PYROELECTRIC EFFECT

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 Pyroelectricity

The property of certain crystals to produce a state of electric pol

arity by a change of temperature. Certain dielectric (electrically
nonconducting) crystals develop an electric polarization (dipole
moment per unit volume) when they are subjected to a uniform
temperature change. This pyroelectric effect occurs only in cryst
als which lack a center of symmetry and
also have polar directions (that is, a polar axis). These conditions
are fulfilled for 10 of the 32 crystal classes. Typical examples of
pyroelectric crystals are tourmaline, lithium sulfate monohydrat
e, cane sugar, and ferroelectric barium titanate.
Pyroelectricity (from the two Greek words pyr meaning
fire, and electricity) is a property of certain crystals
which are naturally electrically polarized and as a result
contain large electric fields.[1] Pyroelectricity can be
described as the ability of certain materials to generate
a temporary voltage when they are heated or
cooled.[2][3] The change in temperature modifies the
positions of the atoms slightly within the crystal
structure, such that the polarization of the material
changes. This polarization change gives rise to a voltage
across the crystal. If the temperature stays constant at
its new value, the pyroelectric voltage gradually
disappears due to leakage current. (The leakage can be
due to electrons moving through the crystal, ions
moving through the air, or current leaking through
a voltmeter attached across the crystal.)[3][4]
Pyroelectric crystals can be regarded as having a built-
in or permanent electric polarization. When the crystal is held at c
onstant temperature, this polarization does not manifest itself bec
ause it is compensated by free charge carriers that have reached t
he surface of the crystal by conduction through the crystal and fro
m the surroundings. However, when the temperature of the crysta
l is raised or lowered, the permanent polarization changes, and thi
s change manifests itself as pyroelectricity.
The magnitude of the pyroelectric effect depends upon whether
the thermal expansion of the crystal is prevented by clamping or
whether the crystal is mechanically unconstrained. In the clamp
ed crystal, the primary pyroelectric effect is observed, whereas i
n the free crystal, a secondary pyroelectric effect is superposed
upon the primary effect. The secondary effect may be regarded
as the piezoelectric polarization arising from thermal expansion,
and is generally much larger than the primary effect.
"initial" dielectric constant for a crystal plate in which.
the polarization is normal to the surface of the place.
We have interpreted this behavior as being a "clamp-
Pyroelectrics have a broad spectrum of potential scientific and
technical applications. The most developed is the detection of
infrared radiation. In addition, pyroelectric detectors can be u
sed to measure the power generated by a radiation source (in
radiometry), or the temperature of a remote hot body (in pyro
metry, with corrections due to deviations from the blackbody
emission)

An infrared image can be projected on a pyroelectric plate and tr

ansformed into a relief of polarization on the surface. Other pote
ntial applications of pyroelectricity include solar energy conversi
on, refrigeration, information storage, and solid-state science.
Pyroelectricity provides one of the best performing principles for
the detection of temperature changes. This occurs in polar
matter and results in the appearance of surface charges
proportional to a temperature change ΔT. The basic structure is
a planar capacitor whose charge Q varies according to ΔQ=ApΔT,
where A is the area of the capacitor and p the pyroelectric
coefficient. A pyroelectric sensor thus directly generates an
electric signal, facilitating the integration into electronic circuits.
Pyroelectric crystals, ceramics of ferroelectric materials, as well
as polymers have therefore been used since the 1960s in
thermal infrared (IR) detectors, joining the earlier thermal IR
detection techniques of bolometers and thermopiles. Since the
late 1980s, pyroelectrics have also been investigated in the form
of thin films and integrated onto micromachined
structures. Pyroelectricity thus made its way from a scientific
curiosity known since 2500 years to a very useful physical effect
that, for instance, enables firemen to see through smoke.
Pyroelectric Properties

The pyroelectric effect is the change in polarization due to the

change in temperature. Ferroelectric materials are expected to
be strongly pyroelectric because ferroelectric materials have a
large range of temperature-dependent spontaneous
polarization (Fatuzzo and Merz, 1967). In addition, even
nonpyroelectric materials will exhibit a pyroelectric-like
response when biased by the electric field due
to dielectric displacement (Damjanovic, 1998). It has also been
reported that in ferroelectric materials, the bias field increases
the transition temperature and changes the dielectric
permittivity, thus leading to a maximum in the pyroelectric
responsivity at a certain field (Lines and Glass, 1977;
Whatmore, 1986; Herbert, 1982). For example, Chynoweth
(1956) reported that the pyroelectric response increases with
the approaching Curie point during the ferroelectric phase in
BaTiO3.
Pyroelectricity and ferroelectricity

Pyroelectricity originates from a permanent electric dipole moment of the unit

cell of the crystal structure or, in macroscopic terms, from an intrinsic
(“spontaneous”) electrical polarization. This polarization is changed by heating
and cooling, thus giving rise to electric charges on certain crystal faces.
In a crystal, a spontaneous polarization can be present only along a polar
direction which has no symmetrically equivalent directions. (In the literature, the
condition for the occurrence of pyroelectricity is frequently expressed as “a
unique (or singular) polar axis.” This term, however, is misleading for point
groups m and 1.) Such polar directions occur in the following ten (“pyroelectric”)
point groups: 6, 4, 3, 2, 1, and their combination with a “parallel” mirror plane:
6mm, 4mm, 3m, mm2, m (Table 5). In point groups with a rotation axis,
the electric polarization (“pyroelectric vector” p) is fixed parallel to this polar
axis. For point group m, the pyroelectric vector p is oriented parallel to the
mirror plane, and for point group 1 any direction of p is possible.
A polar crystal is ferroelectric if the direction of the spontaneous polarization can
be reversed (“switched”) by an electric field, leading to a hysteresis behavior.
Thus, ferroelectricity can only occur in the ten pyroelectric point groups.
 Explanation

Pyroelectricity can be visualized as one side of a triangle,[5] where each corner

represents energy states in the crystal: kinetic, electrical and thermal energies. The
side between electrical and thermal corners represents the pyroelectric effect and
produces no kinetic energy. The side between kinetic and electrical corners
represents the piezoelectric effect and produces no heat.

Pyroelectric charge in minerals develops on the opposite faces of asymmetric

crystals. The direction in which the propagation of the charge tends is usually
constant throughout a pyroelectric material, but, in some materials, this direction
can be changed by a nearby electric field. These materials are said to
exhibit ferroelectricity. All known pyroelectric materials are also piezoelectric.
Despite being pyroelectric, novel materials such as boron aluminum nitride (BAlN)
and boron gallium nitride (BGaN) have zero piezoelectric response for strain along
the c-axis at certain compositions[6], the two properties being closely related.
However, note that some piezoelectric materials have a crystal symmetry that does
not allow pyroelectricity.
Pyroelectric materials are mostly hard and crystals, however, soft pyroelectricity
can be achieved by using electrets.[7]
Pyroelectricity is measured as the change in net polarization (a vector)
proportional to a change in temperature. The total pyroelectric coefficient
measured at constant stress is the sum of the pyroelectric coefficients at
constant strain (primary pyroelectric effect) and the piezoelectric contribution
from thermal expansion (secondary pyroelectric effect). Under normal
circumstances, even polar materials do not display a net dipole moment. As a
consequence there are no electric dipole equivalents of bar magnets because
the intrinsic dipole moment is neutralized by "free" electric charge that builds
up on the surface by internal conduction or from the ambient atmosphere.
Polar crystals only reveal their nature when perturbed in some fashion that
momentarily upsets the balance with the compensating surface charge.

Spontaneous polarization is temperature dependent, so a good perturbation

probe is a change in temperature which induces a flow of charge to and from
the surfaces. This is the pyroelectric effect. All polar crystals are pyroelectric, so
the 10 polar crystal classes are sometimes referred to as the pyroelectric
classes. Pyroelectric materials can be used as infrared and millimeter
wavelength radiation detectors.
An electret is the electrical equivalent of a permanent magnet.
 Mathematical description

he pyroelectric coefficient may be described as the change in

the spontaneous polarization vector with temperature:[8]

where pi (Cm−2K−1) is the vector for the pyroelectric coefficient.

 Crystal classes

All crystal structures belong to one of thirty-two crystal classes based

on the number of rotational axes and reflection planes they possess
that leave the crystal structure unchanged (point groups). Of the
thirty-two crystal classes, twenty-one are non-centrosymmetric (not
having a centre of symmetry). Of these twenty-one, twenty exhibit
direct piezoelectricity, the remaining one being the cubic class 432.
Ten of these twenty piezoelectric classes are polar, i.e., they possess a
spontaneous polarization, having a dipole in their unit cell, and exhibit
pyroelectricity. If this dipole can be reversed by the application of an
electric field, the material is said to be ferroelectric. Any dielectric
material develops a dielectric polarization (electrostatics) when an
electric field is applied, but a substance which has such a natural
charge separation even in the absence of a field is called a polar
material. Whether or not a material is polar is determined solely by its
crystal structure. Only 10 of the 32 point groups are polar. All polar
crystals are pyroelectric, so the ten polar crystal classes are sometimes
referred to as the pyroelectric classes.
Piezoelectric crystal classes: 1, 2, m, 222, mm2, 4, -4, 422, 4mm, -42m,
3, 32, 3m, 6, -6, 622, 6mm, -62m, 23, -43m
Pyroelectric: 1, 2, m, mm2, 3, 3m, 4, 4mm, 6, 6mm
 Related effects

Two effects which are closely related to pyroelectricity

are ferroelectricity and piezoelectricity. Normally materials are very nearly
electrically neutral on the macroscopic level. However, the positive and
negative charges which make up the material are not necessarily
distributed in a symmetric manner. If the sum of charge times distance for
all elements of the basic cell does not equal zero the cell will have an
electric dipole moment (a vector quantity). The dipole moment per unit
volume is defined as the dielectric polarization. If this dipole moment
changes with the effect of applied temperature changes, applied electric
field, or applied pressure, the material is pyroelectric, ferroelectric, or
piezoelectric, respectivel
The ferroelectric effect is exhibited by materials which
possess an electric polarization in the absence of an
externally applied electric field such that the polarization can
be reversed if the electric field is reversed. Since all
ferroelectric materials exhibit a spontaneous polarization, all
ferroelectric materials are also pyroelectric (but not all
pyroelectric materials are ferroelectric).
The piezoelectric effect is exhibited by crystals (such as quartz
or ceramic) for which an electric voltage across the material
appears when pressure is applied. Similar to pyroelectric
effect, the phenomenon is due to the asymmetric structure of
the crystals that allows ions to move more easily along one
axis than the others. As pressure is applied, each side of the
crystal takes on an opposite charge, resulting in a voltage
drop across the crystal.
Pyroelectricity should not be confused
with thermoelectricity: In a typical demonstration of
pyroelectricity, the whole crystal is changed from one
temperature to another, and the result is a temporary
voltage across the crystal. In a typical demonstration of
thermoelectricity, one part of the device is kept at one
temperature and the other part at a different temperature,
and the result is a permanent voltage across the device as
long as there is a temperature difference. Both effects
convert temperature change to electrical potential, but the
pyroelectric effect converts temperature change
over time into electrical potential, while the thermoelectric
effect converts temperature change with position into
electrical potential.
 Pyroelectric materials

Although artificial pyroelectric materials have been engineered, the effect

was first discovered in minerals such as tourmaline. The pyroelectric effect
is also present in bone and tendon.
The most important example is gallium nitride, a semiconductor.[18] The
large electric fields in this material are detrimental in light emitting diodes
(LEDs), but useful for the production of power transistors.
Progress has been made in creating artificial pyroelectric materials, usually
in the form of a thin film, using gallium nitride (GaN), caesium
nitrate (CsNO3), polyvinyl fluorides, derivatives of phenylpyridine,
and cobalt phthalocyanine. Lithium tantalate (LiTaO3) is a crystal exhibiting
both piezoelectric and pyroelectric properties, which has been used to
create small-scale nuclear fusion ("pyroelectric fusion").[19] Recently,
pyroelectric and piezoelectric properties have been discovered in
doped hafnium oxide (HfO2), which is a standard material
in CMOS manufacturing.[20
Heat sensors[edit]
Very small changes in temperature Applications
can produce a pyroelectric potential. Passive
infrared sensors are often designed around pyroelectric materials, as the heat of a
human or animal from several feet away is enough to generate a voltage.[cita

Power generation[edit]
A pyroelectric can be repeatedly heated and cooled (analogously to a heat engine) to
generate usable electrical power. One group calculated that a pyroelectric in
an Ericsson cycle could reach 50% of Carnot efficiency,[21][22] while a different study
found a material that could, in theory, reach 84-92% of Carnot efficiency[23] (these
efficiency values are for the pyroelectric itself, ignoring losses from heating and
cooling the substrate, other heat-transfer losses, and all other losses elsewhere in
the system). Possible advantages of pyroelectric generators for generating electricity
(as compared to the conventional heat engine plus electrical generator) include:
potentially lower operating temperatures, less bulky equipment, and fewer moving
parts.[24] Although a few patents have been filed for such a device,[25] such generators
do not appear to be anywhere close to commercialization.
Nuclear fusion[edit]
Pyroelectric materials have been used to generate large electric fields
necessary to steer deuterium ions in a nuclear fusion process. This is known
as pyroelectric fusion.
Pyroelectricity can be described as the ability of certain materials to
generate a temporary voltage when they are heated or cooled. The change in
temperature modifies the positions of the atoms slightly within the crystal
structure, such that the polarization of the material changes.

What is Pyroelectric Material : Mathematical

Analysis & Its Applications

A dielectric material is an electrical insulator, which has the capacity of

stopping the flow of current through it. They are classified into Centro
symmetric materials and piezoelectric materials, further piezoelectric is
classified as non-pyroelectrics and pyroelectrics, pyro electrics are further
classified as non-ferroelectrics and ferroelectrics. This article specifies
pyroelectric material. It was discovered in the early 20th century by a
Greek scientist. The name pyroelectricity is derived from Greek where
pyro means fire and electricity. It is a general property of certain crystal
which are polarised to obtain large electric field. These pyroelectric
materials are hard in nature and crystalline.
 What is Pyroelectric Material?

Pyroelectricity or pyroelectric material is an electric response of polar

dielectric with a change in temperature. If the temperature in return
changes it causes the movement of atoms from there neutral position
hence the polarization of the material changes, we observe a voltage across
the material. This effect is temporary now suppose the temperature
remains constant at its new value. The pyroelectric voltage becomes zero
due to the leakage current. So, within this same temperature limits, the
charges developed by the effect of heating or cooling are equal and
opposite.
Pyroelectric materials exhibit spontaneous polarization that is polarization
in the absence of electric field, this cannot be changed or reversed on
applying the electric field it does so in ferroelectric materials. Hence all
pyro electro materials are also piezoelectric. The piezoelectric materials
have a certain kind of piezoelectric crystal that does not allow
pyroelectricity. Hence pyroelectric effect takes place below the 1070-
degree F curie temperature, so when the material is heated above curie
temperature 1070-degree F the atoms come back to their equilibrium
positions. So, the electrocaloric effect is considered as a physical inverse of
the pyroelectric effect.
 List of Pyroelectric Materials

Tourmaline
gallium nitride
cesium nitrate (CsNO3)
polyvinyl fluorides
derivatives of phenyl pyridine
cobalt phthalocyanine
Lithium tantalite (LiTaO3).
Comparison between Pyro Electricity and Thermo Electricity

The electrocaloric effect is the phenomenon in which the material shows the
reversible temperature change on the applied electric field. Hence
pyroelectricity is different from thermoelectricity. Pyro crystal changes
temperature from one degree to another resulting in a temporary voltage
across the crystal.
Whereas in the case of thermoelectricity the two ends of the device are
subjected to two different temperatures resulting in a permanent voltage in
the device resulting in as there is the temperature difference.
Parameters Piezoelectric Pyroelectric Ferroelectric

Ferroelectric material
Piezoelectric materials Pyroelectric material
exhibits electric
generate electricity generates electric
Function polarization even in the
whenever mechanical potential whenever
absence of an electric
stress is applied. heated or cooled.
field.
Quartz, Quartz crystal,
Examples Lithium niobite,
crystal,Ammonium, Ammonium,
Barium Titanite
Phosphate Phosphate.
They are unidirectional They are easily
Non-centrosymmetric, polarization, polarized,
Non-polar dielectric, non-centrosymmetric, They exhibit dielectric
Properties
Presence of Piezoelectric It exhibits hysteresis,
effect where P= dσ. pyroelectricity when T They are both pyro and
>= Tc piezoelectric in nature.
Ultrasonic transducers
They are pressure
Acts like a transducer, IR detectors,
transducer
Used in microphones, Image tubes,
Applications It acts as
It generates ultrasonic Temperature sensing
a memory device like a
waves. elements.
random access
memory.
Mathematical Analysis of Pyroelectric Material

A thin piece of a pyroelectric material is an electrode and connected to an

amplifier which is of high impedance, a field-effect transistor (FET) as shown
below. Let it be the pyroelectric current which generates voltage V across the
electric admittance Ye. A voltage amplifier of unity gains couples the high
impedance source of current to a low input impedance following the circuit. If
p’ is a component of pyroelectric coefficient p the orthogonal to the electrode
surface of area A. The generated current is independent of thickness since the
current is associated with the unbounded surface charge.
Charge Q = p’ A Δ T…….. 1
Pyroelectric current ip = Ap’dT/dt …….. 2
Pyroelectric voltage V=i/УE ……… 3
Where electrical admittance УE = GA + GE + jw CA + CE …….4
Shunt and sample conductance GA, GE
Shunt and sample capacitance CA, CE
Equivalent capacitance of the dielectric is
C = €σa/Ad ……5
Stored energy E = ½ p2€σAhΔT2 …….6
d = material thickness; €σ = permittivity constant at stress, A = Area of
protection, p’ = component of pyroelectric coefficient p.
If an electric field E is applied to a material, the total dielectric
displacement d that is a charge per unit area of the plate, on both the
sides of a pyroelectric material is,
d= E s +€ E ……….7
where € is the permittivity of vacuum and Es is spontaneous
polarization of volume density of electric dipole moment.
Effect of Pyroelectric Coefficient with Temperature
From the above analysis, the pyroelectric coefficient has an effect of
temperature
Pyroelectric coefficient increases with an increase in temperature
It depends on the order of phase transition and is larger for second-
order transitions
Tc is a curie temperature where the pyroelectric material increases.
Advantages Pyroelectric Materials
The advantages of pyroelectric materials are
• Pollution Free
• Maintenance cost is less
• Very high-frequency response
Disadvantages Pyroelectric Material
The disadvantage of pyroelectric materials is
• Require high impedance cable
• Static motions cannot be measured easily.
Applications
The applications of Pyroelectric materials are
• PIR – based motion detectors
• Radiometry
• Solar energy pyroelectric converter
• Detection and protection of wildlife
• PIR remote-based thermometer
• Fire detector
• Laser diagnostic.