derivative of the order parameter. Plots of the
spontaneous polarisation vs. temperature appear as follows.

First order Second order

In a first order transition the polarisation varies continuously, until the Curie
temperature at which there is a discontinuity. In a second order transition, the order
parameter itself is a continuous function of temperature, but there is a discontinuity in
its first derivative at TC.

Ferroelectrics - Why?
We have now seen how ferroelectrics behave and why they behave in this way. The
question to ask now is So what?. The answer is simple. Ferroelectrics are very useful
for devices and are used in many different ways today. If a ferroelectric is used in its
linear region, above TC it makes a very good capacitor, as its dielectric constant can be
very high indeed. These are often used in cameras as a way of powering a flash. A
battery slowly stores a charge on a capacitor, which when connected to a bulb, releases
a burst of high current, creating the flash.

First, the battery charges the ferroelectric capacitor and then, once fully charged, the
ferroelectric is connected to the bulb and causes it to flash.

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Ferroelectrics are also being considered as a form of non-volatile computer memory,
FeRAM (Ferroelectric Random Access Memory). Here, a ferroelectric can be in one
polarised state or another, which can act as a 0 or 1, allowing use as binary.

The two states may be distinguished by cycling the charge. They store non-volatile data,
i.e. data even when the power is switched off. However, this is not as fast as current
DRAM structures, so it is still under development, but it is actually used in e.g. the
Sony Playstation 2, because a range of considerations permit it to fulfil this role.

Summary
Ferroelectrics have now been in use for decades, but they are still an expanding field.
Their use in computing will only increase as they are miniaturised. However, to do this,
the way in which their properties vary on the microscale has to be understood, so this
will be a target for future research. Ferroelectrics will be used for a long time to come,
as their properties are unique.

Questions
Quick questions

You should be able to answer these questions without too much difficulty after studying
this TLP. If not, then you should go through it again!

1. What symmetry element must be absent for a material to be ferroelectric?

a) An axis of rotation.
b) A mirror plane.
c) A centre of symmetry.
d) An improper axis of rotation.

2. Which of these is not a correct definition of polarisation?

a) The net dipole moment per unit volume.

b) The surface charge per unit area.

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 c) The movement of atoms giving rise to a dipole moment.
d) The net charge per dipole moment.

3. Why are domains in crystals found in a manner such that their polarisation is
coupled?

To reduce stray field energy. To reduce dislocation strain energy. To grow the
crystal in a regular manner. To give small grains.

4. What is needed to make ferroelectric domains useful as a binary memory store?

a) Large domains.
b) A square hysteresis loop.
c) A large coercive field.
d) Small domains.

5. If a ferroelectric, 50mm by 10 mm, has a measured surface charge of 2.5 x 10-4

Coulombs, and a lattice parameter of 5 x 10-10, what is the dipole moment in a
single cubic unit cell?
a)
6.25 x 10-29
b)
6.25 x 10-35
c)
1.5625 x 10-35
d) 1.5625 x 10-29

6. What field has to be applied to give a ferroelectric, with a square hysteresis loop,
zero net polarisation?

a) The switching field.

b) The polarising field.
c) The coercive field.
d) The stray field.

Books

Ferroelectrics: An Introduction to the Physical Principles by J.C. Burfoot, D.

Van Nostrand Company Ltd., 1967

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