MME 467: Ceramics for Advanced Applications

Lecture 15
Piezoelectricity, Pyroelectricity
and Ferroelectricity
Ref: Richerson, Modern Ceramic Engineering, Dekker, 1992, pp.267–286.
 Piezoelectricity
 Piezoelectricity is the ability of some materials (notably crystals and
certain ceramics) to generate an electric charge in response to
applied mechanical stress. If the material is not short-circuited, the
applied charge induces a voltage across the material.

 The word piezoelectricity means “electricity by pressure” and is derived

from the Greek piezein , which means to squeeze or press.

 The piezoelectric effect is reversible, that is, all piezoelectric

materials exhibit:
 the direct piezoelectric effect – the production of electricity when stress
is applied,
 the converse piezoelectric effect – the production of stress and/or strain
when an electric field is applied. (For example, lead zirconate titanate crystals will
exhibit a maximum shape change of about 0.1% of the original dimension.)
How common is piezoelectricity?

 7 crystal systems, 14 Bravais lattices, 32 crystal classes

 Off which 12 classes have centre of symmetry  not piezoelectric
 Remaining 20 classes show piezoelectric properties, of which only few
shows optimum properties for practical applications.

 Common examples of piezoelectric materials are:

ZnS, CdS, ZnO, BaTiO3, PZT (lead-zirconium-titanate), PLTZ
(lead-lanthanum-zirconium-titanate).

 Common applications of piezoelectric materials are:

[1] ultrasonic devices, [2] microphone, [3] strain gauge,
[4] sonar devices
 PIEZOELECTRICITY

32 CRYSTALLOGRAPHIC POINT GROUPS

20 NON-CENTROSYMMETRY 12 CENTROSYMMETRY

20 PIEZOELECTRIC

10 NON-PYROELECTRIC 10 PYROELECTRIC
Correlation among piezoelectric, pyroelectric,
and ferroelectric properties

ferroelectric

dielectric
pyroelectric

piezoelectric
 Before subjecting the material to some external stress:
 the centres of the negative and positive charges of each molecule coincide,
 the external effects of the charges are reciprocally cancelled,
 as a result, an electrically neutral molecule appears.

 After exerting some pressure on the material:

 the internal structure is deformed,
 that causes separation of the positive and negative centres of the molecules,
 as a result, little dipoles are generated.

 Eventually:
 the facing poles inside the material are mutually cancelled,
 a distribution of a charge appears in the material’s surfaces and the material
is polarized,
 the polarization generates an electric field and can be used to transform the
mechanical energy of the material’s deformation into electrical energy
 PIEZOELECTRICITY

Whatever is the
direction of
applied force, the
center of mass
(CM) of positive
charges will
always coincide
with that of
negative charges
 All piezoelectric crystals are anisotropic and have no centre of symmetry,
and they tend to polarize permanently.
 Even these, they are not piezoelectric in all directions.

Example:
A compressive stress
applied in [100] direction
polarize quartz, while
stress in [001] direction
causes no polarization.
 PIEZOELECTRICITY

There is one important parameter that has to be fulfilled for

piezoelectricity: the axis, where pressure is applied, has to
be polar
 For small deformation and small electric field the relationship
between stress and electric field is linear.
s = applied stress
Field produced by stress, E = gs e = generated strain

e = dE
d = piezoelectric constant
Strain produced by field, g = constant

 The two constants g and d are

related through the modulus of
elasticity E by the equation

1
E=
gd
Telephone/Microphone

 The piezoelectric effect is used in transducers, which convert acoustical

waves (sound) into electric fields or electric fields into acoustical waves.

Sound of a particular
frequency produces a strain in
Transducer A (a piezoelectric
material). The dimensional
changes polarize the crystal,
creating a voltage signal.

This signal is transmitted to

transducer B (another
piezoelectric) where it causes
dimensional change which
produce an acoustical wave
that is amplified.
Use of piezoelectric transducers for telephone
 PIEZOELECTRICITY
11,000 watt-hours of power -- from normal bodily functions
such as motion and the production of body heat

Walking, for example, produces 163 watts of power, while

sprinting generates more than 1,600 watts

NASA's Defense Advanced Research Projects Agency (DARPA)

estimates that a single footstep could provide 1 to 2 watts
Piezoelectric device is laid under
An ordinary dance club -- house music thumping three asphalt layer to create about 400
nights a week -- uses 150 times more energy than a
household of four people each year
KW of power with vibrations from
moving vehicle
PIEZOELECTRICITY
 Pyroelectricity
 Pyroelectric crystals are special class of piezoelectric crystals.

 Pyro means fire, so pyroelectric translates to “fire electricity,” i.e.

electricity released by heat.

 Spontaneous polarization resulted due to a change in temperature

 heating of crystals results in mechanical deformation due to thermal
expansion and causes polarization.

D = e0 E + P
dD dE dP
= e0 +
dT dT dT
Generalised pyroelectric Pyroelectric
coefficient coefficient
 Off the 20 piezoelectric crystal classes, 10 classes are pyroelectric.
 Examples: Wurtzite (hexagonal ZnS), BaTiO3, Pb(Zr, Ti)O3, LiTaO3

 Most pyroelectric materials lose their pyroelectric behaviour as the

temperature is increased to a few 100 degrees.

 But LiTaO3 retains its pyroelectric behaviour to 609 C.

 They are used over a broad temperature range for extremely
accurate measurement of temperature changes.
 Changes of the order of 10–6 C can be detected.
 Uses of LiTaO3: [1] scanning microcalorimeter to measure heat
in submicrocalorie range, [2] micro enthalpimeter to monitor
catalytic process

 Other important uses of pyroelectric ceramics: [1] optical sensor,

[2] infrared detector, [3] gas flow measurement
 Ferroelectricity

 These are subclass of pyroelectric materials.

 Like pyroelectric materials, they contain spontaneous polarization;

but unlike pyroelectric materials, the direction of polarization can be
reversed by the application of an electric field and a hysteresis loop
is resulted.

 Ferroelectric behaviour is dependent on the crystal structure.

[1] Crystal must be non-centric
[2] must contain alternate atom positions or molecular orientation
to permit the reversal of dipole and retention of polarization
after voltage is removed.
Ferroelectric Behaviour of BaTiO3

T = 120 – 1460 ºC

 Cubic structure, not ferroelectric

 Ti4+ shifts positions when E is applied, polarization resulted
 Ti4+ returns to the original position when E is removed.
 no retained polarization, no hysteresis loop

T ≤ 120 ºC

 Tetragonal structure, ferroelectric

 Ti4+ position changes as polarity of E changes
 reversal of polarization, hysteresis loop in E vs. P curve
Ferroelectric Behaviour
 Ferroelectric hysteresis loop

 One consequence of the domain-wall

switching in ferroelectric materials is the
occurrence of the ferroelectric
hysteresis loop.

 As the field is increased the polarization

of domains with an unfavourable
direction of polarization will start to
switch in the direction of the field,
rapidly increasing the measured charge
density (segment BC).
 Ferroelectric hysteresis loop

• The polarization response in this

region is strongly nonlinear.
• Once all the domains are aligned
(point C) the ferroelectricity again
behaves linearly (segment CD).
• If the field strength starts to decrease,
some domains will back-switch, but at
zero field the polarization is nonzero
(point E).
• The value of polarization at zero field
(point E) is called the remanent
polarization, PR.
• To reach a zero polarization state the field
must be reversed (point F).

• The field necessary to bring the polarization

to zero is called the coercive field, EC.

• It should be mentioned that the coercive

field EC that is determined from the
intercept of the hysteresis loop with the
field axis is not an absolute threshold field.

• The spontaneous polarization PS is usually

taken as the intercept of the polarization
axis with the extrapolated linear segment
CD.

• Further increase of the field in the negative

direction will cause a new alignment of
dipoles and saturation (point G).
  Maximum alignment of domains occur when BaTiO3 is cooled
through 120 C transformation while applying an electric field.
This process is called pooling and cause maximum polarization.
 Above 120 C, the Curie temperature, the crystal is paraelectric.

 Doping changes the Curie temperature and hysteresis loop.

Also the shape of hysteresis loop varies with temperature.

As T is increased,
 Loop gets thinner
 Becomes straight-line above Curie point when the material is no longer ferroelectric