8.dielectric and Ferroelectric of Materials

1
Dielectric and Ferroelectric Properties of Materials
Prof.P. Ravindran,
Department of Physics, Central University of Tamil
Nadu, India
http://folk.uio.no/ravi/PMAT2013
P.Ravindran, PHY085 – Properties of Materials, April 2014: Dielectric and Ferroelectric Properties of Materials
Dielectric Materials
Dielectric means a non-conductor or poor conductor of electricity.
Dielectric means a material that presents electric polarization.
The dielectric is an insulating material or a very poor conductor of electric

current. When dielectrics are placed in an electric field, practically no
current flows in them because, unlike metals, they have no loosely bound, or
free, electrons that may drift through the material. Instead, electric
polarization occurs.
The positive charges within the dielectric are displaced minutely in the
direction of the electric field, and the negative charges are displaced minutely
in the direction opposite to the electric field. This slight separation of charge,
or polarization, reduces the electric field within the dielectric.
The resistivity of insulators is:   107  1018   m
Dielectric Materials
If a material contains polar molecules, they will generally be in random

orientations when no electric field is applied. An applied electric field will
polarize the material by orienting the dipole moments of polar molecules.
This decreases the effective electric field between the plates and will increase
the capacitance of the parallel plate structure. The dielectric must be a good
electric insulator so as to minimize any DC leakage current through a
capacitor.
Polarization in dielectrics
 Capacitor – An electronic device, constructed from

alternating layers of a dielectric and a conductor, that is
capable of storing a charge. These can be single layer or
multi-layer devices.
 Permittivity - The ability of a material to polarize and store a
charge within it.
 Linear dielectrics - Materials in which the dielectric
polarization is linearly related to the electric field; the
dielectric constant is not dependent on the electric field.
 Dielectric strength - The maximum electric field that can be
maintained between two conductor plates without causing a
breakdown.
Dielectric strength
 Maximum electric field that an insulator can withstand

before it loses its insulating behavior
 Lower for ceramics than polymers
 Dielectric breakdown - avalanche breakdown or carrier
multiplication
Dielectric Loss
When the relaxation time is much faster than the frequency

of the applied electric field, polarization occurs
instantaneously.
When the relaxation time is much slower than the frequency

of the applied electric field, no polarization (of that type)
occurs.
When the relaxation time and the frequency of the applied

field are similar, a phase lag occurs and energy is absorbed.
This is called dielectric loss, it is normally quantified by the
relationship
tan d = er”/er’
where er’ is the real part of the dielectric constant and er” is
the imaginary part of the dielectric constant.
Polarization mechanisms in materials:
(a) electronic,
(b) atomic or ionic,
(c) high-frequency dipolar or orientation (present in
ferroelectrics),
(d) low-frequency dipolar (present in linear dielectrics and
glasses),
(e) interfacial-space charge at electrodes, and
(f ) interfacial-space charge at heterogeneities such as grain
boundaries.
Dielectric Constant
Ifyou apply an electric field, E, across a material the charges in the material will
respond in such a way as to reduce (shield) the field experienced within the material,
D (electric displacement)
D = eE = e0E + P = e0E + e0ceE = e0(1+ce)E
where e0 is the dielctric permitivity of free space (8.85 x 1012 C2/N-m2), P is the
polarization of the material, and ce is the electric susceptibility. The relative
permitivity or dielectric constant of a material is defined as:
er = e/e0 = 1+ce
When evaluating the dielectric properties of materials it is this quantity we will use
to quantify the response of a material to an applied electric field.
Contributions to Polarizability
a = ae + ai + ad + as
Polarizability
1. Electronic Polarizability (ae) (a) increases
Polarization of localized electrons
2. Ionic Polarizability (ai) Response

Displacement of ions Time
Increases
3. Dipolar Polarizability (ad) (slower
response)
Reorientation of polar molecules
4. Space Charge Polarizability (as)

Long range charge migration
Electronic Polarizability
Let’s limit our discussion to insulating extended solids. In the
absence of charge carriers (ions or electrons) or molecules, we only
need to consider the electronic and ionic polarizabilities.
E
-q
without with field x

field
+q
The presence of an electric field polarizes the electron

distribution about an atom creating a dipole moment,
m=qx
The dipole moment per unit volume, P, is then given by
P = nmm
where nm is the number of atoms per unit volume.
Frequency Dependence
Reorientation of the dipoles in response to an electric field is characterized by a
relaxation time, t. The relaxation time varies for each of the various
contributions to the polarizability:
1. Electronic Polarizability (ae)

Response is fast, t is small
2. Ionic Polarizability (ai)
Response is slower
3. Dipolar Polarizability (ad)
Response is still slower
4. Space Charge Polarizability (as)
Response is quite slow, t is large
Audiofrequencies (~ 103 Hz) a=

ae+ai+ad+as
Radiofrequencies (~ 106 Hz) (as  0) a = ae+ai+ad
Microwave frequencies (~ 109 Hz) (as, ad  0) a = ae+ai
Visible/UV frequencies (~ 1012 Hz) (as, ad, ai  0) a = ae
Symmetry Constraints and Dielectric Properties
Dielectric properties can only be found with certain crystal symmetries
Piezoelectric
 Do not posses an inversion center (noncentrosymmetric)
Ferroelectric/Pyroelectric
 Do not posses an inversion center (noncentrosymmetric)
 Posses a Unique Polar Axis
The 32 point groups can be divided up in the following manner (color

coded according to crystal system: triclinic, monoclinic, etc.).
Piezoelectric
 1, 2, m, 222, mm2, 4, -4, 422, 4mm, 42m, 3, 32, 3m,
 6, -6, 622, 6mm, 6m2, 23, 43m
Ferroelectric/Pyroelectric
 1, 2, m, mm2, 4, 4mm, 3, 3m, 6, 6mm
Centrosymmetric (Neither)
 -1, 2/m, mmm, 4/m, 4/mmm, -3, 3/m, 6/m, 6/mmm, m3, m3m
Frequency Dependence
e(w)
ad+ai+ae
e0
ai+ae er (Dielectric Const.)
ae only
Microwaves
IR
e
UV
tan d
(Loss)
log(w)
Ionic Polarization and Ferroelectricity
Most dielectric materials are insulating (no conductivity of either

electrons or ions) dense solids (no molecules that can reorient). Therefore,
the polarizability must come from either ionic and electronic
polarizability. Of these two ionic polarizability can make the largest
contribution, particularly in a class of solids called ferroelectrics. The
ionic polarizability will be large, and a ferroelectric material will result,
when the following two conditions are met:
1. Certain ions in the structure displace in response to the application

of an external electric field. Typically this requires the presence
of certain types of ions such as d0 or s2p0 cations.
2. The displacements line up in the same direction (or at least they
do not cancel out). This cannot happen if the crystal structure has
an inversion center.
3. The displacements do not disappear when the electric field is
removed.
What is a Ferroelectric
A ferroelectric material develops a spontaneous polarization
(builds up a charge) in response to an external electric field.
•The polarization does not go

away when the external field is
removed.
•The direction of the

polarization is reversible.
Applications of Ferroelectric Materials

•Multilayer capacitors
•Non-volatile FRAM (Ferroelectric Random Access Memory)
Ferroelectricity
 Ferroelectricity is an electrical phenomenon whereby

certain materials may exhibit a spontaneous dipole
moment, the direction of which can be switched between
equivalent states by the application of an external electric
field.
 The internal electric dipoles of a ferroelectric material are
physically tied to the material lattice so anything that
changes the physical lattice will change the strength of the
dipoles and cause a current to flow into or out of the
capacitor even without the presence of an external voltage
across the capacitor.
Ferroelectrics:
•There is a class of materials which shows spontaneous polarization
and for which the relation between P and E is non-linear. Such
materials also exhibit Hysteresis.
•These substances whose properties are similar to ferromagnetics in
many respects are called Ferroelectrics.
Spontaneous polarization is a function of temperature. Ps

decreases with increase in temperature and vanishes at the curie
temperature Tc.
T < Tc
At E = 0
Above Tc , the substance is in
Ferroelectric behavior the paraelectric state in which
the elementary dipoles of the
T > Tc various unit cells in the
At E = 0 crystal are randomly
oriented.
Paraelectric behavior In paraelectric state the substance
is found to obey the Curie-Weiss
Law
C
Electric susceptibility   ,
T  TC
where C and Tc are constants known as and χ
Curie  Weiss temperature .
Tc
T
Ferroelectricity
 Two stimuli that will change the lattice dimensions

of a material are force and temperature.
 The generation of a current in response to the
application of a force to a capacitor is called
piezoelectricity.
 The generation of current in response to a change
in temperature is called pyroelectricity.
Ferroelectricity
 Placing a ferroelectric material between two conductive

plates creates a ferroelectric capacitor.
 Ferroelectric capacitors exhibit nonlinear properties and
usually have very high dielectric constants.
 The fact that the internal electric dipoles can be forced to
change their direction by the application of an external
voltage gives rise to hysteresis in the "polarization vs
voltage" property of the capacitor.
 Polarization is defined as the total charge stored on the
plates of the capacitor divided by the area of the plates.
 Hysteresis means memory and ferroelectric capacitors are
used to make ferroelectric RAM for computers and RFID
cards.
Ferroelectricity
 The combined properties of memory, piezoelectricity, and

pyroelectricity make ferroelectric capacitors some of the
most useful technological devices in modern society.
 Ferroelectric capacitors are at the heart of medical
ultrasound machines, high quality infrared cameras, fire
sensors, sonar, vibration sensors, and even fuel injectors on
diesel engines.
 The high dielectric constants of ferroelectric materials
used to concentrate large values of capacitance into small
volumes, resulting in the very tiny surface mount
capacitor.
 The electrooptic modulators that form the backbone of the
Internet are made with ferroelectric materials.
Ferroelectric properties
 Most ferroelectric materials undergo a structural phase

transition from a high-temperature nonferroelectric (or
paraelectric) phase into a low-temperature ferroelectric
phase.
 The paraelectric phase may be piezoelectric or
nonpiezoelectric and is rarely polar.
 The symmetry of the ferroelectric phase is always lower
than the symmetry of the paraelectric phase.
Ferroelectric properties
 The temperature of the phase transition is called the Curie
point, TC.
 Above the Curie point the dielectric permittivity falls off
with temperature according to the Curie–Weiss law
– where C is the Curie constant, T0 (T0 ≤TC) is the Curie–Weiss

temperature.
 Some ferroelectrics, such as BaTiO3, undergo several
phase transitions into successive ferroelectric phases.
Ferroelectric Materials
 A group of dielectric
materials that display
spontaneous polarization.
In other words, they
possess polarization in the
absence of an electric field.
Types of Ferroelectric Materials
Ferroelectric Materials can be structurally categorized into 4 groups:
1. Corner Sharing Octahedra:

1.1 Perovskite-Type Compounds
(such as BaTiO3, PT, PZT, PMN, and PLZT)
1.2 Tungsten-Bronze-Type Compounds
(such as PbNb2O6)
1.3 Bismuth Oxide Layer Structured Compounds
(such as Bi4Ti3O12 and PbBi2Nb2O9)
1.4 Lithium Niobate and Tantalate
(such as LiNbO3 and LiTaO3)
2. Compounds Containing Hydrogen Bonded Radicals

(such as KDP, TGS, and Rochelle Salt)
3. Organic Polymers (such as PVDF and co-polymers)
4. Ceramic Polymer Composites (such as PZT-PE)
Examples of ferroelectric materials:
KH 2 PO4 (123K )
•There are mainly three types of crystal
structures which exhibit ferroelectricity: KD2 PO4 (213K )
1. Rochelle salt structure or Rochelle salt, RbH 2 PO4 (147K )
NaK(C4H4O6).4H2O:Sodium Potassium
Tartrate RbH 2 AsO4 (111K )
KH 2 AsO4 (96)
2. Perovskite group consisting mainly of
titnates and niobates BaTiO3 (393K )
BaTiO3 : Barium titanate
SrTiO3 (~ 0K )
3. Dihydrogen phosphates and arsenates
KH2PO4 : Potasium di phosphate (KDP) KNbO3 (713K )
• The ferroelectricity can be explained by the PbTiO3 (763K )

domain theory. LiTaO3 (890K )
LiNbO3 (1470K )
Corner Sharing Octahedra
Mixed Oxide Ferroelectrics with
Corner Sharing Octahedra of O2- Ions
Inside each Octahedron  Cation Bb+ (3 < b < 6)

Space between the Octahedra  Aa+ Ions (1 <a < 3)
Corner Sharing Octahedra
In prototypic forms, Aa+, Bb+, and O2- ions geometrically coincide

 Non-Polar Lattice 
Phase Transitions Changes in Lattice Structure 

Aa+ and Bb+ ions displaced w.r.t. O2- ions
 Polarized Lattice 
Ferroelectrics
 When a ferroelectric material is heated above its Curie
Temp. then the unit cell becomes cubic, all the ions assume
symmetric positions within the cubic unit cell and
ferroelectric behavior ceases.
 Spontaneous polarization is a result of interactions between
adjacent permanent dipoles which mutually align, all in the
same direction.
 Ferroelectricity is defined by the appearance of a macroscopic electric
polarization and its reversibility by applying an external field
 For some ferroelectric materials, electron degrees of freedom and/or

electronic interactions directly give rise to a macroscopic electric
polarization and a ferroelectric transition  electronic
ferroelectricity
Outstanding Properties of ferroelectrics
 The reversibility of the permanent polarization by an

electric field. Reversibility is a result of the fact that the
polar structure of a ferroelectric is a slightly distorted
nonpolar structure. The distortion gives rise to nonlinear
dielectric behavior.
 Ferroelectrics have very high dielectric constants at
relatively low applied field frequencies. Capacitors made
from these materials can be significantly smaller than
capacitors made out of other dielectric materials.
 Eg: Barium Titanate, Rochelle salt, potassium
dihydrogen phosphate, potassium niobate, and lead
zirconate-titanate (PZT)
Curie Point & Phase Transitions
 All ferroelectric materials have a transition temperature

called the Curie point (TC).
 At T > TC the crystal does not exhibit ferroelectricity, while
for T < TC it is ferroelectric.
 On decreasing the temperature through the Curie point, a
ferroelectric crystal undergoes a phase transition from a
non-ferroelectric phase to a ferroelectric phase.
 If there are more than one ferroelectric phases, the T at
which the crystal transforms from one phase to another is
called the transition temperature.
 For example, the variation of the relative

permittivity er with temperature as a BaTiO3
crystal is cooled from its paraelectric cubic phase
to the ferroelectric tetragonal, orthorhombic, and
rhombohedral phases.
 Near the Curie point or transition temperatures,
thermodynamic properties including dielectric,
elastic, optical, and thermal constants show an
anomalous behavior.
 This is due to a distortion in the crystal as the
phase structure changes.
Variation of dielectric constants (a and c axis) with temperature for BaTiO3
BaTiO3
 BaTiO3 has a paraelectric cubic phase above its Curie point of

about 130°C.
 In the T of 130°C to 0°C, the ferroelectric tetragonal phase
with a c/a ratio of ~ 1.01 is stable.
 The spontaneous polarization is along one of the [001]
directions in the original cubic structure.
 Between 0°C and -90°C, the ferroelectric orthorhombic phase
is stable with the polarization along one of the [110] directions
in the original cubic structure.
 On decreasing T below -90°C the phase transition from the
orthorhombic to ferroelectric rhombohedral phase leads to
polarization along one of the [111] cubic directions.
[001]
directions
[110] [111]
directions directions
The phase transition sequence in perovskites
Phase diagram of BaTiO3: (a) bulk single crystal and (b) epitaxial (001)
single domain thin films grown on cubic substrates of high
temperatures as a function of the misfit strain. The second- and first-
order phase transitions are shown by thin and thick lines, respectively.
The perovskite structure ABO3 shown here for PbTiO3 which has a cubic
structure in the paraelectric phase and tetragonal structure in the
ferroelectric phase.
Antiferrolectric Materials
 “Crystals that are isomorphous to ferroelectrics,

undergo with decreasing temperature phase transitions
from a state of higher symmetry to a state of lower
symmetry which are connected with slight distortions
of the crystal lattice. This leads to twinning. However,
the twins have no net electric dipole moment. In most
cases the crystal structure of the low symmetry phase
can be described in terms of equivalent sublattices with
equal but opposite polarization.”
PZT Phase Diagram
Pb(Zr1-xTix)O3(PZT) is probably the most important piezoelectric
material. The piezoelectric properties are optimal near x = 0.5,
This composition is near the morphotropic phase boundary, which
separates the tetragonal and rhombohedral phases.
Hysteresis Loops in PbZr1-xTixO3
PbTiO3 PbZr1-xTixO3
Ferroelectric x ~ 0.3
Tetragonal Ferroelectric
Rhombohedral
PbZr1-xTixO3 PbZrO3
Paraelectric Antiferroelectric
Cubic Monoclinic
An antiferroelectic material does not polarize much for low applied fields, but
higher applied fields can lead to a polarization loop reminiscent of a
ferroelectric. The combination gives split hysteresis loops as shown above.

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1

Dielectric and Ferroelectric Properties of Materials

Dielectric means a non-conductor or poor conductor of electricity.

Dielectric means a material that presents electric polarization.

The dielectric is an insulating material or a very poor conductor of electric

The resistivity of insulators is:   107  1018   m

If a material contains polar molecules, they will generally be in random

 Capacitor – An electronic device, constructed from

 Maximum electric field that an insulator can withstand

When the relaxation time is much faster than the frequency

When the relaxation time is much slower than the frequency

When the relaxation time and the frequency of the applied

D = eE = e0E + P = e0E + e0ceE = e0(1+ce)E

er = e/e0 = 1+ce

2. Ionic Polarizability (ai) Response

4. Space Charge Polarizability (as)

without with field x

The presence of an electric field polarizes the electron

1. Electronic Polarizability (ae)

Audiofrequencies (~ 103 Hz) a=

The 32 point groups can be divided up in the following manner (color

Most dielectric materials are insulating (no conductivity of either

1. Certain ions in the structure displace in response to the application

•The polarization does not go

•The direction of the

Applications of Ferroelectric Materials

 Ferroelectricity is an electrical phenomenon whereby

Spontaneous polarization is a function of temperature. Ps

 Two stimuli that will change the lattice dimensions

 Placing a ferroelectric material between two conductive

 The combined properties of memory, piezoelectricity, and

 Most ferroelectric materials undergo a structural phase

– where C is the Curie constant, T0 (T0 ≤TC) is the Curie–Weiss

1. Corner Sharing Octahedra:

2. Compounds Containing Hydrogen Bonded Radicals

3. Organic Polymers (such as PVDF and co-polymers)

4. Ceramic Polymer Composites (such as PZT-PE)

• The ferroelectricity can be explained by the PbTiO3 (763K )

Inside each Octahedron  Cation Bb+ (3 < b < 6)

In prototypic forms, Aa+, Bb+, and O2- ions geometrically coincide

Phase Transitions Changes in Lattice Structure 

 For some ferroelectric materials, electron degrees of freedom and/or

 The reversibility of the permanent polarization by an

 All ferroelectric materials have a transition temperature

 For example, the variation of the relative

Variation of dielectric constants (a and c axis) with temperature for BaTiO3

 BaTiO3 has a paraelectric cubic phase above its Curie point of

The phase transition sequence in perovskites

 “Crystals that are isomorphous to ferroelectrics,

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