Chapter – 6 Electrical properties of Solids

Contents

Dielectric and ferroelectric properties of solids.

Dielectric constant and polarizability.
Liddanne – sachs – Teller Relation .
Dielectric Relaxation Time.
Dipole Theory of Ferro- electricity .
Piezo Electricity
 Dielectric and Ferro-electric Properties of solids
Dielectric materials :
Dielectric substance are those in which atoms or ion’s packed with electron and in presence of
Electric field there is no flow of charge but polarization takes place and dipole is develop.
A dielectric material is a non-metallic substance having high specific resistance, a negative
temperature co-efficient of resistance and a high insulating resistance .
 Dielectric and Ferro-electric Properties of solids
When a dielectric placed in an electric field, the electronic charge do not flow through the
material. Electrical charges slightly shift from their average equilibrium positions causing
dielectric polarization.
Dielectric polarization causes positive charges to flow in the direction of field and negative
charges shift in the opposite direction of the field. This phenomenon yields an internal electric
field, which is turn reduced the electric field within the dielectric material. Electric susceptibility
gives the measure of how easily a dielectric material can be polarized when placed in an electric
field. Dielectric materials are mostly solid. ceramic , plastic , Mica and glass are solid dielectric .
Applications of dielectric properties :
Dielectrics are used as a capacitor for storing energy.
The Dielectric Material in a Transformer is used as a insulator and as a cooling agent.
To enhance the performance of a semiconductor device , high permittivity dielectric materials
are used.
Electrets are a processed dielectric material that act’s as a electrostatic equivalent to magnets .
 Dielectric properties
Dielectric properties

These dielectric substance arrange in such a These dielectric substance arrange in such a manner there
manner there is no net dipole µ =0 is no net dipole µ not equal to zero.

The dielectric properties of solid :

Piezoelectricity
Pyroelectricity
Ferroelectricity
Anti ferroelectricity
 Piezoelectricity
Piezoelectricity is the ability of the material to develop electric charge in response to applied mechanical stress (Direct
piezoelectric effect) and vice versa (inverse piezoelectric effect) . Piezoelectricity was first observed by Yasuda.
Piezoelectric effect is the ability of certain materials to generate an electric charge in response to applied mechanical
stress. The word piezoelectric is derived from the Greek Piezien , which means to the squeeze or press , and piezo
which is Greek for push . One of the unique characteristics of piezoelectric effect is that it is reversible , meaning that
materials exhibiting the direct piezoelectric effect (The generation of electricity when stress is applied) also exhibit
the converse piezoelectric effect (The generation of stress when a electric field is applied ). When piezoelectric
material is placed under the mechanical stress, a shifting of the positive and negative charge centers in the material
takes place , which is then results in the external electrical field . When reversed in a outer electrical field either stress
or compresses the piezoelectric material. Example : Pbzro3 , Rochelle salt NH4 H2 PO4, Quartz etc.
 Piezoelectricity

Piezoelectricity is the process of using crystals to convert mechanical energy into electrical energy and vice– versa .
Regular crystal are defined by their organized and repeating structure of atoms that are held together by bonds, this is
called unit cell . Most crystals such as iron have a symmetrical unit cell , which makes them useless for piezoelectric
purposes. There are other crystals that get lumped together as piezoelectric materials . The structure in these crystals
are not symmetrical but they still exist in an electrically neutral balance. If we apply mechanical pressure to a
piezoelectric crystal, the structure deforms , atoms get pushed around and suddenly crystal that can conduct electric
current. That’s it, a simple applications of mechanical pressure , the squeezing of a crystal and suddenly we have an
electric current. Applying electrical signal to a material as an inverse piezoelectric effect .
 How Piezoelectricity works ?

Applying mechanical energy to a crystal is called a direct piezoelectric effect and works like this:
1. A piezoelectric crystal is placed between two metal plates. At this point the material is in
perfect balance and does not conduct an electric current.
2. Mechanical pressure is then applied to the material by the metal plates, which forces the electric
charges within the crystal out of balance. Excess negative and positive charges appear on opposite
sides of the crystal face.
3.The metal plate collects these charges, which can be used to produce a voltage and send an
electrical current through a circuit.
 How Piezoelectricity works ?

That’s it, a simple application of mechanical pressure, the squeezing of a crystal and suddenly you have an
electric current. You can also do the opposite, applying an electrical signal to a material as an inverse
piezoelectric effect. It works like this:
1.In the same situation as the example above, we have a piezoelectric crystal placed between two metal
plates. The crystal’s structure is in perfect balance.
2.Electrical energy is then applied to the crystal, which shrinks and expands the crystal’s structure.
3.As the crystal’s structure expands and contracts, it converts the received electrical energy and releases
mechanical energy in the form of a sound wave.
 Pyroelectricity
When some polar crystals are heated they produce a small electric potential . The
electric potential thus produced is known as pyroelectricity . This phenomenon is
termed as pyroelectric effect . In these polar crystal the electric impulse is produce
on heating due to displacement of ion’s it is the bridge between ferroelectric and
piezoelectric Material.
Ex : perovskite . It has wide range of research application.
 Ferroelectricity and Ferroelectric properties of solids

Ferroelectricity:
Some piezoelectric crystal have permanent dipoles and are called as ferroelectric crystals. Even in the absence of
electric field , the retain the arrangement of dipoles . By applying an external electric field the direction of the
polarization of dipoles in these kind of crystals can be reversed ferroelectricity is analogous to ferromagnetism. In
these polar crystal the alignment of dipole in same direction. In this case Electricity is develop due to the
displacement of dipoles. Example: KH PO4 , Rochelle salt.
Ferroelectricity, property of certain non conducting crystals, or dielectrics that exhibit spontaneous electric
polarization (separation of the center of positive and negative electric charge , making one side of the crystal positive
and the opposite side negative ) that can be reversed in direction by the application of an appropriate electric field.
Ferroelectricity is named analogy with ferromagnetism , which occurs in such materials as iron. Iron atoms, being tiny
magnets spontaneously align themselves in clusters called ferromagnetic domains, which in turn can be oriented
predominantly in a given direction by the application of an external magnetic field.
Ferroelectric materials are composed of crystal in which the structural units are tiny electric dipoles , that is , in each
unit the center of positive and negative charge are slightly separated. In some crystals these electric dipoles
spontaneously line up in clusters called domains, and in ferroelectric crystals. The domains can be oriented
predominantly in one direction by a strong external electric field.
 Ferroelectricity and Ferroelectric properties of solids
This lag of Electric polarizations behind the applied electric polarizations behind the
applied electric field is ferroelectric hysteresis , named by analogy with
ferromagnetic hysteresis.
Ferroelectricity ceases in a given material above a characteristic temperature ,
called it’s curie temperature.
 Anti-Ferroelectricity
The effect under which the net dipole moments of piezoelectric crystal is zero is referred to as Anti- ferroelectric . In
these polar crystal the alignment of dipole in opposite direction and the electricity is produced due to change in
direction of dipole .
Antiferroelectricity is highly linked to ferroelectricity. They are contrast with each other. So we have to know that
ferroelectricity is also a physical property which polarizes quickly. By varying the direction of the field applied we
can invert the direction of polarization. So, the difference is the direction of dipoles after polarization. The former will
align anti parallel and latter will align in the same direction. Antiferroelectric property is steady than ferroelectric
property in a plain cubic pattern.
The entire macroscopic spontaneous polarization in antiferroelectric material is zero. The reason is that the closest
dipoles will cancel each other. This property can emerge or vanish depending on various parameters. The parameters
are external field, pressure, growth method, temperature etc. The antiferroelectric property is not piezoelectric. That is
there is no change in mechanical character of the material by the application of external field. These materials usually
have high dielectric constant. The dipole orientation of this material is similar to the chess board pattern which is
shown below.
Antiferroelectric Materials : Anti-Ferroelectricity
The examples of antiferroelectric materials are as follows
•PbZrO3 (Lead Zirconate)
•NH4H2PO4 (ADP: Ammonium dihydrogen Phosphate)
•NaNbO3(Sodium Niobate)
Antiferroelectricity and Temperature :
The antiferroelectric property will vanish above a particular temperature. This we can call as Antiferroelectric Curie
point. The materials and their curie temperature are shown in Table no.1. The dielectric constant (relative permittivity)
less and more than this Curie point is investigated. This is done for both first and second order transition. In the
second order transition, dielectric constant is continuous all over the Curie point. In the two cases dielectric constant
must not be very high.
Application of Antiferroelectricity:
•Super capacitors
•MEMS Application
•Used in integration with ferromagnetic materials
•High energy storage devices
•Photonic application
•Liquid crystal etc.
 Anti-Ferroelectricity
Double Hysteresis Loop
The Hysteresis loop of a perfect antiferroelectric material can be drawn as shown in Figure 2
below. The reversal of spontaneous polarization of these materials gives a double hysteresis loops.
The external field applied is a low frequency AC field.
 Dielectric constant and Polarizibility
Dielectric Constant :
The dielectric constant of the material relates to the susceptibility of the material, which relates to
the polarizability of the molecules . Since χ is frequency dependent because of the different
mechanisms that can include polarizations, then є the dielectric constant is also frequency
dependent .
Polarization
 Polarization
Let us consider a electric slab in a electric slab in a electric field which
acting on the direction shown in figure. The arrangement of charges
within the molecules of the dielectric in the electric field shown in figure.
The positive charges moves in the direction of the field, and the negative
charges moves in the opposite direction. In other words, the electric
dipoles align themselves with the direction of the field. In this state, the
entire dielectric and its molecules are said to be polarized. The alignment
of the dipole moments of the permanent or induced dipoles with the
direction of the applied electric field is called polarization.
Polarization can thus also be thought of as a phenomenon in which an
alignment of positive and negative charges takes place within the
dielectric resulting in no net increase in charge of dielectric .
 Polarization
Dipole moment induced inside the dielectric to polarization . The polarization P is equal the sum of the individual dipole moments
inside the dielectric divided by total volume of the dielectric(V).
P = ∑ Pi / V.
P = Polarization inside the dielectric .
Pi = Induced Dipole Moment inside the dielectric .
V = Volume of the Dielectric .
Dipole Moment per unit volume also called Polarization .
In case of Linear Dielectrics the magnitude of polarization is directly proportional to the intensity of electric field at a given point
of Dielectric .
P∞E
P = χe Є 0 E
χe = Electrical susceptibility
Ke Є0 = This product is called absolute Dielectric susceptibility .
In case of non- linear dielectric There is no proportionality between P and E.
Polarizations of Dielectrics:
Polarization is some ordering in space of the electrically charged particles with their displacement in a dielectric under the
influence of an External electric field . This causes the formation of an electric moment in the entire volume of the dielectric and
each separate polarizing particle ( atom, ion, molecules ) . Polarization is directly proportional to electric field E then,
P = α.E
The co-efficient of Proportionality of a given particle polarizability reflects the properties of an individual particle of matter and
not of a certain very large volume of it .
 Polariton
When transverse optical phonon’s and transverse electromagnetic wave are at resonance condition , then the phonon –
photon coupling is called polariton.
Properties of polariton :
I. Polariton is a bosonic quasiparticle .
II. Polariton formed when photons couple strongly with exciton.
III. Phonon – photon coupling can be expressed by dielectric function .
Types of polariton :
Phonon polariton :
Result from coupling of visible light with an exciton polariton.
Exciton polariton :
Result from coupling of visible light with exciton .
Intersubband polariton :
Result from coupling of surface plasmon with light .
Surface plasma polariton :
Result from coupling of surface plasmon with light .
Bragg polariton :
Result from coupling of bragg photon with bulk exciton.
Magnon Polariton:
Result from coupling of magnon with light .
 Liddane –sachs – Teller Relation
According to electromagnetic wave equation we have ,
e2 K2 E = W2 (E + 4πP ) --------(1)
Here, P = Polarization , E = Electric Field of the Phonon .
Now from equation of motion of Polariton :
(WT )2 P – (W)2 P = Nq2 / M ×E --------------(2)
Here, V = No. of ion Pairs , q = effective mass , M = Reduced Mass .
The solution of equ(1) and equ (2) We can write ,
C2 K2 – W2 4πW2
= 0 -----------(3)
Nq2 / M (WT )2 – W2
But , From the definition of Dielectric Function we have,
Є (w) = 1 + 4πP / E -----------(4)
From Equ (2) we have ,
( WT)2 P – W2 P = N q2 /m × E
P [ (WT )2 - W2 ] = Nq2 / M ×E
 P = (Nq2 / M ×E) / [ (WT )2 - W2 ]
 Liddane –sachs – Teller Relation

Now we substitute p value in equ (4) and we can write ,

Є (w) = 1 + 4π / E × (Nq2 / M ×E) / [ (WT )2 - W2 ] -----------(5)
In the infrared frequency range equ(5) can be re-write as,
Є (w) = є (α) + 4π / M × (Nq2 / [ (WT )2 - W2 ] ) -----------------(6)
To finding static dielectric function we just putting w = 0 in equ (6) and we can write ,
Є (0) = є (α) + 4π / M × (Nq2 / [ (WT )2 ] ) -----------(7)
Thus Form equ (6) and (7) we can write ,
Є (W) = є(α ) [ {(WL )2 – (W)2 } / {(WT )2 – (W)2 } ----------(8)
Here , WL = optical phonon frequency
So, if we putting w = 0 in equ(8) and we can write ,
Є (0) = є (α )[ {(WL )2 – (0)2 } / {(WT )2 – (0)2 }
(WL )2 / (WT )2 = Є (0) / Є (α )
This is known as the Liddane – sachs – Teller relation .
 The Dipole Theory of Ferroelectricity
The dipole moment per unit cell may result partly from electric and ionic displacements and partly from permanent
dipoles. The exact theory explain the properties of Rochelle salt were based on the assumption that the permanent
dipole moments of the water groups were responsible for the spontaneous polarizations. This dipoles were assumed to
be freely rotating and theory analogous to the Langevin – Weiss theory of ferromagnetism was developed.
The internal field Ei which tends to orient a given dipole is assumed to be in the form ,
Ei = E + γP -----------(1)
Where ,Ei is the exactly applied field .
γ is the internal field constant .
P is the polarization .
For high temperature region, an internal field of the form equ(1) indeed leads to the curie – Weiss law :
 The Dipole Theory of Ferroelectricity
Langevin function ,
L(x) = < cosϴ > = a / 3 = 1/3 × µE / KT
Polarizations ,
P = Nµ < cosϴ > = N ( µ2 / 3KT) Ei ----------(2)
Where N is the number of dipoles per unit volume , µ is the permanent dipole moment .
From (1) and (2) =>
χ = P / E = {N ( µ2 / 3KT) Ei }/ Ei ( 1 - Nγ2 µ2 / 3KT ) = (ϴ / γ) / T - ϴ = C / T - ϴ --------(3)
Ei = E + γP
E = Ei – γP = Ei – γ × N ( µ2 / 3KT) Ei
E = Ei (1 - N γ2 µ2 / 3KT)
Where , curie temperature , ϴ = N γ2 µ2 / 3K
Curie constant , C = ϴ / γ
P = Nµ<cosϴ> = Nµ L(a) = NµL ( µEi / Kr ) = NµL [ µ /Kr × ( E + γP ) ] ---------(4)
Where L(a) = L(x) is the Langevin functions put E =0 in (4) then ,
P / Nµ = P / Psat = L(x) -------(5)
Where, X = µγP / KT (α) P / Nµ = ( KT / Nµγ ) α ----------(6)
 The Dipole Theory of Ferroelectricity
Nµ = P represent evidently of saturation polarization corresponding to complete alignment of the
dipoles .

T>ϴ
ϴ
T<ϴ

P / Psat K
L (a)

α
 The Dipole Theory of Ferroelectricity
The solution for P/Psat corresponding to the temperature T is determined by the intersection of
L(X) and the line of slope
KTi / Nµ2 γ.
It is observed that as T decreases , the slope of the straight line equ (6) decreases as the solution P
/ P approaches to unity also, when the temperature is higher than a critical value determined by ,
K Te / Nµ2 γ = 1 /3 , Te = N µ2 γ / 3K = ϴ ---------(7)
It is observed that Equ (5) and equ (6) intersect only at the origin.
In other words , There is no spontaneous polarization for T >ϴ.
It is observed that below the curie temperature the spontaneous polarizations increases rapidly .

P / Psat

T/ϴ