Lectura 3 Piezoelectric Materials

DoITPoMS Teaching and Learning Packages
Piezoelectric Materials
This teaching and learning package (TLP) provides an introduction to piezoelectric materials.
• Aims
• Before you start
• Introduction
• The piezoelectric dipole moment
• Polarisation
• Atomic basis of non-spontaneously polarized piezoelectrics
• Spontaneously polarized piezoelectrics (on the atomic scale)
• Spontaneously polarized piezoelectrics (on the macro scale)
• Depolarization
• Applications of piezoelectric materials
• PZT
• Summary
• Questions
Going further
Aims
On completion of this tutorial you should:
• Understand the atomic basis for piezoelectricity.

• Understand how this basis scales up to a full effect on the macro scale.
• Understand how piezoelectrics tie in with ferroelectrics and how their
properties arise from the same basis.
• Understand how the properties of piezoelectrics are put to use both
industrially and commercially.
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 TLPs on Atomic Scale
Structure Of Materials and also Ferroelectrics before you start this TLP.
Introduction
The direct piezoelectric effect was originally discovered in 1880 by Jacques and
Pierre Curie. They did not come into widespread use until the first world war,
when quartz was used in SONAR. This was replaced in the second world war by
Barium Titanate, and this has become one of the most important piezoelectric
materials in the world. They are both now commonly used in many ways.
© University of Cambridge
DoITPoMS, Department of Materials Science and Metallurgy, University of Cambridge
Information provided by doitpoms@msm.cam.ac.uk
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The piezoelectric dipole moment

When a piezoelectric is placed under a mechanical stress, the atomic structure of
the crystal changes, such that ions in the structure separate, and a dipole
moment is formed. For a net polarisation to develop, the dipole formed must not
be cancelled out by other dipoles in the unit cell. To do this, the piezoelectric
atomic structure must be non-centrosymmetric, i.e. there must be no centre of
symmetry. Materials which are centrosymmetric, when placed under stress,
experience symmetrical movement of ions, meaning there isn't a net polarisation.
This can be seen in the following picture, in which there is an atom in a
tetrahedral interstice. This material is ZnS, sphalerite, a Zn f.c.c. structure, which
has an S atom in half of the tetrahedral interstices.
Locally, in each interstice, there is no centre of symmetry, so when a stress is

applied, the motion of the central atom results in a dipole moment. Consider a
single tetrahedra:
2
When the central atom moves, a dipole moment forms:
See the section on The dipole moment in the Ferroelectric Materials TLP for
more information on the associated mathematics.
Polarisation
The polarisation is defined as the dipole moment per unit volume:
In a piezoelectric which is not ferroelectric, there is no spontaneous polarisation.

An applied stress therefore, will generate a polarisation in every unit cell of the
crystal, assuming the crystal is homogenous. This polarisation is therefore the
same throughout the crystal, and will cause a charge to be developed on the
surfaces of the piezoelectric, due to the large number of small charges moving. If
the piezoelectric is placed in a closed circuit and subjected to a stress, then a
current will be recorded, produced by the movement of charge from one face of
the crystal to another.
The polarisation can be described as the charge per unit area developed on the
surface, as by the equation:
This polarisation is directly proportional to the stress applied, as described by the

equation:
3
where P = polarisation, d = piezoelectric coefficient, σ = stress.
However, while this is a direct effect, the stress can be multi-axial, so d can be an
array of coefficients. (Also called a 3rd rank tensor .)
The reverse effect can also be seen if an electric field is applied to a

piezoelectric. In a reverse process to the movement of atoms causing a dipole
moment, the application of an electric field causes a dipole moment to be created
in order to oppose the field. This dipole moment is created by the motion of
atoms. This may result in the contraction or expansion of the unit cell. As this
occurs throughout the crystal, there is a large change overall, which changes the
shape of the crystal. (It must be noted however, that as there are a very large
number of unit cells in the typical crystal, the actual shape change is small. The
maximum strain usually seen is about 0.1%.)
This effect is described by the equation:
where ε = strain, d = piezoelectric coefficient, E = electric field.
4
Tensile Stress Tensile Stress
Atomic basis of non-spontaneously polarised piezoelectrics

Consider quartz, SiO2. In its non-stressed state, the ions are in positions which
do not allow any net dipole moment to be formed.
The structure of quartz is shown below:
5
In quartz, there are tetrahedra of O atoms around Si atoms, which are able to
twist and change shape when a stress is applied. The change in their position
leads to the formation of net dipole moments as seen in the piezoelectric dipole
moment section.
A tetrahedra of O atoms around a Si atom is marked within the quartz structure

below:
The dipole moment appears in every unit cell in the crystal and causes
polarisation.
6
Spontaneously polarised piezoelectrics (on the atomic scale)

Ferroelectrics are spontaneously polarised, but are also piezoelectric, in that their
polarisation changes under the influence of a stress.This is because while all
ferroelectrics are piezoelectric, not all piezoelectrics are ferroelectric.
This relationship can be viewed as:
Pyroelectrics are materials which typically experience a decrease in polarisation

when their temperature is increased. They will not be considered in this TLP but
a short aside on pyroelectrics can be found in the Ferroelectric Materials TLP.
The piezoelectric effect in ferroelectrics is very dependent on its atomic structure.

Depending on the orientation of a crystal, applying a compressive stress can
increase or decrease the polarisation, or sometimes, have no effect at all.
To illustrate this, consider the tetragonal phase of BaTiO3, which is commonly

seen at room temperature:
7
It possesses a spontaneous polarisation, Below 120°C this unit cell becomes

formed by the dipole moment in each unit tetragonal, and gains a spontaneous dipole
cell. To make it simple, we will only moment:
consider a single unit cell first. Consider
the unit cell of BaTiO3:
If the material is compressed along the x-

Compressed along the z-axis, the dipole
axis, the important charged ions move
moment decreases as the ions move
further from their original positions, giving
towards their original position.
a higher dipole moment.
This shows how polarisation can easily arise on the atomic level.
8
Spontaneously polarised piezoelectrics (on the macro scale)

Now, ferroelectric materials possess multiple domains. For background on this,
read the TLP on Ferroelectric Materials.
To make it simple, we will only consider single crystal ferroelectrics. These, when
first made, have domains of the form:
If a mechanical stress is applied to the ferroelectric, then there are domains

which will experience an increase in dipole moment and some which will
experience a decrease in dipole moment. Overall, there is no net increase in
polarisation. This makes BaTiO3 useless as a piezoelectric unless it is put
through some additional processing. This process is called poling. An electric
field is applied to the ferroelectric as it passes through its Curie temperature, so
as its spontaneous polarisation develops, it is aligned in a single direction:
All of the domains in the piezoelectric have a dipole moment pointing in the same
direction, so there is a net spontaneous polarisation. Now, when a mechanical
stress is applied, the polarisation will increase:
9
or decrease:
but still remain pointing in the original direction. This makes ferroelectrics into
useful piezoelectrics.
10
Depolarisation
The poling effect turns ferroelectrics into useful piezoelectrics. However, this
means they can only be used within certain well defined limits. If piezoelectrics
are used outside of these limits, the alignment of dipoles can disappear, leading
to the depolarisation of the ferroelectric, and removing its piezoelectric
properties. This can occur in a number of ways.
1. Thermal depoling
If the material is exposed to excessive heat, such that its temperature
approaches its Curie temperature, the dipole moments regain their unaligned
state. At the Curie temperature, a ferroelectric becomes entirely unaligned. In
order to prevent this occurring, it is sensible to use piezoelectrics well below their
Curie temperature.
11
2. Electrical depoling
A strong electric field, when applied in the reverse direction to the already poled
material, will lead to depoling. If an alternating field is used to produce ultrasound
waves (see later) the field will depolarise the piezoelectric during the periods in
which it is opposing the polarisation.
12
3. Mechanical depoling
If the stress placed on a piezoelectric is too high, it is possible to immediately
depolarise the piezoelectric as the atom positions are altered. This completely
ruins its properties.
13
Applications of piezoelectric materials

Piezoelectrics are used both commercially and industrially. Commercially, their
most common use is as gas lighters. These are capable of producing a spark:
14
15
Industrially, they are mainly used for imaging, mostly in medicine. They are used
to produce ultrasound, which is used to check on unborn babies. In a non-
medicinal manner, it can be used to detect cracks.
However, this effect can be utilised, without generating the wave with the
piezoelectric. In this way, the piezoelectric is used solely as a mechanical sensor.
As it picks up a mechanical deformation, it generates a voltage, and this can be
detected, allowing them to be used as sensors.
Another very common use of piezoelectrics is in watches. A small piece of quartz

crystal is used to regulate the movement of hands, as its shape will oscillate at
some known frequency when a particular voltage is applied. This oscillation can
be translated into a very accurate timekeeping device. For more information, see
this external web page: http://electronics.howstuffworks.com/quartz-watch.htm
A final possible use is that of an actuator. If the electric field applied over a
piezoelectric is not oscillated, but instead simply applied, the change in shape of
the piezoelectric can be used to move objects. This is useful in micro-scale
positioning, as the change in shape of the piezoelectric can be measured in
microns.
For more information, see:
http://www.morganelectroceramics.com/piezo_products.html
PZT
PZT, or Lead Zirconium Titanate, Pb(ZrxTi1-x)O3, is the most widely used
piezoelectric. It has the perovskite structure, with Zr and Ti ions randomly placed
in the B sites in perovskite.
16
Its composition is varied by altering the value x. This greatly changes the
properties, giving the phase diagram below.
If the PZT is used at 50% Mol PbTiO3, then it is near the

rhombohedral/tetragonal phase boundary. This allows it to form many different
polarisation states, in the <100> and <111> directions. There are many possible
orientations for dipole moments to form, giving easy poling, and making it a
useful piezoelectric.
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Summary
We have now seen how piezoelectrics are used in everyday life, and how they
are made for this task. It is certain that they will continue to be used, in the
medical profession, and possibly more as crack detectors. To this end, we need
to continue improving them so that they can be used in more extreme conditions.
To do this will require a greater knowledge of piezoelectricity, so the field will
continue to expand in future years.
Going further
Books
• Electroceramics by A.J. Moulson and J.M. Herbert, Chapman and Hall,

1990
• Piezoelectric Ceramics edited by J. van Randeraat and R.E. Setterington,
Mullard House, 1974
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DoITPoMS Teaching and Learning Packages

• Understand the atomic basis for piezoelectricity.

Before you start

The piezoelectric dipole moment

Locally, in each interstice, there is no centre of symmetry, so when a stress is

In a piezoelectric which is not ferroelectric, there is no spontaneous polarisation.

This polarisation is directly proportional to the stress applied, as described by the

where P = polarisation, d = piezoelectric coefficient, σ = stress.

The reverse effect can also be seen if an electric field is applied to a

This effect is described by the equation:

where ε = strain, d = piezoelectric coefficient, E = electric field.

Tensile Stress Tensile Stress

Atomic basis of non-spontaneously polarised piezoelectrics

The structure of quartz is shown below:

A tetrahedra of O atoms around a Si atom is marked within the quartz structure

Spontaneously polarised piezoelectrics (on the atomic scale)

This relationship can be viewed as:

Pyroelectrics are materials which typically experience a decrease in polarisation

The piezoelectric effect in ferroelectrics is very dependent on its atomic structure.

To illustrate this, consider the tetragonal phase of BaTiO3, which is commonly

It possesses a spontaneous polarisation, Below 120°C this unit cell becomes

If the material is compressed along the x-

Spontaneously polarised piezoelectrics (on the macro scale)

If a mechanical stress is applied to the ferroelectric, then there are domains

Applications of piezoelectric materials

Another very common use of piezoelectrics is in watches. A small piece of quartz

If the PZT is used at 50% Mol PbTiO3, then it is near the

• Electroceramics by A.J. Moulson and J.M. Herbert, Chapman and Hall,

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