Pyroelectric Materials: Doitpoms Teaching and Learning Packages

DoITPoMS Teaching and Learning Packages
Pyroelectric Materials
Pyroelectric materials are found in almost every home, in the form of intrusion
detectors and other devices, and this TLP will consider how they work, and what
the most common ones are made of.
Aims
Before you start
Introduction
Polarisation
Variation of Polarisation with Temperature
Behaviour around the Curie point
The Direct and Indirect Effect
Example Pyroelectric Materials
Triglycine sulphate
Polyvinylidene fluoride
Application of a Pyroelectric-Infrared detection
Pollutant Control
Summary
Questions
Going further
Aims
On completion of this tutorial you should:
• Understand the difference between pyroelectrics and ferroelectrics.

• Understand the main uses of pyroelectrics.
• Understand the difficulties involved in using pyroelectrics, and how these
issues are overcome.
Before you start

This TLP follows on well from those on ferroelectrics and piezoelectrics. It would be
useful to read this after those.
Introduction
Pyroelectrics are the bridge between ferroelectrics and piezoelectrics – a Venn
diagram showing this interrelations is here:
© 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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They possess a spontaneous polarisation which is not necessarily switchable by

an electric field. If their polarisation is electrically switchable then they are
ferroelectric, a property that may be exploited e.g. for data storage. Pyroelectrics
fill an entirely separate niche.
The pyroelectric effect has been known of for a very long time. The Greek
philosopher Theophrastus first noted (in approximately 400 B.C.) that Tourmaline
would attract straw and bits of wood when heated. This was due to the fact that
the changing the temperature produces surface charges that are capable of
attracting other charged materials. Naturally, how this occurred has only recently
been discovered, but it is interesting to note how early on the effect was
documented.
Polarisation
A pyroelectric material possesses a spontaneous dipole moment, interpreted via
the ionic positions. This dipole moment, when normalised by the amount of
material present, yields a polarisation. Whether a given sample possesses a net
dipole moment depends on domain configurations, which in turn depend on
sample history. This polarisation will change when a stress is applied to the
material, as pyroelectrics are a subsubset of pyroelectrics. Below we compare a
ferroelectric with a pyroelectric that is not ferroelectric.
2
3
Whether or not a material is pyroelectric or ferroelectric depends upon whether

the point group it belongs to is polar, i.e. whether there is at least one direction
along which no point group symmetry element forces both sides of the crystal to
be the same. The polar point groups are:
1, 2, m, mm2, 3, 3m, 4, 4mm, 6, 6mm.
Note that in some of these point groups, e.g. class 4, the polar axis is unique.
Variation of Polarisation with Temperature

With a pyroelectric, the polarisation P will typically decrease when its
temperature is raised. This is because the increasing disorder results in a
reduced segregation of charge, and so the arising dipoles are lessened in
magnitude. The drop off in polarisation can be seen on the next slide.
Here the polarisation drops off to the Curie point, where it is zero.
where p = pyroelectric coefficient (C m-2 T-1). The pyroelectric coefficient is a

vector, with three components:
Typically, however, the electrodes which measure this are placed along a
principal crystallographic direction, and therefore, the coefficient is often
measured as a scalar.
The pyroelectric coefficient measured under an applied field E is liable to differ

from its true value as explained below.
4
When an electric field, E is applied to a polar material, a moment arises, and the
total response D (as measured as a charge per unit area on metallic plates either
side of the pyroelectric) is expressed as:
where = electrical permittivity of the pyroelectric and Ps = spontaneous

polarisation.
This means that:
Since the pyroelectric coefficient pg relates changes in D to changes in T, we

have a ‘generalised’ pyroelectric coefficient, given by:
which includes a factor based on the permittivity of the material being

temperature dependent. This is what is measured.
The true pyroelectric coefficient is given by:
as this defines the variation of the spontaneous polarisation with T.
The effect due to changes in permittivity can sometimes be comparable in

magnitude to true pyroelectricity, and can also be seen above the Curie point.
Behaviour around the Curie point

On warming towards the Curie point, above which the spontaneous polarisation
of a pyroelectric disappears, the pyroelectric coefficient typically increases as the
temperature dependence of the polarization becomes stronger.
The polarisation also depends on the order of the phase transition, covered in
more detail elsewhere.
The diagram below demonstrates how the polarisation changes near the Curie
point.
5
For second order transitions, the pyroelectric coefficient is observed to be large.
Materials which undergo first order transitions cannot be used for applications as
they undergo hysteresis, such that the transition occurs at different temperatures
depending on whether the material is being heated or cooled. This makes the
Curie point unreliable.
These factors mean that the pyroelectric is typically used at temperatures much
lower than the Curie point. This results in pyroelectric coefficients being lower (as
they are directly related to the temperature), but less variable with ambient
temperature.
The Direct and Indirect Effect

As a pyroelectric material is also piezoelectric, then thermal expansion can result
in an indirect contribution to changes in polarisation, in addition to the direct
effect discussed previously.
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Example Pyroelectric Materials

Like other dielectric materials, the predominant pyroelectric structure is the
perovskite.
Two examples are:

0.75Pb(Mg1/3-Nb2/3)O3-0.25PbTiO3, which has a pyroelectric coefficient of
1300*10-6 C m-2 K-1 as a single crystal.
It is more commonly referred to as PMN-PT.
and
Ba0.65Sr0.35TiO3, which has a pyroelectric coefficient of 7.57*10-7 C cm-2 K-1.
It is also known as BST.
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However, there are other types of pyroelectric material which do not have a
perovskite structure. Two of the more common of these will also be considered.
Triglycine sulphate
This has the formula (NH2CH2COOH)3H2SO4, and variations on this have given
some of the highest pyroelectric coefficients. The structure is shown below:
The glycine (NH2CH2COOH) groups are polar, but the most important is the
glycine 1 group, as the reversal of the polarization of the material is associated
with a rotation about the ‘a’ axis of this group. This changes the crystal into a
mirror image of itself. In either state, below the Curie point, (~50oC) the crystal is
point group 2, with a polar axis along the ‘b’ axis. Typically, the crystal is grown
from aqueous solution, with whatever modifications are required. Modifications
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may include deuteration or more esoteric ideas such as substituting glycine for
other amino acid style groups. These have altered properties such as Curie
temp., or the thermal stability of the pyroelectric coefficient.
It has a pyroelectric coefficient of 5.5*10-4 C m-2 K-1, measured at 30oC. It is

useful for the pyroelectric ‘vidicon’, a device used as a camera, for thermal
imaging. This is used by disaster teams to find people trapped under rubble, etc.
Polyvinylidene fluoride
This is a carbon backbone polymer, with repeat unit (-CH2-CF2-). It takes up
several different conformations, which possess different varying properties. The
trans-gauche configuration results in molecules stacked so as to produce a non-
polar unit cell, whereas the all-trans configuration results in a polar unit cell.
Possible configurations:
Unit cells:
10
PVDF does not possess a particularly impressive pyroelectric coefficient,

(0.27*10-4 C m-2 K-1) but it is highly useful in that large area thin films can very
easily be made. These structures are important, as they generate a large charge
which can be easily detected. This overcomes most of the other failings of PVDF.
The large area thin film is most often used for measuring the energy of laser
beams in laboratories, as a large area is required to detect the entire beam.
Since it is also possible to very cheaply make small area thin films, PVDF is
easily made use of in burglar alarms.
(This information sourced from; Pyroelectric devices and materials (review

article) R W Whatmore, Rep. Prog. Phys. 49 (1986) 1335-1386.
Which provides plenty of good information on pyroelectrics.)
Application of a Pyroelectric-Infrared detection
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There are problems with this situation. As discussed in the previous section,
there is the possibility of an indirect effect, with the thermal expansion of the
detector causing a polarisation to develop by piezoelectricity. This produces
‘noise’ of a sort, and can mask the signal generated by the target object. There is
also the possibility of external stresses being applied. This is a problem, as it
means the detector does not work as well as it should. These problems are
typically counteracted by the use of a second pyroelectric component, i.e. a
reference element.
See below:
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Pollutant Control
Today (summer 2007), pollution is a very important issue. The reduction of
pollution and greenhouse gases has become a major priority for parliament. We
need to be able to monitor levels of pollution, in order to monitor the situation.
This is where the pyroelectric comes in.
Pyroelectrics, as shown previously, are excellent detectors of IR radiation.

Therefore, they make perfect devices for testing the level of IR radiation that
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passes through a gas sample. As the wavelength at which a gas absorbs usually
uniquely identifies that gas, this makes an excellent means of detection.
See below for the mechanics of this:
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Summary
As seen, the pyroelectric has somewhat limited use. However, it is a rather
important type of material, due to the position it holds between piezoelectrics and
ferroelectrics. It must also be considered that while it does not have a wide range
of uses, its use in the motion detector (see the ‘Infrared Detection’ section) is
very common, and as such it can be considered important to understand it.
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DoITPoMS Teaching and Learning Packages

• Understand the difference between pyroelectrics and ferroelectrics.

Before you start

They possess a spontaneous polarisation which is not necessarily switchable by

Whether or not a material is pyroelectric or ferroelectric depends upon whether

1, 2, m, mm2, 3, 3m, 4, 4mm, 6, 6mm.

Variation of Polarisation with Temperature

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

The pyroelectric coefficient measured under an applied field E is liable to differ

where = electrical permittivity of the pyroelectric and Ps = spontaneous

This means that:

Since the pyroelectric coefficient pg relates changes in D to changes in T, we

which includes a factor based on the permittivity of the material being

The true pyroelectric coefficient is given by:

as this defines the variation of the spontaneous polarisation with T.

The effect due to changes in permittivity can sometimes be comparable in

Behaviour around the Curie point

For second order transitions, the pyroelectric coefficient is observed to be large.

The Direct and Indirect Effect

Example Pyroelectric Materials

Two examples are:

It has a pyroelectric coefficient of 5.5*10-4 C m-2 K-1, measured at 30oC. It is

PVDF does not possess a particularly impressive pyroelectric coefficient,

(This information sourced from; Pyroelectric devices and materials (review

Which provides plenty of good information on pyroelectrics.)

Application of a Pyroelectric-Infrared detection

Pyroelectrics, as shown previously, are excellent detectors of IR radiation.

See below for the mechanics of this:

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