Mphs 43 Cmp2 Final

MASTER OF SCIENCE IN PHYSICS
CONDENSED MATTER PHYSICS – II
MPHS-43
SEMESTER - IV
Department of Physics
School of Sciences
Tamil Nadu Open University
577, Anna Salai, Saidapet, Chennai - 600 015
www.tnou.ac.in
March 2023
Name of the Programme: M.Sc., Physics
Course Code: MPHS-43
Course Title: Condensed Matter Physics – II
Curriculum Design
Dr. E. Kumar
Assistant Professor of Physics
School of Sciences
Tamil Nadu Open University, Chennai - 15
Dr. P. Shanmugavelan
Assistant Professor of Chemistry
Department of Chemistry
School of Sciences
Tamil Nadu Open University, Chennai -15
Course Writer
Dr. S. Paulraj,
Assistant Professor & HOD, Department of Physics,
Vels Institute of Science Technology and Advanced Studies,
Chennai.
Course Coordinator & Content Editor

Dr. E. Kumar
Assistant Professor of Physics
School of Sciences
Tamil Nadu Open University, Chennai - 15
Total No of Pages: 210
March 2023 ( First Edition)
ISBN No: 978-93-5706-518-4
©Tamil Nadu Open University

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SYLLABUS
COURSE TITLE : CONDENSED MATTER PHYSICS – II
COURSE CODE : MPHS 43
COURSE CREDIT : 4
COURSE OBJECTIVES
While studying the CONDENSED MATTER PHYSICS – II, the Learner shall be able
to:
CO 1: Learn the basics of theories of dielectrics

CO 2: Study about fundamental theory of ferroelectrics and piezo electrics
CO 3: Discuss the various types of magnetic materials
CO 4: Study about the different parameters associated with superconductivity and
the theory of superconductivity, idea of high temperature superconductivity.
CO 5: Define the term physics of nanosolids, and outline the various properties of
nano materials and their fabrication techniques.
COURSE SYLLABUS
BLOCK I: THEORY OF DIELECTRICS

Dipole moment – Polarization – The electric field of a dipole – Local electric field at an
atom – Clausius –Mosotti equation - Dielectric constants and its measurements -
Polarizability – The Classical theory of electronic polarizability – Ionic polarizabilities
- Orientational polarizabilities - The polarizability catastrophe - Dipole orientation in
solids - Dipole relaxation and dielectric losses – Debye Relaxation time - Relaxation in
solids - Complex dielectric constants and the loss angle - Frequency and temperature
effects on Polarization – Dielectric breakdown and dielectric loss
BLOCK II: THEORY OF FERROELECTRICS AND PIEZO ELECTRICS

Ferroelectric Crystals – Classifications of Ferroelectric crystals - Dipole theory of
ferroelectricity – Landau Theory of the phase transition – Second order Transition –
First Order Transition - Ferroelectric Transition - One-Dimensional Model of the Soft
Mode of Ferroelectric Transitions – Antiferroelectricity - Ferroelectric domains –
Ferroelectric domain wall motion – Piezoelectricity - Phenomenological Approach to
Piezoelectric Effects - Piezoelectric Parameters and Their Measurements - Piezoelectric
Materials
BLOCK III: MAGNETIC PROPERTIES OF MATERIALS

Terms and definitions used in magnetism – Classification of magnetic materials –
Atomic theory of magnetism – The quantum numbers- The origin of permanent
magnetic moments – Langevin’s classical theory of diamagnetism – Sources of
paramagnetism – Langevin’s classical theory of paramagnetism – Quantum theory of
paramagnetism – Paramagnetism of free electrons - Ferromagnetism – The Weiss
molecular field – Temperature dependence of Spontaneous magnetization – The
physical origin of Weiss Molecular field - Ferromagnetic domains - Domain theory –
Antiferromagnetism – Ferrimagnetism – Structure of Ferrite.
BLOCK IV: SUPERCONDUCTIVITY

Occurence of super conductivity - Destruction of super conductivity by magnetic
fields - Meissner Effect – Type I and Type II Super conductors - Heat Capacity -
Energy gap - Microwave and infrared properties - Isotope effect - Thermodynamics of
the superconducting transition - London equation - Coherence Length - BCS theory of
superconductivity, BCS ground state - Flux quantisation in a super conduction ring -
Duration of persistence currents - Single particle tunnelling - DC Josephson effect -
AC Josephson effect - Macroscopic quantum interference – High temperature super
conductors – Applications.
BLOCK V: PHYSICS OF NANOSOLIDS

Definition of nanoscience and nanotechnology – Preparation of nanomaterials –
Surface to volume ratio – Quantum confinement – Qualitative and Quantitative
description – Density of states of nanostructures – Excitons in Nano semiconductors –
Carbon in nanotechnology – Buckminsterfullerene – Carbon nanotubes – Nano
diamond – BN nano tubes – Nanoelectronics – Single electron transistor – Molecular
machine – nano biometrics.
BOOKS FOR STUDY:
1. Charles Kittel, Introduction to Solid State Physics, 7th Edition, Wiley India Pvt.
Ltd. , New Delhi, 2004.
2. Rita John, Solid State Physics, Tata Mc Graw Hill Publications, 2014.
3. M. A. Wahab, Solid State Physics – Structure and Properties of Materials. Narosa,
New Delhi, 1999.
4. J.D. Patterson, B.C. Bailey Solid-State Physics: Introduction to the Theory, Springer
Publications, 2007.
5. M. Ali Omar, Elementary Solid State Physics – Principles and Applications,
Pearson, 1999.
BOOKS FOR REFERENCE:
1. J. Blakemore, Solid State Physics, 2nd Edition, W. B. Saunders Co, Philadelphia,
1974.
2. C. M. Kachhava, Solid State Physics, Tata Mcgraw Hill, New Delhi, 1990.
3. N. W. Aschroft and N. D., Mermin, Solid State Physics, Rhinehart and Winton,
New York. 1976.
4. M. Tinkham, Introduction to Superconductivity, Tata Mcgraw Hill, New Delhi,
1996.
5. K.K.Chattopadhyay, A.N.Banerjee, Introduction to Nanoscience and
Nanotechnology, PHI Learning private Ltd., Delhi 2014.
6. A. J. Dekker, Electrical Engineering Materials, Prentice Hall of India, 1975.
7. S.O. Pillai, Problems and Solutions in Solid State Physics, New Age international
Publishers, New Delhi, 1994.
8. A.K. Bain, P. Chand, Ferroelectrics, Wiley, 2017.
9. Kwan Chi Kao, Dielectric phenomena in solids with eMPHSasis on physical
concepts of electronic processes, Elsevier Academic Press, 2004
10. Alexander O. E. Animalu, Intermediate Quantum Theory of Crystalline solids,
Prentice Hall of India, New Delhi, 1978.
11. Eleftherios N. Economou, The Physics of Solids – Essentials and Beyond,
Springer, 2010.
Web Resources
1. Dielectrics - Definition, Classification, Dielectric Polarization, Examples (byjus.com)
2. Clausius Mossotti Equation | Dielectric Constant | MSc Physics | Condensed
Physics |CSIR NET Physics - YouTube
3. 29 Dielectric Materials - Introduction - YouTube
4. Lec 33 Polarization of Dielectrics | HC VERMA | GDS K S - YouTube
5. Lec 34 Bound charge densities | HC VERMA | GDS K S - YouTube
6. Lec 35 Electric field due to a polarized material | HC VERMA | GDS K S - YouTube
7. LEC 36 Problem Solving with Dielectrics | HC VERMA | GDS K S - YouTube
8. LEC 37 Displacement field | HC VERMA | GDS K S - YouTube
9. LEC 38 Linear Dielectrics | HC VERMA | GDS K S - YouTube
10. MSc#Physics#Dipole theory of ferroelectricity - YouTube
11. Ferroelectric Materials - YouTube
12. https://www.youtube.com/watch?v=CO0E9QTDBbs
13. Ferroelectrics- Part IV : Curie Wiess law for Ferroelectricity - YouTube
14. Ferroelectric, Pyroelectric and Piezoelectric Materials #msc #gate #bsc #chemistry
#csirnetjrf - YouTube
15. Mod-08 Lec-19 Ferroelectric , Piezoelectric and Pyroelectric Ceramics - YouTube
16. Mod-08 Lec-20 Ferroelectric , Piezoelectric and Pyroelectric Ceramics (Contd.) -
YouTube
17. Magnetic Properties - YouTube
18. What Is Magnetic Susceptibility? - Formula, Definition, Unit (byjus.com)
19. 29- MAGNETIC PROPERTIES OF MATERIALS - YouTube
20. MAGNETIC PROPERTIES OF SOLIDS & EFFECT OF TEMPERATURE ON SUCH
MATERIALS - YouTube
21. L 07 | Magnetic materials | Bound and free currents | Ampere's law in a magnetised
material | BSc | - YouTube
22. Magnetism, Magnetic Field Force, Right Hand Rule, Ampere's Law, Torque,
Solenoid, Physics Problems - YouTube
23. Superconductivity#Lecture 1#Solid State Physics#M.Sc. Final - YouTube
24. Superconductivity#Lecture 2#M.Sc. Final#Solid State Physics - YouTube
25. Superconductivity#Lecture 3rd#Solid state Physics#M.Sc. Final - YouTube
26. Superconductivity#Lecture4#Solid state physics#M.Sc. Final - YouTube
27. Superconductors and Supercapacitors Session 1 (Superconductors, Critical
temperature and field) - YouTube
28. Mod-01 Lec-27 Superconductivity - Perfect Electrical Conductivity and Perfect
Diamagnetism - YouTube
29. Mod-01 Lec-28 Type I and Type II Superconductors - YouTube
30. Mod-01 Lec-29 Ginsburg - Landau Theory, Flux Quantization - YouTube
31. Mod-01 Lec-30 Cooper Pairs - YouTube
32. Mod-01 Lec-31 Microscopic (BCS) Theory of Superconductivity - YouTube
33. Mod-01 Lec-32 BCS Theory (Continued): Josephson Tunneling: Quantum
Interference - YouTube
34. Physics of Nano Scale Materials; Course Summary - YouTube
35. Introduction To Nanophysics | Nanoscience and Nanotechnology - YouTube
36. Introduction To Nanophysics | Nanoscience and Nanotechnology - YouTube
37. Size Dependent Properties Of Nanoparticles | Size Dependence Of Properties -
YouTube
38. Surface Energy And Melting Point Depression Of Nanoparticles In Hindi | Physics
Of Nanomaterials - YouTube
39. Properties And Applications Of Carbon Nanotubes | Properties Of CNT - YouTube
40. CARBON NANOTUBES - PROPERTIES & APPLICATIONS - YouTube
COURSE LEARNING OUTCOMES
After completion of the CONDENSED MATTER PHYSICS – II, the Learner will be
able to:
CLO 1: Describe the Local electric field at an atom, Clausius –Mosotti equation and
the Classical theory of electronic polarizability and its types
CLO 2: Discuss the Classifications of Ferroelectric crystalsand Various theories of
ferroelectricites (Dipole theory of ferroelectricity, Landau Theory of the
phase transition).
CLO 3: Differentiate the Various Types of Magentic materials (dia, para and Ferro)
on the basis of Langevin’s classical theory and domain theory
CLO 4: Distinguish between type-I and type-II superconductors and their theories
and explain the behavior of superconductors, applications and high
temperature superconductivity.
CLO 5: Explain the concept of quantum confinement, electron confinement in deep
square well and two and three dimensions, idea of quantum well, dot and
wires.
Contents
Page
S.No. Title
No
1 BLOCK I - THEORY OF DIELECTRICS 1
1.1 Unit 1: Polarization 2
1.2 Unit 2: Types of Polarization 16
1.3 Unit 3: Dielectric Relaxation 28

BLOCK II: THEORY OF FERROELECTRICS AND PIEZO
2 46
ELECTRICS
2.1 Unit 4: Ferroelectric Crystals and Phase Transition 47
2.2 Unit 5: Phase Transitions 56
2.3 Unit 6: Antiferroelectricity and Piezoelectricity 67
3 BLOCK III: MAGNETIC PROPERTIES 80
3.1 Unit 7: Classification of Magnetic Materials 81
3.2 Unit 8: Diamagnetism and Para magnetism 91
Unit 9: Ferromagnetism, Anti-ferromagnetism and Ferrimagnetism 102

3.3
4 BLOCK IV: SUPERCONDUCTIVITY 118
4.1 Unit 10: Introduction to Superconductivity 119
4.2 Unit 11: BCS Theory 132
4.3 Unit 12: Applications of Superconductivity 143
5 BLOCK V: PHYSICS OF NANOSOLIDS 157
5.1 Unit 13: Physics of Nanosolids 158
5.2 Unit 14: Carbon Nanotechnology 177
5.3 Unit 15: Nanoelectronics 187
Appendix – Plagiarism Certificate 199

BLOCK I - THEORY OF DIELECTRICS
Unit 1: Polarization
Unit 2: Types of Polarization
Unit 3: Dielectric Relaxation
1
UNIT 1
POLARIZATION
Structure
Overview
Objectives
1.1 Dipole moment
1.2 Polarization
1.3 The electric field of a dipole
1.4 Local electric field at an atom
1.5 Clausius –Mosotti equation
1.6 Dielectric constants and its measurements
Let Us Sum Up
Check Your Progress
Answers to check your progress
Unit End Exercises
Suggested Readings
OVERVIEW
The term dielectric is used in broad sense, as relating to various electrical

phenomena, primarily in ceramics and polymers. Dielectric materials are
electrical insulators and they are principally used in capacitors and
electrical insulators. The energy band model of a dielectric (insulator) is
similar to that of a semiconductor except that the forbidden gap in
dielectric materials is comparatively larger. In such materials, the
electrons are tightly bound to the atoms so that at ordinary temperatures
they cannot be dislodged either by thermal vibrations or with ordinary
fields. However, they can only move a bit within the molecule and their
cumulative effect account for the characteristic behaviour of dielectric
materials.
2
The dielectric material for the practical applications should possess the
following properties:
High electrical strength, i.e they should be able to withstand high voltage
without undergoing degradation and becoming electrically conducting
Low electric loss, i.e in an alternative electric field, the loss of electrical
energy, which appears as heat should be minimised.
Dielectric materials include some solids such as glass, porcelain, etc.,

liquids such as chemically pure water, methyl chloride (CH3Cl), etc., and
gases such as hydrogen, nitrogen, carbon tetra chloride (CCl4) ammonia
(NH3) etc.
The negative and positive charges in each part of the crystal can be
considered to be centred at the same point, and since no conductivity is
possible, the localised charges remain practically undisturbed. When an
electric field is applied sufficiently to the crystal, the centres of the positive
charges are displaced slightly in one direction (i.e the direction of the field)
and that of the negative charges in the opposite direction. This produces
local electric dipole throughout the crystal, where an electric dipole is an
entity in which equal and opposite charges are separated by a small
distance. In the case of polar molecules, the nuclei and electrons in the
molecule are arranged in such a way that the centres of mass of the
positive and negative charges do not coincide even in the absence of
electric field and they behave like rigid dipoles.
OBJECTIVES
After learning this unit, learners will be able to

➢ Describe the dipole moment and polarization of an atom
➢ Explain the local field and derive the Clausius –Mosotti equation
➢ Understand the Dielectric constant and its measurements
1.1 DIPOLE MOMENT
If we have two equal and opposite charges, +q and -q as shown in

the Fig. 1.1, the moment of this dipole can be defined as
3
Fig 1.1 An electric dipole
𝜇 = 𝑞𝑟 (1)
And is defined from the negative to the positive charge. The dipole
moment is thus equal to one of the charges times the distance between
them. The total dipole moment is defined as
𝜇 = ∑ 𝑞𝑛 𝑟𝑛 (2)
Where rn is the position vector of the charge qn.
1.2 POLARIZATION
When a dielectric is placed in an external electric field, it becomes

polarised, i.e within a small volume of substance the geometric sum of the
electric dipole moment vectors of the molecules becomes non zero. The
polarization P is thus defined as the dipole moment per unit volume.
𝜇
𝑃=𝑉 (3)
If the number of molecules per unit volume is N and if each has a moment
μ, then the polarization is given by
𝑃 = 𝑁𝜇 (4)
The mechanism of polarization differs for non-polar and polar dielectric

materials.
4
1.3 THE ELECTRIC FIELD OF A DIPOLE
If we choose the coordinates such that polarization vector P lies at the

origin and points in the z-direction (Fig. 1.2), then the potential at a point
(r, θ) from the centre of the dipole is given by
𝑃 cos 𝜃
𝑉(𝑟, 𝜃) = 4𝜋𝜀 2 (5)
0𝑟
Fig 1.2 Electric field of a dipole
The electric field is equal to the negative of the potential gradient, we can
write various components of the field in the spherical polar coordinate
system as:
𝜕𝑉 2𝑃 cos 𝜃
𝐸𝑟 = − =
𝜕𝑟 4𝜋𝜀0 𝑟 3
1 𝜕𝑉 𝑃 sin 𝜃
𝐸𝜃 = − =
𝑟 𝜕𝜃 4𝜋𝜀0 𝑟 3
and
1 𝜕𝑉
𝐸∅ = − =0
𝑟 sin 𝜃 𝜕∅
5
Thus,
𝑃
̂=
𝐸(𝑟, 𝜃) = 𝐸𝑟 𝑟̂ + 𝐸𝜃 𝜃̂ + 𝐸∅ ∅ (2 cos 𝜃 𝑟̂ + sin 𝜃 𝜃̂)
4𝜋𝜀 3
0𝑟
(6)
To simplify this, let us make the following substitution
𝑦 = 𝑟 sin 𝜃 and 𝑧 = 𝑟 cos 𝜃
The radius vector r lying in the yz plane can be written as
𝑟̅ = 𝑗̂𝑦 + 𝑘̂𝑧
= 𝑗̂𝑟 sin 𝜃 + 𝑘̂𝑟 cos 𝜃
Therefore,
𝑟̅
𝑟̂ = = 𝑗̂ sin 𝜃 + 𝑘̂ cos 𝜃
𝑟
Similarly,
𝜃̂ = 𝑗̂ cos 𝜃 − 𝑘̂ cos 𝜃
Where 𝑟̂ and 𝜃̂ are unit vectors along their respective axes. Now
substituting the value of 𝑟̂ and 𝜃̂ in eq. 6 we get,
𝑃
𝐸(𝑟, 𝜃) = {2 cos 𝜃 (𝑗̂ sin 𝜃 + 𝑘̂ cos 𝜃)
4𝜋𝜀0 𝑟 3
+ sin 𝜃 (𝑗̂ cos 𝜃 − 𝑘̂ sin 𝜃)}
𝑃
= {𝑗̂ 2 cos 𝜃 sin 𝜃 + 2 𝑘̂ 𝑐𝑜𝑠 2 𝜃 + 𝑗̂ sin 𝜃 cos 𝜃 − 𝑘̂ 𝑠𝑖𝑛2 𝜃}
4𝜋𝜀0 𝑟 3
𝑃
= {𝑗̂ 3 cos 𝜃 sin 𝜃 + 𝑘̂(2 𝑐𝑜𝑠 2 𝜃 − 𝑠𝑖𝑛2 𝜃)}
4𝜋𝜀0 𝑟 3
𝑃
= {𝑗̂ 3 cos 𝜃 sin 𝜃 + 𝑘̂(3 𝑐𝑜𝑠 2 𝜃 − 1)}
4𝜋𝜀0 𝑟 3
6
𝑃
= {3 cos 𝜃 (𝑗̂ sin 𝜃 + 𝑘̂ cos 𝜃) − 𝑘̂}
4𝜋𝜀0 𝑟 3
1
= 5
{3𝑟 2 𝑃 cos 𝜃 (𝑗̂ sin 𝜃 + 𝑘̂ cos 𝜃) − 𝑘̂𝑟 2 𝑃}
4𝜋𝜀0 𝑟
1
= {3 (𝑃⃗. 𝑟)𝑟 − 𝑘̂𝑟 2 𝑃⃗}
4𝜋𝜀0 𝑟 5
1.4 LOCAL ELECTRIC FIELD AT AN ATOM
When a dielectric material is placed in an external electrical field, it

produces an induced dipole moment. Now, two fields are acting at any
point inside dielectrics are
(i) Macroscopic electrical field due to external electrical field.
(ii) Electrical field due to electric dipole moment
These long-range coulomb field produced due to dipoles is known as
internal field or local field. This internal field is responsible for polarization
of each atom or molecule in a solid.
Fig 1.3 (a) The procedure for computing the local field, (b) The
procedure for calculating E2, the field due to the polarization charge
on the surface of the Lorentz sphere
Lorentz method to find internal field (Derivation)

The dielectric material is uniformly polarized by placing it in between two
plates of a parallel plate capacitor (uniform electrical field) as shown in
Fig. 1.3
7
The local field (Elocal) at the atom site is considered to be made up of the
following four components. E0, E1, E2 and E3.
The local field acting on the reference dipole is given by:
𝐸𝑙𝑜𝑐𝑎𝑙 = 𝐸0 + 𝐸1 + 𝐸2 + 𝐸3 (7)
Where,
E0 → The applied external field
E1 → Electrical field due to polarized charges (induced charges) on the
plane surface of the dielectric, known as depolarization field.
E2 → Electrical field due to polarized charges induced on the surface of
the imaginary spherical cavity, known as Lorentz field.
E3 → Electrical field due to permanent dipoles of atoms inside the
spherical cavity considered
Macroscopically, we can take E = E0 + E1, i.e., the electrical field externally

applied (E0) and the electrical field induced on the plane surface of the
dielectric (E1) can be considered as a single electrical field (E).
If we consider a dielectric that is highly symmetric, the electrical field due

to dipoles present inside the imaginary cavity will cancel out each other.
Therefore, the electrical field due to permanent dipoles E3 = 0
Now, the equation is rewritten as
𝐸𝑙𝑜𝑐𝑎𝑙 = 𝐸 + 𝐸2 (8)
Lorentz field, E2
The polarization charges on the surface of the sphere produces this field.
In order to calculate this field at the centre in the applied field direction, let
us consider an enlarged view of the spherical cavity. If θ is the polar angle
that an element of area dA is making with respect to the polarization
direction (taken as x-axis), the induced charge density on the surface of
the cavity is equal to the normal component of the polarization times the
surface element, i.e
𝑃 cos 𝜃 × 𝑑𝐴
8
According to Coulomb’s law, this charge on the surface element of area
dA produces a force dFr acting on the referred test charge q (assuming at
the centre of the cavity) in the direction of r
𝑞 𝑞2 𝑞𝑃 cos 𝜃 𝑑𝐴
𝑑𝐹𝑟 = 4𝜋𝜀1 2
= (9)
0𝑟 4𝜋𝜀0 𝑟 2
Where
𝑑𝐴 = 2𝜋𝑟 sin 𝜃 𝑟𝑑𝜃 = 2𝜋𝑟 2 sin 𝜃 𝑑𝜃
The force acting in the direction of the applied electric field,
𝐹𝑥 = +𝐹𝑟 cos 𝜃
From eq. 9 we have,
𝑞𝑃 cos 𝜃
𝑑𝐹𝑥 = 2𝜋𝑟 2 sin 𝜃 𝑑𝜃 cos 𝜃 (10)
4𝜋𝜀0 𝑟 2
The Lorentz force Fx can be determined by integrating eq. 10 over the

range of θ = 0 to θ = π. Therefore,
𝑞𝑃 𝜋
𝐹𝑥 = 2𝜀 ∫0 𝑐𝑜𝑠 2 𝜃 sin 𝜃 𝑑𝜃 (11)
0
Substituting z = cos θ in eq. 11, we have dz = - sin θ dθ, so that

−1
𝑞𝑃 −1 2 𝑞𝑃 𝑧 3 𝑞𝑃
𝐹𝑥 = ∫ 𝑧 𝑑𝑧 = [ ] =
2𝜀0 +1 2𝜀0 3 +1 3𝜀0
The Lorenz field, E2 becomes,

𝐹𝑥 𝑃
𝐸2 = = 3𝜀 (12)
𝑞 0
Now substituting eq. 12 in eq., the local field acting on the reference dipole
is given by,
𝐸𝑙𝑜𝑐𝑎𝑙 = 𝐸 + 𝐸2
𝑃
= 𝐸 + 3𝜀 (13)
0
9
This is known as Lorentz relation. The field E is macroscopic field and is
an average field. In the present situation, this is constant throughout the
medium. Elocal is a microscopic field and is periodic in nature. This is quite
large at molecular sites indicating that the molecules are more effectively
polarized than they are under the average field.
1.5 CLAUSIUS MOSSOTTI EQUATION
Let N be the number of molecules per unit volume and α be the molecular
polarizability. Then total polarization,
𝑃 = 𝑁𝛼𝐸𝑙𝑜𝑐𝑎𝑙 (14)
𝑃
𝐸𝑙𝑜𝑐𝑎𝑙 = (15)
𝑁𝛼
Further, we know that
𝐷 = 𝜀𝐸 = 𝜀0 𝐸 + 𝑃
(𝜀 − 𝜀0 )𝐸 = 𝑃
𝑃
𝐸 = (𝜀−𝜀 (16)
0)
Lorentz field is given by

𝑃
𝐸𝑙𝑜𝑐𝑎𝑙 = 𝐸 + 3𝜀 (17)
0
Substituting eq. 16 in eq. 17 we get
𝑃 𝑃
𝐸𝑙𝑜𝑐𝑎𝑙 = +
(𝜀 − 𝜀0 ) 3𝜀0
3𝜀0 + 𝜀 − 𝜀0
= 𝑃[ ]
3𝜀0 (𝜀 − 𝜀0 )
𝑃 𝜀+2𝜀
𝐸𝑙𝑜𝑐𝑎𝑙 = 3𝜀 ( 𝜀−𝜀 0) (18)
0 0
Equating the eqns (15) and (18)
10
𝑃 𝑃 𝜀 + 2𝜀0
= ( )
𝑁𝛼 3𝜀0 𝜀 − 𝜀0
𝑁𝛼 𝜀 + 2𝜀0
=
3𝜀0 𝜀 − 𝜀0
𝜀⁄ − 1
𝜀
=𝜀 0
⁄𝜀0 + 2
𝑁𝛼 𝜀 −1
= 𝜀𝑟 +2 (19)
3𝜀0 𝑟
Where,
𝜀⁄ = 𝜀 ,
𝜀0 𝑟
the relative permittivity. Eq. 19 is the Clausius-Mosotti relation which

relates the dielectric constant (a macroscopic quantity) of the material with
polarizability (a microscopic quantity).
1.6 DIELECTRIC CONSTANTS AND ITS MEASUREMENTS
Dielectric constant is a measure of the degree to which a medium can

resist the flow of charge. It is also defined as the ratio for the dielectric
displacement D to the electric field intensity E, i.e
𝐷
𝜀= = 𝜀𝑟 𝜀0 (20)
𝐸
Where 𝜀𝑟 is the relative permittivity of the medium and 𝜀0 is the permittivity

of free space. If 𝜀𝑟 =1 then 𝜀 = 𝜀0 .
Fig. 1.4 shows the simple experimental setup to measure the dielectric
constant. In this, the plates of a capacitor are connected to a battery which
charges them. In the absence of a dielectric the field produced by the
charges is E0, which can be measured by measuring the potential
difference V0 across the capacitor using the relation,
𝑉0
𝐸0 = (21)
𝑑
11
Fig 1.4 Experimental setup to measure dielectric constant
Where d is the distance between the plates. When the dielectric medium
is introduced between the plates, the E0 polarizes the charges in the
medium, which in turn modifies the field to a new value E. Similarly, the
new field can be determined by measuring the potential difference V
across the capacitor using the relation
𝑉
𝐸 = 𝑑 (22)
The dielectric constant in terms of the field E0 and E is given by

𝐸0
𝜀𝑟 = (23)
𝐸
From eqs. 21 and 22, eq. 23 will become

𝑉0
𝜀𝑟 = (24)
𝑉
Thus, we can obtain the dielectric constant by measuring the potential

difference across the capacitor with and without dielectric and taking their
ratio.
Similarly, the dielectric constant can also be obtained by measuring
capacities of condenser with and without dielectric and taking their ratio
as,
𝐶
𝜀𝑟 = 𝐶 (25)
0
12
Where C0 and C are the capacities in the absence and presence of
dielectric medium, respectively.
Further we know that the capacity of a parallel plate capacitor is given by
𝑄
𝐶 = 𝑉 or 𝑄 = 𝐶𝑉 (26)
Eq. 26 indicates that the increase in the capacity by a factor means a

decrease in the potential difference as well as in the field by the same
factor, i.e C = εrC0 then the decrease in the field in the presence of
dielectric medium is
𝐸0
𝐸=
𝜀𝑟
This decrease in field induces dipoles and the medium gets polarised. The
polarization produced in the material is a measure of the charge in the
capacitance such that
𝑃 = (𝐶 − 𝐶0 )𝑉
= (𝜀 − 𝜀0 )𝐸
= (𝜀𝑟 − 1)𝜀0 𝐸
Rearranging the terms, we get

𝑃
𝜀𝑟 = 1 + 𝜀 = 1 + 𝜒𝑒 (27)
0𝐸
Where,
𝑃
𝜒𝑒 = 𝜀
0𝐸
is the electric susceptibility.

Eq. 27 gives the dielectric constant of an isotropic medium or a solid with
cubic structure.
13
LET US SUM UP
❖ The polarization P is thus defined as the dipole moment per unit

volume
❖ The local electrical field is the contribution from the applied
external field, the polarized charges (induced charges) on the
plane surface of the dielectric, polarized charges induced on the
surface of the imaginary spherical cavity and permanent dipoles
of atoms inside the spherical cavity considered.
❖ The Clausius-Mosotti relation relates the dielectric constant (a
macroscopic quantity) of the material with polarizability (a
microscopic quantity)
𝑁𝛼 𝜀𝑟 − 1
=
3𝜀0 𝜀𝑟 + 2
CHECK YOUR PROGRESS:
1. Define dipole moment

2. What is polarization?
ANSWERS TO CHECK YOUR PROGRESS
1. If we have two equal and opposite charges, +q and -q, the moment
of this dipole can be defined as 𝜇 = 𝑞𝑟
2. The polarization P is thus defined as the dipole moment per unit
𝜇
volume 𝑃 = 𝑉.
UNIT END EXERCISES
1. Derive the expression for local electric field acting at an atom using
Lorentz method.
2. Stating with the internal field expression, derive Clausis – Mosotti
equation.
14
SUGGESTED READINGS
1. M. A. Wahab (2015), Solid State Physics: Structure and

Properties of Materials, Narosa Publishing House Pvt. Ltd. - New
Delhi
2. C. Kittel (2012) Introduction to Solid State Physics, 8th Edition,
John Wiley & Sons, New York.
Web Resources
1. http://www.infocobuild.com/education/audio-video-
courses/physics/SolidStatePhysics-IIT-Kharagpur/lecture-74.html
2. https://www.youtube.com/watch?v=dwudC0R_Xy4
3. https://www.youtube.com/watch?v=Fk-ryzSetw4
4. https://www.youtube.com/watch?app=desktop&v=d0SelgGispI
5. https://www.youtube.com/watch?v=ACsvRb5q58Q
6. https://www.youtube.com/watch?v=etjZmdmrjSU
7. https://www.youtube.com/watch?v=4hpLxJYEBHA
15
UNIT 2
TYPES OF POLARIZATION
Structure
Overview
Objectives
2.1 Polarizability
2.2 The classical theory of electronic polarizability
2.3 Ionic polarizabilities
2.4 Orientational polarizabilities
2.5 The polarizability catastrophe
Let Us Sum Up
Check Your Progress
Unit end exercises

Suggested readings
OVERVIEW
Polarizability occurs because of the molecules are composed of positive

charges (nuclei) and negative charges (electrons). When an electric field
applied constantly to a molecule, at some point the positive charge goes
along the field direction while the negative charge opposes the direction.
This leads to a situation where opposite charges are pulled apart. This
results in polarization of the molecule.
OBJECTIVES

❖ Explain the types of Polarization
❖ Describe the classical theory of electronic polizability
16
❖ Understand the difference between Ionic and Orientational
polarizabilities
2.1 POLARIZABILITY
When an electric field is applied to a solid, electric charges are displaced

causing polarization in it. The induced dipoles of moments µ are
proportional to the local field, Elocal i.e
𝜇 = 𝛼𝐸𝑙𝑜𝑐𝑎𝑙 (28)
Where α is known as electrical polarizability of the atom. The polarization

of the dielectric containing N atoms is given by
𝑃 = ∑𝑁
𝑖=1 𝑁𝑖 𝛼𝑖 𝐸𝑙𝑜𝑐𝑎𝑙 (𝑖) (29)
Where Ni is the number of i atoms having polarizabilities 𝛼𝑖 and Elocal (i) is

the local field at the atoms of type i.
Polarization depends on the molecular structure. Depending on the
structure of molecule, polarizability can be classified into the following
three types
i. Electronic polarizability
ii. Ionic polarizability
iii. Orientational polarizability
2.2 THE CLASSICAL THEORY OF ELECTRONIC POLARIZABILITY
In a free atom, in the absence of external electric field, the centre of gravity
of the electron distribution coincides with the nucleus. When the atom is
placed in a homogeneous external electric field E, the force exerted on
the nucleus and on the electrons is oppositely directed. This will result in
the creation of dipole moment in the dielectric.
𝜇𝑖𝑛𝑑 = 𝛼𝑒 𝐸𝑙𝑜𝑐𝑎𝑙 (30)
Where αe is proportionality constant and it is known as electronic

polarizability.
17
Calculation of Electronic polarizability (αe)
Consider an atom of a dielectric material of nuclear charge Ze, where Z is
the atomic number. The electrons of charge (-Ze) are distributed
uniformly throughout the atom (sphere) of radius R as shown in Fig. 2.1a
The centers of the electron cloud and the positive nucleus are at the same
point and hence there is no dipole moment. The negative charge density
of an atom of radius R is
𝑇𝑜𝑡𝑎𝑙 𝑛𝑒𝑔𝑎𝑡𝑖𝑣𝑒 𝐶ℎ𝑎𝑟𝑔𝑒

𝜌=
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑎𝑡𝑜𝑚
−𝑍𝑒 3 𝑍𝑒
𝜌=4 = − 4 𝜋𝑅3 (31)
𝜋𝑅 3
3
When the atom of the dielectric is placed in an electrical field of strength

E, two phenomena occur.
a) Lorentz force (due to electrical field) will tend to move the nucleus
and electron cloud of that atom from their equilibrium positions.
The positive nucleus will move towards the field direction and the
electron cloud will move in the opposite direction of the field as
shown in Fig. 2.1b
b) After separation, an attractive Coulomb force arises between the

nucleus and the electron cloud which will tend to maintain the
original equilibrium position.
Fig. 2.1 (a) An atom without any field (b) Electronic polarization
18
The electron cloud and the nucleus move in opposite directions and they
are separated by a distance ‘x’, where there is a formation of electrical
dipole in the atom. When these two forces are equal and opposite, there
will be a new equilibrium between the nucleus and electron cloud of the
atom.
The Lorentz force between the nucleus and the electron is
𝐹𝐿 = 𝑐ℎ𝑎𝑟𝑔𝑒 × 𝑒𝑙𝑒𝑐𝑡𝑟𝑖𝑐 𝑓𝑖𝑒𝑙𝑑 = 𝑍𝑒𝐸 (32)
Coulomb attractive force (FC) between the nucleus and the electron cloud
being separated at a distance x,
1 𝑄𝑝 𝑄𝑒
𝐹𝐶 = 4𝜋𝜀 (33)
0 𝑥2
𝑄𝑝 -Total positive charge of an atom present in the sphere of radius = +Ze
𝑄𝑒 - Total negative charges enclosed in the sphere of radius x
𝑇𝑜𝑡𝑎𝑙 𝑛𝑒𝑔𝑎𝑡𝑖𝑣𝑒 𝑐ℎ𝑎𝑟𝑔𝑒𝑠

{𝑒𝑛𝑐𝑙𝑜𝑠𝑒𝑑 𝑖𝑛 𝑡ℎ𝑒 𝑠𝑝ℎ𝑒𝑟𝑒 𝑜𝑓 }
𝑟𝑎𝑑𝑖𝑢𝑠 𝑥
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑝ℎ𝑒𝑟𝑒
= {𝑐ℎ𝑎𝑟𝑔𝑒 𝑑𝑒𝑛𝑠𝑖𝑡𝑦 (𝜌)} × { }
𝑜𝑓 𝑟𝑎𝑑𝑖𝑢𝑠 𝑥
3 𝑍𝑒 4 3
=− × 𝜋𝑥
4 𝜋𝑅 3 3
𝑥3
= −𝑍𝑒 (𝑅3) (34)
Hence the eq. 33 becomes
𝑥3
1 (𝑍𝑒) × 𝑍𝑒 ( )
𝑅3
𝐹𝐶 = −
4𝜋𝜀0 𝑥2
1 𝑍 2𝑒 2𝑥
𝐹𝐶 = − 4𝜋𝜀 (35)
0 𝑅3
19
At equilibrium, Coulomb force and Lorentz force must be equal and
opposite.
𝐹𝐿 = −𝐹𝐶
From eq. 32 and 35
1 𝑍2𝑒 2𝑥
𝑍𝑒𝐸 =
4𝜋𝜀0 𝑅 3
1 𝑍𝑒𝑥
𝐸=
4𝜋𝜀0 𝑅 3
4𝜋𝜀0 𝑅 3 𝐸
𝑥= (34)
𝑍𝑒
Due to the application of electrical field on the atom, the charge centers
are displaced from their equilibrium position and hence the atom gains
some dipole moment.
From the definition of dipole moment, induced dipole moment (µind) is
given by
𝜇𝑖𝑛𝑑 = 𝑚𝑎𝑔𝑛𝑖𝑡𝑢𝑑𝑒 𝑜𝑓 𝑐ℎ𝑎𝑟𝑔𝑒 × 𝑑𝑖𝑠𝑝𝑎𝑙𝑐𝑒𝑚𝑒𝑛𝑡
𝜇𝑖𝑛𝑑 = 𝑍𝑒 𝑥
4𝜋𝜀0 𝑅 3 𝐸
𝜇𝑖𝑛𝑑 = 𝑍𝑒
𝑍𝑒
𝜇𝑖𝑛𝑑 = 4𝜋𝜀0 𝑅 3 𝐸 (35)
Comparing the eq. 30 and 35, we have
𝛼𝑒 = 4𝜋𝜀0 𝑅 3 (36)
where αe is called electronic polarizability. From eq. 36 the electronic

polarizability is independent of temperature and proportional to the
volume of atoms in the material. The electronic polarization takes place in
all dielectrics.
20
2.3 IONIC POLARIZABILITY
Ionic polarization is due to the displacement of cations (positive ions) and

anions (negative ions) in opposite directions. This occurs in ionic
dielectrics (e.g. NaCl crystal) by the influence of external electrical field.
When an electrical field (E) is applied on an ionic dielectric, there is a shift

of one ion with respect to another from their mean positions. The positive
ions displace in the direction of applied electrical field through the distance
x1 (Fig. 2.2). The negative ions displace in opposite direction through the
distance x2.
Fig. 2.2 Ionic polarization

We assume that there is one cation and one anion in each unit cell of that
ionic crystal.
Hence, the net distance between two ions
x = x1 + x2 (37)
When the ions are displacing from their mean positions in their respective
directions the restoring forces appear which tend the ions back to their
mean position. The restoring force produced is proportional to the
displacement.
For positive ion
Restoring force, 𝐹 ∝ 𝑥1
or
Restoring force acting on the positive ion 𝐹 = 𝛽1 𝑥1 (38)
For negative ion
Restoring force, 𝐹 ∝ 𝑥2
21
Or
Restoring force acting on the positive ion 𝐹 = 𝛽2 𝑥2 (39)
Where 1 and 2 are restoring force constants which depend upon the
masses of ions and angular frequency of the molecule in which ions are
present.
If m is the mass of positive ion, M is the mass of negative ion and
0 is the angular frequency, then
𝛽1 = 𝑚𝜔02 (40)
and
𝛽2 = 𝑀𝜔02 (41)
Substituting for eq. 40 in 38, the restoring force for positive ion can be
rewritten as
𝐹 = 𝑚𝜔02 𝑥1 (42)
We know that
𝐹 = 𝑒𝐸 (43)
From eq. 41 and 42
𝑒𝐸 = 𝑚𝜔02 𝑥1
𝑒𝐸
𝑥1 = 𝑚𝜔2 (44)
0
Similarly for the negative ion, we can write

𝑒𝐸
𝑥2 = 𝑀𝜔2 (45)
0
Adding equation 44 and 45, we have
𝑒𝐸 𝑒𝐸
𝑥 = 𝑥1 + 𝑥2 = +
𝑚𝜔02 𝑀𝜔02
𝑒𝐸 1 1
𝑥 = 𝜔2 (𝑚 + 𝑀) (46)
0
22
The dipole moment is equal to the product of charge and distance of
separation between the charges.
𝜇 = 𝑒. 𝑥 (47)
Substituting for x from eq. 46, we have
𝑒𝐸 1 1
𝜇 = 𝑒 𝜔2 (𝑚 + 𝑀)
0
𝑒 2𝐸 1 1
= (𝑚 + 𝑀) (48)
𝜔02
Also
𝜇 = 𝛼𝑖 𝐸 (49)
where αi is the ionic polarizability of dielectric material

On comparing eq. 48 and 49, we have
𝑒 2𝐸 1 1
𝛼𝑖 = (𝑚 + 𝑀) (50)
𝜔02
The ionic polarizability (αi) is inversely proportional to the square of

angular frequency of the ionic molecule. It is directly proportional to its
reduced mass given by
1 1
(𝑚 + 𝑀).
It is independent of temperature.
2.4 ORIENTATIONAL POLARIZABILITIY
Orientational polarization takes place only in polar dielectrics. Polar

dielectrics have molecules with permanent dipole moments even in the
absence of an electrical field as shown in Fig. 2.3. Due to random
orientation of dipoles or molecules, the net dipole moment is zero. When
the polar dielectrics are subjected to an electrical field, the molecular
dipoles are oriented in the direction of electric field. This type of
polarization is known as orientational polarization.
23
Fig. 2.3 (a) Orientation of dipoles in the absence of electric field and
(b) Orientation of dipoles in the direction of the applied electric
field
In case of polar dielectrics, the orientational polarization is given by
𝑁𝜇 2 𝐸
𝑃𝑜 = (50)
3𝑘𝐵 𝑇
But, orientational polarization is proportional to applied field (E) and it is

given by
𝑃𝑜 = 𝑁𝛼𝑜 𝐸 (51)
Comparing eq. 50 and 51 then the orientational polarizability 𝛼𝑜 is
𝜇2
𝛼𝑜 = 3𝑘 (50)
𝐵𝑇
Where kB is Boltzman constant, T is the temperature and µ is the

permanent dipole moment. Thus, the orientational polarizability is
inversely proportional to the temperature. Orientational polarization
occurs only in polar dielectrics such as H2O, HCl and CO etc.
2.5 POLARIZABILITY CATASTROPHE
In terms of a polarization catastrophe in which for some critical condition

the polarization becomes very large. In a polarization catastrophe the
local electric field caused by the polarization increases faster than the
24
elastic restoring force on an ion in the crystal, thereby leading to an
asymmetrical shift in ionic positions. The shift is limited to a finite
displacement by higher order re-storing forces. The occurrence of ferro
electricity in an appreciable number of crystals with the perovskite
structure suggests that this structure is favourably disposed to a
polarizability catastrophe. Calculations of local fields have made clear the
physical reason for the favoured position of the perovskite structure.
The simple form of the catastrophe theory:
The local field at all atoms is equal to
𝑃
𝐸𝑙𝑜𝑐𝑎𝑙 = 𝐸 + 3𝜀 (51)
0
The theory given now leads to a second-order transition; the physical

ideas can be carried over to a first order transition. In a second-order
transition there is no latent heat; the order parameter (in this instance, the
polarization) is not discontinuous at the transition temperature. In a first
order transition there is a latent heat; the order parameter changes
discontinuously at the transition temperature.
We know that the Clausius-Mosotti relation (from eq. 19) is,
∑ 𝑁𝑖 𝛼𝑖 𝜀 −1
= 𝜀𝑟 +2 (52)
3𝜀0 𝑟
By rearranging the eq. 52 and we get the dielectric constant in the form
2
1+ ∑ 𝑁𝑖 𝛼𝑖
3𝜀0
𝜀𝑟 = 1 (53)
1− ∑ 𝑁𝑖 𝛼𝑖
3𝜀0
Where 𝛼𝑖 is the electronic plus ionic polarizability of an ion of type i and Ni

is the number of ions i per unit volume. The dielectric constant becomes
infinite and permits a finite polarization in zero applied field when comes
infinite and permits a finite polarization in zero applied field when
∑ 𝑁𝑖 𝛼𝑖 = 3𝜀0 (54)
This is the condition for a polarization catastrophe. The value of 𝜀𝑟 in eq.

53 is sensitive to small departure of ∑ 𝑁𝑖 𝛼𝑖 from the critical value 3𝜀0 . If
we write
1
∑ 𝑁𝑖 𝛼𝑖 = 1 − 3𝑠 (55)
3𝜀0
25
Where s≪1, the dielectric constant in eq. 53 becomes
𝜀𝑟 ≃ 1⁄𝑠 (56)
Suppose near the critical temperature s varies linearly with temperature
𝑠 ≃ (𝑇 − 𝑇𝑐 )⁄𝜉 (57)
Where 𝜉 is a constant. Such a variation of s or ∑ 𝑁𝑖 𝛼𝑖 might come from

normal thermal expansion of the lattice. The dielectric constant has the
form
𝜀𝑟 ≃ 𝜉 ⁄(𝑇 − 𝑇𝑐 ) (58)
close to the observed temperature variation in the paraelectric state.
LET US SUM UP
❖ Ionic polarization is due to the displacement of cations (positive

ions) and anions (negative ions) in opposite directions. This occurs
in ionic dielectrics (e.g. NaCl crystal) by the influence of external
electrical field.
❖ Orientational polarization takes place only in polar dielectrics.
When the polar dielectrics are subjected to an electrical field, the
molecular dipoles are oriented in the direction of electric field.
❖ Under for some critical condition the polarization becomes very
large. This is called polarization catastrophe. In a polarization
catastrophe, the local electric field caused by the polarization
increases faster than the elastic restoring force on an ion in the
crystal, thereby leading to an asymmetrical shift in ionic positions.
The shift is limited to a finite displacement by higher order re-
storing forces.
1. Define ionic polarization

2. What is polarizability catastrophe?
26
1. Ionic polarization is due to the displacement of cations (positive

ions) and anions (negative ions) in opposite directions. This occurs
in ionic dielectrics (e.g. NaCl crystal) by the influence of external
electrical field.
2. At certain temperature, the polarization becomes very large
(infinite) is called polarization catastrophe.
UNIT END EXERCISES
1. Discuss the different types of polarization mechanism and

polarizability involved in dielectrics.
2. Discuss the polarization catastrophe in dielectrics.
SUGGESTED READINGS

Delhi
3. Rajnikant (2011), Applied Solid State Physics, Wiley India Pvt.
Ltd., New Delhi
Web Resources
1. https://www.youtube.com/watch?v=axKxpC4sLS4
2. https://www.youtube.com/watch?v=4YIf8FbvWpk
3. https://www.youtube.com/watch?v=FSwJ2bM0noA
4. https://www.youtube.com/watch?v=wzR5kORzA3k
5. https://www.youtube.com/watch?v=etjZmdmrjSU
6. https://www.youtube.com/watch?v=_nL6a21q1a4
7. https://www.youtube.com/watch?v=5e_RBvSj0TE
27
UNIT 3
DIELECTRIC REALAXATION
Structure
Overview
Objectives
3.1 Dipole relaxation and dielectric losses
3.2 Debye relaxation time
3.3 Relaxation in solids
3.4 Complex dielectric constants and the loss angle
3.5 Frequency and temperature effects on polarization
3.6 Dielectric breakdown and dielectric loss
Let Us Sum Up
Check Your Progress
Unit end exercises
Suggested readings
OVERVIEW
Dielectric relaxation is the momentary delay (or lag) in the dielectric

constant of a material. This is usually caused by the delay in molecular
polarization with respect to a changing electric field in a dielectric medium
(e.g., inside capacitors or between two large conducting surfaces).
Dielectric relaxation in changing electric fields could be considered
analogous to hysteresis in changing magnetic fields (e.g.,
in inductor or transformer cores). Relaxation in general is a delay or lag in
the response of a linear system, and therefore dielectric relaxation is
measured relative to the expected linear steady state (equilibrium)
dielectric values. The time lag between electrical field and polarization
implies an irreversible degradation of Gibbs free energy.
In physics, dielectric relaxation refers to the relaxation response of a
dielectric medium to an external, oscillating electric field. This relaxation
is often described in terms of permittivity as a function of frequency, which
28
can, for ideal systems, be described by the Debye equation. On the other
hand, the distortion related to ionic and electronic polarization shows
behaviour of the resonance or oscillator type. The character of the
distortion process depends on the structure, composition, and
surroundings of the sample.
OBJECTIVES
❖ Understand the Dipole relaxation and dielectric losses

❖ Describe Complex dielectric constants and the loss angle
❖ Explain the Frequency and temperature effects on polarization
3.1 DIPOLE RELAXATION (LORENTZ RELAXATION)
When the applied electric field is suddenly switched off, the dipoles will
randomize i.e their dipole moment or polarization will go to zero. However,
that cannot happen instantaneously. A specific dipole will have a certain
orientation at the time, the field will be switched off, and it will change that
orientation only by some interaction with other dipoles (or, in a solid, with
phonons), in other words upon collisions or other "violent" encounters. It
will take a characteristic time, roughly the time between collisions, before
the dipole moment will have disappeared. the individual characteristic
time for a given dipole will be small for some, and large for others. But
there will be an average value which we will call the relaxation time τ of
the system.
Fig 3.1 Electric field vs time and polarization vs time for dipole
relaxation
29
The polarization P decays starting at the time of the switch-off according
to
−𝑡⁄
𝑃(𝑡) = 𝑃0 𝑒 𝜏 (51)
Polarization in terms of frequency with ω = 2πν i.e the output to a periodic

harmonic input of electric field E = E0 sin ωt
∞ −𝑡⁄
𝑃(𝜔) = ∫0 𝑃0 𝑒 𝜏 . 𝑒 −𝑖𝜔𝑡 . 𝑑𝑡 (52)
P0 is the static polarization, i.e the value of P(ω) for ω = 0 Hz, τ is the
relaxation time and i = (-1)1/2 is the imaginary unit. Solving the integral we
get P(ω),
𝑃0
𝑃(𝜔) = 𝜔 (53)
0 +𝑖𝜔
1
𝜔0 = (54)
𝜏
Here ω0 is not 2π/τ, as usual, but 1/τ
3.2 DEBYE RELAXATION TIME
In polar materials containing permanent dipoles, in thermal equilibrium,

the dipoles are randomly oriented. A partial alignment of the dipoles by
any electric field is usually disrupted by thermal agitation, and once the
field is withdrawn, the thermal agitation tries to relax a polarized region to
the unpolarized equilibrium state of random orientation. This is
conceptually very different from the Lorentz oscillator model. This kind of
relaxation of polarization is usually associated with Debye, and therefore
sometimes called Debye relaxation. For polar liquids, Debye relaxation by
molecular rotations determine the optical constants at low frequencies
(usually in the microwave range). Many solids also show Debye
relaxations.
A Debye oscillator (i.e., permanent dipole), if initially polarized, returns to

equilibrium as
𝑃𝐷 (𝑡) = 𝑃𝐷 (0)𝑒 −𝑡⁄𝜏𝐷 (55)
30
Without any oscillation. The relaxation time τD is larger than τ, determined
mainly by the diffusive rotational motion of the dipoles.
To describe a polar system within the Debye model, consider an

ensemble of Debye oscillators (dipoles), subject to a constant electric field
E0 applied at t = t0. The response of the oscillators are usually slow
(because the dipole are heavy) compared with the polarizations of free
electrons, lattice ions, and internal transitions (including vibrational) in the
dipoles, and these may be regarded as instantaneous. This means, when
the field is applied at t0, the polarization, is P(t0) = ε0χ0νE0, is instantly
induced; here χ0 is the dielectric susceptibility at frequencies low
compared with vibrational frequencies. As time increases, the polarization
approaches a limiting value P(t→∞) = ε0χ0dE0, where χ0d is the static or dc
dielectric susceptibility. Thus, one can write
𝑃(𝑡) = 𝑃(∞) − [𝑃(∞) − 𝑃(𝑡0 )𝑒 −(𝑡−𝑡0 )⁄𝜏𝐷 ] (56)
which can be rewritten as
𝑃(𝑡) = 𝜀0 𝜒0𝜈 𝐸0 + 𝜀0 (𝜒0𝑑 − 𝜒0𝜈 )[1 − 𝑒 −(𝑡−𝑡0)⁄𝜏𝐷 ]𝐸0 (57)
Since the electric field has the form 𝐸(𝑡) = 𝐸0 Θ(𝑡 − 𝑡0 ), where Θ is the
step function, we can write this as
𝑡
𝑃(𝑡) = 𝜀0 𝜒0𝜈 𝐸0 + 𝜀0 ∫−∞ 𝐸(𝑡 ′ )𝑓(𝑡 − 𝑡 ′ ) 𝑑𝑡 ′ (58)
Where the function f is called Debye relaxation function and defined as

∆
𝑓(𝑡) = 𝜏 𝑒 −𝑡⁄𝜏𝐷 (59)
𝐷
With
∆= 𝜒0𝑑 − 𝜒0𝜈 = 𝜀0𝑑 − 𝜀0𝜈
(a notation traditionally used by dielectricians)

For a time-harmonic field of the form
𝐸(𝑡) = 𝐸0 𝑒 −𝑖𝜔𝑡 ,
the eq. 58 then leads a dielectric function of the form
31
∆
𝜀(𝜔) = 𝜀0𝜈 + 1−𝑖𝜔𝜏 (60)
𝐷
So that
∆
𝜀 ′ = 𝜀0𝜈 +
1 + 𝜔 2 𝜏𝐷2
And
𝜔𝜏 ∆
𝜀 " = 1+𝜔𝐷2𝜏2 (61)
𝐷
Where 𝜀 " has a maximum at 𝜔 = 1⁄𝜏𝐷 with 𝜀𝑚𝑎𝑥 "

= ∆⁄2. However, 𝜀 ′ is
very different now, having neither maxima nor minima, decreasing
monotonically from 𝜀0𝑑 at low frequency to 𝜀0𝜈 at high frequency. For a
typical polar liquid such as water, the Debye model works fairly well, and
the measured dielectric function of water at microwave frequencies can
be fit very well with 𝜏𝐷 = 8 × 10−12 𝑠𝑒𝑐, 𝜀0𝑑 = 77.5 and 𝜀0𝜈 = 5.27 as
shown in Fig. 3.2
Fig. 3.2 ε’ and ε” vs ωτD for water
32
On physical grounds, relaxation of permanent dipoles is expected to be
highly temperature dependent. Debye showed that the relaxation time for
a sphere of radius a in a fluid of viscosity η is
4𝜋𝜂𝑎3
𝜏𝐷 = (62)
𝑘𝐵 𝑇
At room temperature, taking 𝜂 = 0.01 𝑔⁄𝑐𝑚. 𝑠𝑒𝑐 and 𝑎 ≈ 10−8 𝑐𝑚 gives

𝜏𝐷 ≈ 3 × 10−12 𝑠𝑒𝑐, which is close to the simple Debye model.
3.3 RELAXATION IN SOLIDS
Relaxation processes occur in many ceramics and ionic solids, especially

glasses and these materials applying damped forced oscillator approach
does not work in the low frequency region. In such cases, the structure of
the solid plays an important role because movement of charges may have
to occur over many atomic distances and can be classified as diffusional
in nature. These processes can be strongly temperature dependent in
nature. As a result, it may take considerable amount of time in the
distribution of charges.
For instance, in an ionic solid, application of a field leads to first almost
instantaneous development of ionic and electronic polarization followed
by slow development of dipolar polarization, Pd to a saturation
polarization, Ps
Fig 3.3 Dependence of dipolar polarisation on time
33
We can approximately express the rate of change of polarization as
𝑑𝑃 1
= 𝜏 (𝑃𝑠 − 𝑃𝑑 (𝑡)) (63)
𝑑𝑡
where 1/τ is the proportionality constant. The above equation is also called
Relaxation Equation.
The initial and final conditions are

At t = 0, Pd = 0 and at some reasonably large t, P = Ps
Integrating within these limits yield
−𝑡⁄
𝑃𝑑 =𝑃𝑠 (1 − 𝑒 𝜏) (64)
where τ is defined as relaxation time
3.4 COMPLEX DIELECTRIC CONSTANT AND THE LOSS ANGLE
If a dielectric is under the influence of an alternating electric field, the

polarization P will also vary periodically with time and hence the
displacement vector D. In general, P and D may lag behind in phase
relative to the applied potential V.
Let
𝑉 = 𝑉0 cos 𝜔𝑡
Then
𝐷 = 𝐷0 cos(𝜔𝑡 − 𝜎)
𝐷 = 𝐷0 cos 𝜔𝑡 cos 𝜎 + 𝐷0 sin 𝜔𝑡 sin 𝜎
= 𝐷1 cos 𝜔𝑡 + 𝐷2 sin 𝜔𝑡
Where D1 = D0 cos σ and D2 = D0 sin σ

For most of the dielectrics D0 is proportional to V0 and D0/V0 is frequency
dependent. For the same, we can introduce frequency dependent
dielectric constants as-
𝐷1 𝐷0
𝜀 ′ (𝜔) = = 𝐷0 cos 𝛿 (65)
𝑉0 𝑉0
34
𝐷2 𝐷0
𝜀 " (𝜔) = = 𝐷0 sin 𝛿 (66)
𝑉0 𝑉0
Which results into complex dielectric constant
𝜀 ∗ = 𝜀 ′ (𝜔) + 𝑖𝜀 " (𝜔)
where ԑ’ describes the dielectric property of the material at frequency ω

and ԑ” describes the loss factor which for a perfect dielectric is zero.
Thus, in general we can write
𝐷 = 𝜀 ∗ 𝑉0 𝑒 𝑖𝜔𝑡
Now current density J is
𝜕𝐷
𝐽= = (𝜀 ′ 𝑉0 𝑖𝜔 − 𝑖(𝑖𝜔)𝜀 " 𝑉0 )𝑒 𝑖𝜔𝑡
𝜕𝑡
= (𝑖𝜀 ′ 𝑉0 𝜔 + 𝜀 " 𝑉0 𝜔)𝑒 𝑖𝜔𝑡
= 𝐽𝐶 + 𝐽𝐿
Where, JC is the current density corresponding to charging current IC and

JL to that of loss current IL which is in phase with applied potential V. The
total current density J leads the applied potential V by a phase angle θ
(<90°) as shown in Fig. 3.3
Fig. 3.3 (a) Dielectric under AC field and (b) charging current JC and
loss current density JL of a capacitor with dielectric
Now, the power dissipated due to Joule heating per unit volume will be
𝑃𝐿 = 𝐽𝐿 . 𝑉
35
= 𝜀 " 𝑉0 𝜔𝑒 𝑖𝜔𝑡 . 𝑉
= 𝜀 " 𝜔𝑉. 𝑉
𝑃𝐿 = 𝜀 " 𝜔𝑉 2 (67)
But the loss tangent:
𝜀"
tan 𝛿 = 𝜀′ (68)
Then
𝑃𝐿 = 𝜀 ′ 𝜔 tan 𝛿 𝑉 2
Also
𝑉0
𝑉=
√2
And
𝜔 = 2𝜋𝑓
Therefore
′
𝑉02
𝑃𝐿 = 𝜀 2𝜋𝑓 tan 𝛿
2
𝑃𝐿 = 𝜋𝑓𝜀 ′ 𝑉02 tan 𝛿 (69)
3.5FREQUENCY AND TEMPERATURE EFFECTS ON POLARISATION
When an alternating electrical field is applied across the material,

polarization occurs as a function of time.
Polarization as a function of time t is given by
−𝑡⁄
𝑃(𝑡) = 𝑃 [1 − 𝑒 𝑡𝑟 ] (70)
Where P is maximum polarization that occurs due to the static field applied
for a long time. tr is relaxation time (time taken for a particular polarizations
process to take place).
36
Frequency dependence
Electronic polarization is the fastest polarization which will complete at
the instant the field is applied; the reason is that the electrons are lighter
elementary particles than ions. Therefore, even for every high frequency
applied electrical field [in the optical range (≈ 1015 Hz)], electronic
polarization occurs during every cycle of the applied field.
Ionic polarization is little slower than electronic polarization. Because

ions are heavier than the electron cloud, the time taken for displacement
is large. In addition, the frequency of applied electrical field with which the
ions will be displaced is equal to the frequency of lattice vibration (~ 1013
Hz). This means that for optical frequency, the ions do not respond, as
the time required for lattice vibrations is nearly 100 times more than the
period of applied field at optical frequency. Hence at optical frequencies,
there is no ionic polarization. If the frequency of the applied field is less
than 1013 Hz. (i.e. infrared range), the ions have enough time to respond
during each cycle of the applied field.
Orientational polarization is even slower than ionic polarization. This
type of polarization occurs only at electrical frequency (audio and radio
frequency) range (≈ 106 Hz) as shown in Fig. 3.4
Space charge polarization is the slowest because ions have to diffuse
(jump) over several atomic distances. This process occurs at very low
frequency i.e. power frequency (102 Hz) as shown in Fig. 3.4.
Figure explains the four types of polarization at different frequency
ranges. At optical frequencies (-1015 HZ), electronic polarization alone is
present. At -1013 Hz range, ionic polarization occurs in addition to
electronic polarization.
At 106 to 1010 Hz range, contribution due to orientation polarization gets
added while at 102 Hz range space-charge polarization also contributes.
It is noted that at lower frequencies, all the four types of polarizations
occur and total polarization is very high (maximum). Total polarization
decreases with the increases in frequency and becomes minimum at
optical frequency range. Hence at high frequencies, the value of
polarization is very small (minimum).
37
Fig 3.4 Frequency dependence of polarization
Temperature dependence
When a dielectric material is subjected to ordinary conditions of increasing
temperature, electronic distribution in the constituent molecules is not
affected. Hence, there will be no temperature influence on electronic and
ionic polarization mechanisms. Therefore, electronic and ionic
polarizations are practically independent of temperature.
An increase in temperature brings a higher degree of randomness in
molecular orientation of the material. This will affect the tendency of
permanent dipoles to align along the direction of the field. Hence,
orientation polarization decreases with the increase in temperature.
However, in space-charge polarization, increase in temperature helps the
ion movement by diffusion. As a result, it will increase the polarization.
Thus, both orientational and space-charge polarization mechanisms are
strongly temperature dependent.
3.6 DIELECTRIC BREAKDOWN AND DIELECTRIC LOSS
Dielectric breakdown
Dielectric materials are not perfect insulators. When the externally applied
voltage to the dielectrics exceeds a critical value, then the dielectrics
break down, very large current flows through it. This value of voltage is
known as breakdown voltage.
38
Dielectric breakdown can be explained on the basis of band theory of
solids. In insulators (dielectrics), there is a large gap between the
conduction band and valence band. When the applied voltage exceeds a
certain maximum value, then the electrons of valence band get sufficient
energy to jump to the conduction band. Due to the availability of sufficient
number electrons in the conduction band, the insulating properties of
dielectric material break down. This mechanism of dielectric material is
known as dielectric breakdown.
Some important types of dielectric breakdown are:
i. Intrinsic breakdown and avalanche breakdown.

ii. Thermal breakdown
iii. Chemical and electrochemical breakdown
iv. Discharge breakdown
v. Defect breakdown
Intrinsic breakdown
For a dielectric, the charge displacement increases with increasing
electrical field strength. Beyond a critical value of electrical field strength,
there is an electrical breakdown due to physical deterioration in the
dielectric material.
When the applied electrical field is large, some of the electrons in the
valence band cross over to the conduction band across the large
forbidden energy gap. They become conduction electrons producing large
conduction current.
As a result, a large current flow through the dielectric and breakdown
occurs. This type of breakdown is called intrinsic breakdown.
Avalanche breakdown
The conduction electrons are accelerated to very high velocity and energy
on further application of electrical field.
These conduction electrons collide with valence electrons in the covalent
bond and they transfer their energy to valence electron. The valence
electrons on acquiring this energy, jump from the valence band to the
conduction band.
This process continues as more and more valence electrons jump to the
conduction band by breaking the covalent bond.
39
As a result, a large current flow through the dielectric and breakdown
occurs. This type of breakdown is called Avalanche breakdown.
Thermal breakdown
When an electrical field is applied to a dielectric material, some account
of heat is produced. This heat must be dissipated from the material.
In some cases, the amount of heat produced is very large as compared

to the heat dissipated. Due to excess of heat, the temperature inside the
dielectric increases and may produce local melting in the dielectric
material.
During this process, a large amount of current flows through the material
and causes the dielectric to breakdown. This type of breakdown is known
as thermal breakdown.
Chemical and Electrochemical breakdown
Electrochemical breakdown is similar to thermal breakdown. When the
temperature of a dielectric material increases, mobility of ions increases
and hence the electrochemical reaction may take place. This leads to
leakage current and energy loss in the material and finally dielectric
breakdown occurs. This type of breakdown is known as chemical and
electrochemical breakdown.
Discharge breakdown
Discharge breakdown occurs when a dielectric contains occluded gas

bubbles. When this type of dielectric is subjected to electrical field, the
gases present in the material will easily ionize and thus produce large
ionization current. The gaseous ions bombard the solid dielectric. This
causes electrical deterioration and leads to dielectric breakdown. This is
known as discharge breakdown.
Defect breakdown
The surface of the dielectric material may have defects such as cracks,
porosity and blow holes. Impurities like dust or moisture may collect at
these discontinuities. This will lead to a breakdown in a dielectric material.
Remedies for dielectric breakdown
To avoid breakdown, the insulating material should have the following
properties.
• It should have high resistivity to reduce leakage current.
40
• It should have high dielectric strength to withstand high
voltage.
• It should have small dielectric loss.
• It should have sufficient mechanical strength.

• It should be resistant to oils, liquids, gas fumes, acids and
alkalies.
• It should be fire-proof.
Dielectric loss
When a dielectric is applied with AC voltage, the electrical energy is

absorbed by the dielectric and certain quantity of electrical energy is
dissipated in the form of heat energy. This is known as dielectric loss.
Fig. 3.5 Dielectric loss
Expression for dielectric loss (or loss tangent)

When an AC voltage is applied to a perfect, dielectric like vacuum or
purified gas, it does not absorb electrical energy and there is no loss of
electrical energy.
Polarization of the dielectric is in phase with the voltage. In such a case,
the charging current leads the applied voltage by an angle of 90o as shown
in Fig. 3.5
We know that power loss,
𝑃𝐿 = 𝑉𝐼 cos 𝜃 (71)
When  = 90o, 𝑃𝐿 = 𝑉𝐼 cos 90°
𝑃𝐿 = 0 [Hence, cos 90o = 0]
This means that there is no power loss in the perfect dielectric.
41
However, a practical dielectric has always some loss of electrical energy.
In this case, the leakage current does not lead the applied voltage exactly
by 90o. The phase angle () is always less than 90o as shown in Fig.
The current leads the voltage by (90 - ). This shows that there is some
loss in electrical energy.  is called dielectric loss angle. This loss angle
is a measure of the power dissipated in each cycle.
The power loss for a dielectric having a capacitance C and a voltage V
applied to it at a frequency f is given by
𝑃𝐿 = 𝑉𝐼 cos 𝜃
Since  = 90 - , we have
𝑃𝐿 = 𝑉𝐼 cos(90° − 𝛿)
𝑃𝐿 = 𝑉𝐼 sin 𝛿 (72)
[Hence, cos ((90o - ) = sin - ]

We know that
𝑉
𝑉 = 𝐼𝑅 or 𝐼 = 𝑅
If the capacitive reactance is Xc, we can write

𝑉
𝐼=
𝑋𝑐
Further Xc depends on frequency of applied a.c voltage and capacitance.
It is given by
1
𝑋𝑐 =
2𝜋𝑓𝐶
Hence
𝑉
𝐼= = 𝑉2𝜋𝑓𝐶
1⁄
2𝜋𝑓𝐶
Substituting in eq. 72
42
𝑃𝐿 = 𝑉𝑉2𝜋𝑓𝐶 sin 𝛿
𝑃𝐿 = 2𝜋𝑓𝐶𝑉 2 sin 𝛿 (73)
In most of the dielectrics, the angle  is very small.
Therefore
sin 𝛿 = tan 𝛿
Dielectric power loss,
𝑃𝐿 = 2𝜋𝑓𝐶𝑉 2 tan 𝛿 (74)
It is noted that the power loss will depend on tan  as long as other factors
like voltage, frequency and capacitance are constant. tan  is called the
power factor of the dielectric.
LET US SUM UP
❖ When the applied electric field is suddenly switched off, the dipoles
will randomize i.e their dipole moment or polarization will go to
zero. However, that cannot happen instantaneously. The
individual characteristic time for a given dipole will be small for
some, and large for others. The average value is called as
the relaxation time τ of the system.
❖ At lower frequencies, all the four types of polarizations occur and
total polarization is very high (maximum). Total polarization
decreases with the increases in frequency and becomes minimum
at optical frequency range. Hence at high frequencies, the value
of polarization is very small (minimum).
❖ When the externally applied voltage to the dielectrics exceeds a
critical value, then the dielectrics break down, very large current
flows through it. This value of voltage is known as breakdown
voltage.
❖ When a dielectric is applied with AC voltage, the electrical energy
is absorbed by the dielectric and certain quantity of electrical
energy is dissipated in the form of heat energy. This is known as
dielectric loss.
43
1. Define dielectric relaxation

2. What is dielectric breakdown?
3. Define dielectric loss
ANSWERS TO CHECK YOUR
1. Dielectric relaxation refers to the relaxation response of a

dielectric medium to an external, oscillating electric field.
2. When the externally applied voltage to the dielectrics exceeds a
critical value, then the dielectrics break down, very large current
flows through it. This value of voltage is known as breakdown
voltage.
3. When a dielectric is applied with AC voltage, the electrical energy
is absorbed by the dielectric and certain quantity of electrical
energy is dissipated in the form of heat energy.
UNIT END EXERCISES
1. Explain the dipole relaxation in detail and arrive the Debye

relaxation time.
2. Explain the frequency and temperature dependence of various
polarization mechanisms in dielectric materials.
3. Give a detailed discussion on the various types of dielectric
breakdown in dielectric materials.
SUGGESTED READINGS

Delhi
Ltd., New Delhi.
Web Resources
1. https://www.youtube.com/watch?v=gtzNdfUD2wc
2. https://www.youtube.com/watch?v=Abmdmli2Qgs
3. https://www.youtube.com/watch?v=xaNYeu5Wi6E
44
4. https://www.youtube.com/watch?v=uIODQEwP0FQ
5. https://www.youtube.com/watch?v=j1-OWXSM9RQ
6. https://www.youtube.com/watch?v=11ppehbTYFE
7. https://www.youtube.com/watch?v=G3rB51mRgAo
8. https://www.youtube.com/watch?v=HeXnz6wnCmg
9. https://www.youtube.com/watch?v=cywMgqrQuvE
10. https://www.youtube.com/watch?v=6Qn1o0f6Abw
45
BLOCK II: THEORY OF FERROELECTRICS AND
PIEZO ELECTRICS
Unit 4: Ferroelectric Crystals and Phase Transition

Unit 5: Phase Transitions
Unit 6: Antiferroelectricity and Piezoelectricity
46
UNIT 4
FERROELECTRIC CRYSTALS AND PHASE TRANSITION
Structure
Overview
Objectives
4.1 Ferroelectric crystals

4.2 Classification of ferroelectric crystals
4.3 Dipole theory of ferroelectricity
Let Us Sum Up
Check Your Progress
Unit End Exercises
Suggested Readings
4.1 OVERVIEW
Ferroelectricity is the phenomenon where spontaneous electric

polarization of the material takes place. The reverse electric polarization
is possible by applying an electric field. Ferroelectricity was discovered in
1920 and Rochelle salt (scientific name-Potassium Sodium Tartrate)
exhibited the properties of sudden electric polarization. Since its
discovery, various uses have been devised and today, Ferroelectricity is
used in various fields of electronics. The materials exhibiting the
phenomenon of Ferroelectricity are called Ferroelectric Materials.
Ironically, the Ferroelectricity or the Ferroelectric Materials do not have
any connection to Iron (ferrite).
47
OBJECTIVES
➢ Describe the ferroelectric crystals.

➢ Explain the classification of ferroelectric crystals.
➢ Explain the Dipole theory of ferroelectricity.
4.1 FERROELECTRIC CRYSTALS
Rochelle salt was the first crystal known to be ferroelectric of chemical

composition (NaKC4H4O6·4H2O) sodium potassium tartrate tetrahydrate.
Rochelle salt was prepared in 17th century by Seignette in La Rochelle
(France). Fockel reported anomalously large piezoelectric constants of
Rochelle salt. Valasek (1920) discovered ferroelectricity in Rochelle salt.
Muller (1940) proposed a phenomenological theory which first brought us
systematic understanding of the relations between anomalous dielectric
piezoelectric and elastic behaviour of this crystal.
The second ferroelectric crystal discovered, by Bush and Scherrer (1935),
was potassium dihydrogen phosphate (KH2PO4) and other compounds
isomorphous with KH2PO4 also were found to be ferroelectric. Slater
(1941) published a theory of the phase transition of KH2PO4.
Wainer and Solomon (1943) in US, Oqawa (1943) in Japan and Wul and
Goldman (1945) in Russia discovered independently the anomalous
dielectric properties of BaTiO3. The ferroelectric properties of BaTiO3 were
reported by Wul and Goldman (1945) and Von Hippel et. al (1946). After
the discovery of ferroelectricity in BaTiO3, compounds with the perovskite
structure were studied extensively.
4.2 CLASSIFICATION OF FERROELECTRIC CRYSTALS
Ferroelectric crystals may be classified into two main groups, order-

disorder and displacive. One may define the character of the transition
in terms of the dynamics of the lowest frequency (“soft”) optical phonon
modes. If a soft mode can propagate in the crystal at the transition, then
the transition is displacive. If the soft mode is only diffusive (non-
propagating) there is really not a phonon at all, but is only a large
48
amplitude hopping motion between the wells of the order-disorder system.
Many ferroelectrics have soft modes that fall between these two extremes.
Order-disorder class
The order-disorder class of ferroelectrics includes crystals with hydrogen
bonds in which the motion of the protons is related to the ferroelectric
properties.
Example: Rochelle Salt (NaKC4H4O6·4H2O); Potassium dihydrogen
phosphate (KH2PO4)
Rochelle Salt: Rochelle salt has the peculiar property of being

ferroelectric only in the temperature region between -18°C and 23°C, i.e.,
it has two transition temperatures. In the region above 23°C and below -
l8°C it crystallizes in the orthorhombic structure. In the ferroelectric phase
the crystal is monoclinic. The spontaneous polarization occurs along the
direction of the original orthorhombic a-axis. Thus, Rochelle salt has only
one polar axis and two possible polarization directions (+ and - along the
a-axis). Fig. 1 shows the variation of spontaneous polarization of Rochelle
salt with temperature.
Fig. 1 Variation of spontaneous polarization of Rochelle salt with

temperature
Potassium dihydrogen phosphate, KH2PO4: A typical example of this

category is KH2PO4. Fig. 2 shows the spontaneous polarization vs
temperature curve of this material. In contrast with Rochelle salt, KH2PO4
has one Curie temperature, Tc = 123°K. Above the transition temperature
49
it has a tetragonal structure (3 mutually perpendicular axes a, a, c); below
Tc it is orthorhombic (3 mutually perpendicular axes a, b, c). The c-axis is
the spontaneous polarization direction.
Fig. 2 Spontaneous polarization of KH2PO4 as a function of

temperature
Displacive class
Barium titanate (BaTiO3): BaTiO3 is the most important and most
thoroughly studied representative of the perovskites. In the nonpolarized
phase it has cubic symmetry (Fig. 3). The Ba2+ ions occupy the corners of
a cube, the oxygen ions are located at the centers of the faces, and the
Ti4+ ion is at the center. Below the Curie temperature, the direction of the
spontaneous polarization and the crystal structure vary in the following
fashion:
50
Fig. 3 The cube structure of BaTiO3 at T > Tc and T < Tc.
BaTiO3 has three ferroelectric phases. As the spontaneous polarization

sets in at 393°K, the crystal expands in the direction of polarization (c-
axis) and contracts perpendicular to it (a-axis). These three transition
temperatures are reflected in the dielectric constant and in the
spontaneous polarisation of the material, as may be seen in Fig. 4
Fig. 4 The dielectric constant of BaTiO3 as a function of

temperature and the spontaneous polarisation of BaTiO3 measured
along a cube edge.
4.3 DIPOLE THEORY OF FERROELECTRICITY
The existence of spontaneous polarization in general requires a physical

model in which the dipole moments of the different unit cells are oriented
along a common direction. This brings ferroelectrics in the class of
cooperative phenomena, the cooperation between the different unit cells
51
in this case consisting of a tendency for a given unit cell to have its dipole
direction parallel to that of its neighbours.
The essential point in the dipole theory is that the internal field Ei which
tends to orient a given dipole is assumed to be of the form,
𝐸𝑖 = 𝐸 + 𝛾𝑃 (2.1)
where E is the externally applied field, P is the polarization, and γ is the

internal field constant. This expresses the cooperation between the
dipoles, because the larger P, the larger Ei and the stronger the tendency
for the dipole under consideration to align itself in the
direction of the polarization of its surroundings.
As long as one is far away from saturation of the polarization, one may
write,
𝑃 = 𝑁𝜇〈cos 𝜃〉 = 𝑁(𝜇 2 ⁄3𝑘𝑇)𝐸𝑖 (2.2)
where N is the number of dipoles per unit volume.

From eq. 2.1 & 2.2
𝑃
𝜒=
𝐸
= 𝑁(𝜇 2 ⁄3𝑘𝑇) 𝐸𝑖 ⁄𝐸
𝑁(𝜇 2 ⁄3𝑘𝑇)𝐸𝑖
=
𝐸𝑖 − 𝛾𝑃
𝑁(𝜇 2 ⁄3𝑘𝑇)
=
1 − (𝛾𝑃⁄𝐸𝑖 )
𝑁(𝜇 2 ⁄3𝑘𝑇)
=
1 − {𝛾[𝑁(𝜇 2 ⁄3𝑘𝑇)𝐸𝑖 ]⁄𝐸𝑖 }
𝑁(𝜇 2 ⁄3𝑘𝑇)
=
1 − (𝑁𝛾𝜇 2 ⁄3𝑘𝑇 )
(𝜃⁄𝛾𝑇)
=
1 − (𝜃⁄𝑇)
52
𝜃⁄𝛾
= 𝑇−𝜃 (2.3)
Here, 𝜃 = 𝑁(𝜇2 ⁄3𝑘 ) is the extrapolated Curie temperature and 𝜃⁄𝛾 being
Curie constant.
To show that Eq. (2.1) also leads to spontaneous polarization, we make
use of the Langevin
expression, which allows for saturation effects.

This gives
𝑃 = 𝑁𝜇〈cos 𝜃〉 = 𝑁𝜇𝐿(𝜇𝐸𝑖 ⁄3𝑘𝑇) = 𝑁𝜇𝐿(𝜇(𝐸 + 𝛾𝑃 )⁄3𝑘𝑇) (2.4)
L(x) is the Langevin function. To show Eq. (2.1) indeed leads to the
possibility of spontaneous polarization. Putting E = 0 in Eq. (2.4), we may
write
𝑃⁄𝑁𝜇 = 𝑃⁄𝑃𝑠𝑎𝑡 = 𝐿(𝑥) (2.5)
Where
𝑥 = 𝜇𝛾𝑃⁄𝑘𝑇
Or
𝑃⁄𝑁𝜇 = (𝑘𝑇⁄𝑁𝜇 2 𝛾 )𝑥 (2.6)
𝑁𝜇 = 𝑃𝑠𝑎𝑡 represents evidently the saturation polarization corresponding

to complete alignment of the dipoles
Fig. 5 Langevin function
53
The fully drawn curve represents the Langevin function. The slope of L(x)
at the origin is 1/3.
However, P/Psat should also satisfy Eq. (2.6), which corresponds to a set
of straight lines passing through the origin, the slope of the lines being
given by 𝑘𝑇⁄𝑁𝜇2 𝛾. Thus, the solution for P/Psat corresponding to the
temperature T1 is determined by the intersection of L(x) and the line of
slope 𝑘𝑇1 ⁄𝑁𝜇2 𝛾. It is observed that as T decreases, the slope of the
straight-line Eq. (2.6) decreases and the solution P/Psat approaches unity.
Also, when the temperature is higher than a critical value determined by,
𝑘𝑇𝑐 ⁄𝑁𝜇 2 𝛾 = 1/3
𝑇𝑐 = 𝑁𝜇 2 𝛾/3𝑘 (2.7)
LET US SUM UP
• Rochelle salt was the first crystal known to be ferroelectric of

chemical composition (NaKC4H4O6·4H2O) sodium potassium
tartrate tetrahydrate.
• The order-disorder class of ferroelectrics includes crystals with
hydrogen bonds in which the motion of the protons is related to the
ferroelectric properties. Example: Rochelle Salt
(NaKC4H4O6·4H2O); Potassium dihydrogen phosphate (KH2PO4).
• The displacive class of ferroelectrics includes ionic crystal
structures closely related to the perovskite structures. Example:
BaTiO3. It has cubic structure above TC, below TC lattice structure
is changed. Ba2+ and Ti4+ ions displaced relatively to the O2- ions,
which is the root of spontaneous polarization.
1. What is ferroelectricity?
2. Define order-disorder class of ferroelectric crystals.
3. Define displacive class of ferroelectric crystals.
54
1. If we have two equal and opposite charges, +q and -q, the moment
of this dipole can be defined as 𝜇 = 𝑞𝑟
2. The displacive class of ferroelectrics includes ionic crystal
structures closely related to the perovskite structures.
UNIT END EXERCISES
1. Ferroelectricity is a characteristic of certain materials that have

a spontaneous electric polarization that can be reversed by the
application of an external electric field
2. The order-disorder class of ferroelectrics includes crystals with
hydrogen bonds in which the motion of the protons is related to the
ferroelectric properties.
3. Describe the dipole theory of ferroelectricity in detail.
SUGGESTED READINGS

Delhi
2. S. O. Pillai (2006), Solid State Physics, 6th Edition, New Age
International (P) Ltd., Publishers, New Delhi
Web Resources
1. https://www.youtube.com/watch?v=qTRFTyQ2f3w
2. https://www.youtube.com/watch?v=ztNoL0F7WgI
3. https://www.youtube.com/watch?v=lDlcCrp90Ak
4. https://www.youtube.com/watch?v=MSf3KLtoaJI
5. https://www.youtube.com/watch?v=VOddAj9y3pE
6. https://www.youtube.com/watch?v=4fdh3oKgiWE
7. https://www.youtube.com/watch?v=bDA9SBeddlU
8. https://www.youtube.com/watch?v=82kO9ypI834
55
UNIT 5
PHASE TRANSITIONS
Structure
Overview
Objectives
5.1 Landau theory of the phase transition
5.2 Second order transition
5.3 First order transition
5.4 Ferroelectric transition
Let Us Sum Up
Check Your Progress
Unit End Exercises
Suggested Readings
OVERVIEW
The study of phase transitions is at the very core of structural condensed-

matter physics, to the point that one might consider all we have learned in
the previous lectures as a mere preparation for the last one. The reason
why the structural physicist has so much to offer here is that, in a large
class of phase transitions, the system undergoes a symmetry change.
Here is a reminder of a few generic facts about phase transitions.
A phase transition can be driven by many parameters - temperature,
pressure, chemical composition, magnetic or electric field etc. If the
driving parameter is temperature, the high-temperature phase is almost
always more disordered, i.e., has a higher symmetry than the low-
temperature phase.
As for the point here above, phase transitions entail a change in the
entropy of the system. The change can be:
Discontinuous. In this case, the phase transition is accompanied by
release of heat (latent heat), and all the other thermodynamic quantities
56
(internal energy, entropy, enthalpy, volume etc.) are discontinuous as
well. Such a phase transition is known as first-order transition.
Continuous. In this case, the phase transition is continuous across the
transition temperature (or other transition parameter). The thermodynamic
quantities are continuous, but their first derivatives are discontinuous. In
particular, the specific heat has a pronounced anomaly and the thermal
expansion coefficient has a step at the transition. It is known as second-
order transition.
Some important phase transitions do not entail a change in symmetry –
e.g., the liquid-to-gas transition. Such phase transitions can only be first-
order.
OBJECTIVES
➢ Describe the Landau theory of the phase transition.

➢ Explain the First and Second Order Transition
➢ Understand the basis of Ferroelectric transition
5.1 LANDAU THEORY OF THE PHASE TANSITIONS
A ferroelectric with a first-order phase transition between the ferroelectric

and the paraelectric state is distinguished by a discontinuous change of
the saturation polarization at the transition temperature. In the second-
order transition the degree of order goes to zero without a discontinuous
change as the temperature is increased. A thermodynamic theory has the
advantage of being independent of any particular atomic model and thus
leads to quite general conclusions. Such a theory does not provide the
physical mechanism responsible for the ferroelectric properties of a given
material.
Let us consider a solid which is ferroelectric for temperatures T < Tc; let
the external pressure be zero and let there be no applied electric field. If
the crystal is in equilibrium at a given temperature, the free energy of the
crystal F should be a minimum. For simplicity we shall assume that in the
ferroelectric region the spontaneous polarization occurs along a single
axis; this would be the case for the Rochelle salt, KH2PO4 and for the
upper transition of BaTiO3. Let F0 represent the free energy of the
57
unpolarized crystal; the free energy F of the polarized crystal may then be
expanded as a power series in the polarization
1 1 1
𝐹 − 𝐹0 = 2 𝑐1 𝑃2 + 4 𝑐2 𝑃4 + 6 𝑐3 𝑃6 + ⋯ (2.8)
The coefficients c are functions of temperature; the numerical factors are

introduced for
𝜕𝐹
later convenience. In thermal equilibrium, (𝜕𝑃) = 0. The spontaneous
𝑇
polarization, thereby, satisfies the equation:
𝑐1 𝑃𝑠 + 𝑐2 𝑃𝑠3 + 𝑐3 𝑃𝑠5 + ⋯ = 0 (2.9)
It is observed that Ps = 0 is always a root of this equation and that and c1,
c2, c3 are all positive, the root Ps = 0 will correspond to the only minimum
of the free energy and thus spontaneous polarization would not occur.
However, if as a result of the temperature dependence the coefficient c1
would become negative, F would have a maximum for Ps = 0 and there
would be at least one nonvanishing value for Ps for which F would be a
minimum, i.e., spontaneous polarization would occur.
5.2 SECOND ORDER TRANSITION
If the coefficients c1, c2, c3 are all positive and the value of c1 varies from
positive to negative as the temperature is lowered, one obtains free
energy curves as illustrated in Fig. 6. The corresponding spontaneous
polarization as function of temperature is indicated in Fig. 7.
Fig. 6 Free energy as a function of polarization for various values of

χ for a second-order transition.
58
The transition temperature corresponds to c1 = 0. Assuming in Eq. (15)
that the term with c3 is
negligible, one obtains for the spontaneous polarization,

𝑐
𝑃𝑠2 = − 1⁄𝑐2 (2.10)
Ps is a continuous function of temperature; a transition of this type is not

associated with a latent heat but with a discontinuity in the specific heat
and is called a second-order transition.
Let us now consider the susceptibility of the crystal above and below the
transition temperature. For this purpose, it is necessary to apply a small
electric field to the crystal. Now, for a crystal under zero pressure in an
applied field E, we may write according to thermodynamics,
dF = −SdT + EdP.
Above the transition temperature the polarization will be small for small
applied fields, and in this region, we may neglect all terms on the right-
hand side of Eq. (2.8) except the first. For T > Tc,
𝐸 = 𝜕𝐹 ⁄𝜕𝑃 = 𝑐1 𝑃
and
1⁄𝜒𝑎 = 𝜕𝐹 ⁄𝜕𝑃 = 𝑐1 (2.11)
χa being susceptibility above the Curie temperature. The susceptibility in

this temperature range is given by the Curie-Weiss law
𝐶 𝑇−𝜃
𝜒𝑎 = ⟹ 𝑐1 =
𝑇−𝜃 𝐶
Where C is the Curie constant. Since the transition at T= Tc corresponds

to c1 = 0, we have θ = Tc which leads to
𝑇−𝑇𝑐
𝑐1 = = 1⁄𝜒𝑎 (2.12)
𝐶
Similarly, in the ferroelectric region, we obtain,
𝐸 = 𝜕𝐹 ⁄𝜕𝑃 = 𝑐1 𝑃 + 𝑐2 𝑃23 ⟹ 1⁄𝜒𝑏 = 𝜕𝐸 ⁄𝜕𝑃 = 𝑐1 + 3𝑐2 𝑃2 (2.13)
59
χa being susceptibility above the Curie temperature.
For small applied fields, Ps ≈ P in this region, so that according to Eqs.
(2.12) and (2.13) we have
1⁄𝜒𝑏 = 𝑐1 + 3𝑐2 (− 𝑐1⁄𝑐2 ) = −2𝑐1 (2.14)
Fig. 7 Spontaneous polarization and reciprocal susceptibility near

the transition temperature Tc for a second-order transition
If we still assume the temperature dependence of c1 on the ferroelectric
side of Tc, we further obtain from eq. (2.13 and (2.14),
2(𝑇−𝑇𝑐 )
1⁄𝜒𝑏 = −2𝑐1 = (2.15)
𝐶
In connection with the entropy associate with spontaneous polarization,

the entropy is
1 1
𝑆 = −(𝜕𝐹 ⁄𝜕𝑇)𝑃 = 𝑆0 − 𝑃2 (𝜕𝑐1 ⁄𝜕𝑇) − 𝑃4 (𝜕𝑐2 ⁄𝜕𝑇) + ⋯
2 4
where S0 is the entropy of the unpolarized crystal. To a first approximation,

we may write
1
𝑆 − 𝑆0 = − 2 𝑃2 (𝜕𝑐1 ⁄𝜕𝑇) (2.16)
Since P is a continuous function of temperature for the case under

consideration and since
60
the slope of P2 has a discontinuity at T = Tc, there should be a
discontinuity in the specific
heat, but no latent heat, i.e., the transition is of the second order.
5.3 FIRST ORDER TRANSITION
We have seen that spontaneous polarization requires the coefficient c1 to

be negative. Furthermore, we have seen that if at the same time c2 is
positive, a second-order transition results.
Fig. 8 Free energy as a function of polarization for various values of

χ for a first-order transition.
We shall now consider the case for which c2 is negative and c3 is positive.
Under these circumstances it is possible for the free energy curves to
have a minimum value for a nonzero value of the polarization to coexist
with a minimum for Ps = 0. Assuming that c1 varies from positive to
negative values as the temperature is lowered, one obtains free energy
curves of the type indicated in Fig. 8.
In the absence of an external field we obtain from the equilibrium condition
(𝜕𝐹 ⁄𝜕𝑇) 𝑇 and from Eq. (2.8) for the nonvanishing value of the
spontaneous polarization the equation
61
Fig. 9 Spontaneous polarization and reciprocal susceptibility near
the transition temperature Tc for a first-order transition
𝑐1 − |𝑐2 |𝑃𝑠2 + 𝑐3 𝑃𝑠4 = 0 (2.17)
A transition from the non-polarized state to a spontaneously polarized

state will now occur when the minimum of the free energy corresponding
to Ps = 0 becomes equal to the minimum associated with a nonzero value
for Ps. So we can write that
1 1 1
𝐹(𝑃𝑠 , 𝑇𝑐 ) = 𝐹0 (0, 𝑇𝑐 ) ⇒ 2 𝑐1 𝑃𝑠2 (𝑇𝑐 ) − 4 |𝑐2 |𝑃𝑠4 (𝑇𝑐 ) − 6 𝑐3 𝑃𝑠6 (𝑇𝑐 )+= 0
(2.18)
From eq. (2.17)
𝑐1 = |𝑐2 |𝑃𝑠2 + 𝑐3 𝑃𝑠4 (2.19)
Putting the value of c1 in Eq. (2.18), we obtain
1 2 1 1
𝑃𝑠 (𝑇𝑐 )[|𝑐2 |𝑃𝑠2 + 𝑐3 𝑃𝑠4 ] − |𝑐2 |𝑃𝑠4 (𝑇𝑐 ) − 𝑐3 𝑃𝑠6 (𝑇𝑐 ) + ⋯ = 0
2 4 6
1 1
|𝑐2 |𝑃𝑠4 (𝑇𝑐 ) − 𝑐3 𝑃𝑠6 (𝑇𝑐 ) + ⋯ = 0
4 3
1 1
𝑃𝑠4 (𝑇𝑐 ) [ |𝑐2 | − 𝑐3 𝑃𝑠2 (𝑇𝑐 )] = 0
4 3
62
Either Ps = 0 or
3|𝑐2 |
𝑃𝑠2 (𝑇𝑐 ) = (2.20)
4𝑐3
It is evident that in this case the polarization jumps at the critical

temperature from zero to some non-zero value, i.e., the polarization as
function of temperature exhibits a discontinuity at T = Tc. According to Eq.
(2.16), the entropy will also be discontinuous at T = Tc and there will be a
latent heat, i.e., the transition is of the first order.
Using the condition of Eq. (2.19) in Eq. (2.20),
3|𝑐2 | 3|𝑐 | 2 3|𝑐2 |2

𝑐1 = |𝑐2 |𝑃𝑠2 + 𝑐3 𝑃𝑠4 = |𝑐2 | − 𝑐3 ( 4𝑐2 ) = (2.21)
4𝑐3 3 16𝑐3
Hence,
3|𝑐2 |2 9 |𝑐2 |2 1 9 16𝑐1 1 3𝑐1

𝑃𝑠4 = = 16 = 16 × ×𝑐 = (2.22)
4𝑐3 𝑐3 𝑐3 3 3 𝑐3
We now consider the susceptibility on both sides of the critical

temperature. As in case of second-order transition, the coefficient c1 in
the region above the temperature Tc is again equal to 1/χa. In this region
the susceptibility follows the Curie-Weiss law, so that
𝑇−𝜃
𝑐1 = = 1⁄𝜒𝑎 (2.23)
𝐶
We find also susceptibility below the critical temperature in following

manner:
𝐸 = 𝜕𝐹 ⁄𝜕𝑃 = 𝑐1 𝑃 − |𝑐2 |𝑃23 + 𝑐3 𝑃25 ⇒ 1⁄𝜒𝑏 = 𝜕𝐸 ⁄𝜕𝑃

= 𝑐1 − 3|𝑐2 |𝑃2 + 5𝑐3 𝑃4
3|𝑐2 | 3𝑐1 9|𝑐2 |2 16𝑐1

⇒ 1⁄𝜒𝑏 = 𝑐1 − 3|𝑐2 | + 5𝑐3 = 16𝑐1 −
4𝑐3 𝑐3 4 3|𝑐2 |2
𝑇−𝜃
= 16𝑐1 − 12𝑐1 = 4𝑐1 = 4
𝐶
63
𝑇𝑐 −𝜃
At the critical temperature c1 is, according to Eq. (2.23), equal to 𝐶
and
the susceptibilities just above and just below Tc are given by
1⁄ = 𝑇𝑐−𝜃 and 1⁄ = 4(𝑇𝑐−𝜃)

𝜒𝑎 𝐶 𝜒𝑏 𝐶
5.4 FERROELECTRIC TRANSITION
It is common to observe that as the temperature is raised, the bulk

polarisation decreases and vanishes abruptly at a temperature Tc. This is
a phase transition, just as in a ferromagnet raised above its Curie
temperature, or a solid raised above its melting point.
It arises microscopically because as temperature is raised the thermal
vibrations of the atoms in the solid cause fluctuations which overcome the
potential barrier between the two (or more) wells. It is most easily
understood in a molecular crystal such as NaNO2, where one can imagine
that each molecule can fluctuate between two configurations. Each of
which has a double potential well as in Fig. 10, and some interactions
between the dipoles that tend to align them. The detailed microscopic
theory of how this happens will be different from material to material, but
the macroscopic properties of the phase transition will be similar across
many different classes of materials.
Fig. 10 Schematic potential well
64
LET US SUM UP
• The phase transition is accompanied by release of heat (latent

heat), and all the other thermodynamic quantities (internal energy,
entropy, enthalpy, volume etc.) are discontinuous as well. Such a
phase transition is known as first-order transition.
• The phase transition is continuous across the transition
temperature (or other transition parameter). The thermodynamic
quantities are continuous, but their first derivatives are
discontinuous. It is known as second-order transition.
1. What is first-order phase transition?

2. What is second-order phase transition?
1. The phase transition is accompanied by release of heat (latent

heat), and all the other thermodynamic quantities (internal energy,
entropy, enthalpy, volume etc.) are discontinuous as well. Such a
phase transition is known as first-order transition.
2. The phase transition is continuous across the transition
temperature (or other transition parameter). The thermodynamic
quantities are continuous, but their first derivatives are
discontinuous. It is known as second-order transition.
UNIT END EXERCISES
1. Discuss the Landau theory of phase transition in ferroelectric

crystals.
2. Describe the second order phase transition in ferroelectric
materials.
3. Describe the first order phase transition in ferroelectric materials
65
SUGGESTED READINGS

Delhi
Ltd., New Delhi
Web Resources
1. https://www.youtube.com/watch?v=zbXy_J-HLG8
2. https://www.youtube.com/watch?v=40rB2nBmFAU
3. https://www.youtube.com/watch?v=J-PmKDywEAM
4. https://www.youtube.com/watch?v=L9WLBgUwvDA
5. https://www.youtube.com/watch?v=R9Xj3bII0jg
6. https://www.youtube.com/watch?v=TrCCQru2ru0
7. https://www.youtube.com/watch?v=82kO9ypI834
8. https://www.youtube.com/watch?v=kl0lqRnfUWg
9. https://www.youtube.com/watch?v=MIL7M0GKDOM
10. https://www.youtube.com/watch?v=Wya57SmeN00
11. https://www.youtube.com/watch?v=LX6dJwpd4AA
66
UNIT 6
ANTIFERROELECTRICITY AND PIEZOELECTRICITY
Structure
Overview
Objectives
6.1 Antiferroelectricity
6.2 Ferroelectric domains
6.3 Piezoelectricity
6.4 Phenomenological approach to piezoelectric effects
6.5 Piezoelectric parameters and measurements
6.6 Piezoelectric materials
Let Us Sum Up
Check Your Progress
Unit End Exercises
Suggested Readings
OVERVIEW
Antiferroelectricity is a physical property of certain materials. It is closely

related to ferroelectricity; the relation between antiferroelectricity and
ferroelectricity is analogous to the relation between anti-
ferromagnetism and ferromagnetism.
An antiferroelectric material consists of an ordered (crystalline) array
of electric dipoles (from the ions and electrons in the material), but with
adjacent dipoles oriented in opposite (antiparallel) directions (the dipoles
of each orientation form interpenetrating sublattices, loosely analogous to
a checkerboard pattern). This can be contrasted with a ferroelectric, in
which the dipoles all point in the same direction.
In an antiferroelectric, unlike a ferroelectric, the total,
macroscopic spontaneous polarization is zero, since the adjacent dipoles
cancel each other out.
67
Antiferroelectricity is a property of a material, and it can appear or
disappear (more generally, strengthen or weaken) depending on
temperature, pressure, external electric field, growth method, and other
parameters. In particular, at a high enough temperature,
antiferroelectricity disappears; this temperature is known as the Néel
point or Curie point.
OBJECTIVES

➢ Describe the term Antiferroelectricity.
➢ Explain Piezoelectricity Piezoelectric parameters and
measurements.
6.1 ANTIFERROELECTRCITY
As in the case of magnetism, the electric dipole moments orient

themselves in a parallel or antiparallel fashion. Figure 6 displays
schematically two different polarization patterns. In Figure 6a, positively
and negatively charged ions are displaced alternately in the downward
and upward direction. The associated dipoles create an antiferroelectric
order. Functionally, a material is referred to as antiferroelectric if it can be
field-forced to a ferroelectric state (i.e. the free energies of the ferroelectric
and antiferroelectric states must be similar). In contrast to this case,
Figure 6b displays the behaviour of the displacements close to a domain
wall of a ferroelectric phase. Whether a given structure forms a
ferroelectric or antiferroelectric order depends on the overall lattice forces
and dipolar interactions.
Figure 7 displays the polarization dependence on the electric field in an
antiferroelectric crystal. With a low electric field, a weak polarization is
exhibited. Only if a critical field Ec, which breaks the antiferroelectric order
is surpassed, will a major polarization occur. Around this critical field,
hysteresis effects are observed in a similar way to those that occur in
ferroelectric materials around E = 0 (see Figure 3), although in this case,
the hysteresis is due to the field forcing a phase transition from the
antiferroelectric to a ferroelectric phase. An example of an antiferroelectric
is the material lead zirconate (PbZrO3).
68
Figure 6: Sketch of perovskite structures. The big circles present
the O2− lattice, the small grey dots the sublattices with positive
charges. (a) antiferroelectric structure and (b) two oppositely
polarized ferroelectric domains.
Figure 10: Antiferroelectric hysteresis loop. For |Eext| > Ec the

system transforms into a ferroelectric state
6.2 FERROELECTRIC DOMAINS
In a ferroelectric crystal, it is likely that the alignment of dipoles in one of

the polar directions extends only over a region of the crystal and there can
69
be different regions in the crystal with aligned dipoles which are oriented
in many different directions with respect to one another.
Regions of uniform polarization are called domains, separated by a
boundary called domain wall. We should not confuse ferroelectric domain
walls with the grain boundaries. Depending upon the grain size, one grain
can have more than one or more domains. The types of domain walls that
can occur in a ferroelectric crystal depend upon the crystal structure and
symmetry of both paraelectric and ferroelectric phases. For instance,
rhombohedral phase of lead zirconate titanate, Pb(Zr,Ti)O3 has Ps vector
along [111]-direction which gives eight possible directions of spontaneous
polarization with 180°, 71° and 109° domain walls. On the other hand, a
tetragonal perovskite like PbTiO3 has Ps along the [001]-axis and here
domain walls are either 180° or 90° domain walls.
Fig. 11 Schematic representation of a 180° and 90° domain walls in

a tetragonal perovskite crystal such as BaTiO3
Formation of the domains may also be the result of mechanical constraints

associated with the stresses created by the ferroelectric phase transition
e.g. from cubic paraelectric phase to tetragonal paraelectric phase in
PbTiO3. Both 180° and 90° domains minimize the energy associated with
the depolarizing field but elastic energy is minimized only by the formation
of 90° domains. Combination of both effects leads to a complex domain
structure in the material with both 90° and 180° domain walls.
The driving force for the formation of domain walls is the minimization of
the electrostatic energy of the depolarizing field (Ed), due to surface
70
charges due to polarization, and the elastic energy associated with the
mechanical constraints arising due to ferroelectric paraelectric phase
transition. This electrostatic energy associated with the depolarizing field
can be minimized by splitting of the material into oppositely oriented
domains or compensation of the electrical charge via electrical conduction
through the crystal.
6.3 PIEZOELECTRCITY
In 1880, Pierre Curie and Jacques Curie discovered the (direct)

piezoelectric effect in quartz (SiO2) and other single crystals, which
generates an electric charge proportional to a mechanical stress. The
converse piezoelectric effect, a geometric strain proportional to an applied
voltage, was also soon realized. Since then, quartz has been one of the
most well-known and widely used piezoelectric materials. Many decades
later, polycrystalline piezoelectric ceramics (oxides) have been
discovered.
6.4 PHENOMENOLOGICAL APPROACH TO PIEZOELECTRIC

EFFECTS
A piezoelectric substance is one that produces an electric charge when a

mechanical stress is applied (the substance is squeezed or stretched).
Conversely, a mechanical deformation (the substance shrinks or
expands) is produced when an electric field is applied. This effect is
formed in crystals that have no center of symmetry. To explain this, we
have to look at the individual molecules that make up the crystal. Each
molecule has a polarization, one end is more negatively charged and the
other end is positively charged, and is called a dipole. This is a result of
the atoms that make up the molecule and the way the molecules are
shaped. The polar axis is an imaginary line that runs through the center
of both charges on the molecule. In a monocrystal the polar axes of all of
the dipoles lie in one direction. The crystal is said to be symmetrical
because if you were to cut the crystal at any point, the resultant polar axes
of the two pieces would lie in the same direction as the original. In a
polycrystal, there are different regions within the material that have a
different polar axis. It is asymmetrical because there is no point at which
the crystal could be cut that would leave the two remaining pieces with
the same resultant polar axis. Fig. 12 illustrates this concept.
71
Fig. 12 Mono vs poly crystals
In order to produce the piezoelectric effect, the polycrystal is heated under

the application of a strong electric field. The heat allows the molecules to
move more freely and the electric field forces all of the dipoles in the
crystal to line up and face in nearly the same direction (Fig. 13).
Fig. 13 Polarization of Ceramic Material to Generate Piezoelectric

Effect
The piezoelectric effect can now be observed in the crystal. Fig.14

illustrates the piezoelectric effect. Fig. 14a shows the piezoelectric
material without a stress or charge. If the material is compressed, then a
voltage of the same polarity as the poling voltage will appear between the
electrodes (b). If stretched, a voltage of opposite polarity will appear (c).
Conversely, if a voltage is applied the material will deform. A voltage with
the opposite polarity as the poling voltage will cause the material to
expand, (d), and a voltage with the same polarity will cause the material
to compress (e). If an AC signal is applied then the material will vibrate at
the same frequency as the signal (f).
72
Fig. 14 Example of Piezoelectric Effect
6.5 PEIZOELECTRIC PARAMETERS AND THEIR MEASUREMENTS
Piezoelectric Charge (Strain) Constant
The piezoelectric charge coefficient relates the electric charge generated

per unit area with an applied mechanical force and is expressed in the unit
of Coulomb/Newton (C/N). This constant is most frequently used to
evaluate the goodness of a piezoelectric material.
𝑆𝑡𝑟𝑎𝑖𝑛 𝑑𝑒𝑣𝑒𝑙𝑜𝑝𝑒𝑑 𝐶ℎ𝑎𝑟𝑔𝑒 𝑑𝑒𝑛𝑠𝑖𝑡𝑦 (𝑜𝑝𝑒𝑛 𝑐𝑖𝑟𝑐𝑢𝑖𝑡)

𝑑= =
𝐴𝑝𝑝𝑙𝑖𝑒𝑑 𝑓𝑖𝑒𝑙𝑑 𝐴𝑝𝑝𝑙𝑖𝑒𝑑 𝑆𝑡𝑟𝑒𝑠𝑠
The d constant is associated with three important materials properties

through the following the equation:
𝑑 = 𝑘√𝜀0 𝑘 𝑇 𝑆𝐸
where k is electro-mechanical coupling coefficient, kT denotes relative

dielectric constant at a constant stress, and SE is elastic compliance (10
m/N) at a constant electrical field.
There are two important d constants:
73
𝑑31 = 𝑘√𝜀0 𝑘3𝑇 𝑆11
𝐸
𝑑33 = 𝑘√𝜀0 𝑘3𝑇 𝑆33

𝐸
It is useful to remember that large d constants relate to large mechanical

displacements, which are usually sought in motional transducer devices.
Conversely, the coefficient may be viewed as relating the charge collected
on the electrodes, to the applied mechanical stress. d33 applies when the
force is along the three direction (parallel with the polarization axis) and is
impressed on the same surface from which the charge is collected. d31
applies when the charge is collected from the same surface as with d33,
but the force is applied at right angles to the polarization axis. It is
commonly known that they have the following empirical relation.
𝑑33 = −2.5 𝑑31
Piezoelectric Voltage Coefficient (G-constant)

The piezoelectric voltage coefficient is also called voltage output constant,
which is defined as the ratio of the electric field produced to the
mechanical stress applied and is expressed in the unit of voltage-
meter/Newton (Vm/N).
𝑆𝑡𝑟𝑎𝑖𝑛 𝑑𝑒𝑣𝑒𝑙𝑜𝑝𝑒𝑑 𝐹𝑖𝑒𝑙𝑑 𝑑𝑒𝑣𝑒𝑙𝑜𝑝𝑒𝑑

𝑔= =
𝐴𝑝𝑝𝑙𝑖𝑒𝑑 𝑐ℎ𝑎𝑟𝑔𝑒 𝑑𝑒𝑛𝑠𝑖𝑡𝑦 𝐴𝑝𝑝𝑙𝑖𝑒𝑑 𝑚𝑒𝑐ℎ𝑎𝑛𝑖𝑐𝑎𝑙 𝑠𝑡𝑟𝑒𝑠𝑠
The g-constants are calculated from the piezoelectric charge (strain)

constant (d) and relative permittivity (𝜀) from the equation:
𝑑
𝑔=
𝜀
Depending on the type of relative directions, the g constant can be

categorized as g33, g31, or g15, corresponding to d33, d31, or d15,
respectively.
Piezoelectric Coupling Coefficient

The piezoelectric coupling coefficient (sometimes referred as the
electromechanical coupling coefficient) is defined as the ratio of the
74
mechanical energy accumulated in response to an electrical input or vice
versa. It also corresponds to the fraction of electrical energy that can be
converted into mechanical energy and vice versa. Thus, the piezoelectric
coupling coefficient can be expressed by the following equation:
𝑀𝑒𝑐ℎ𝑎𝑛𝑖𝑐𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 𝑠𝑡𝑜𝑟𝑒𝑑 𝐸𝑙𝑒𝑐𝑡𝑟𝑖𝑐𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 𝑠𝑡𝑜𝑟𝑒𝑑

𝑔=√ =√
𝐸𝑙𝑒𝑐𝑡𝑟𝑖𝑐𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 𝑎𝑝𝑝𝑙𝑖𝑒𝑑 𝑀𝑒𝑐ℎ𝑎𝑛𝑖𝑐𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 𝑎𝑝𝑝𝑙𝑖𝑒𝑑
The coupling factor can be calculated based on the measured resonance

and anti-resonance frequencies of a piezoelectric element, depending on
the vibration mode at which the element is excited. The most used
coupling factors are kp and kt for the vibration along the radial and
thickness directions in a circle-shaped disk, respectively. In general, a
useful parameter keff is frequently used to express the effective coupling
coefficient of an resonator with an arbitrary shape, either at its
fundamental resonance or at any overtone modes, and is expressed as
follows:
2
𝑓𝑟 2
𝑘𝑒𝑓𝑓 = 1−( )
𝑓𝑎
where fr and fa stand for resonating frequency and anti-resonating

frequency, respectively. The coupling coefficients can be calculated for
the various modes of vibration from the following equations:
where
J - Bessel function of the first kind and zero order
J1 - Bessel function of the first kind and first order

𝜎E - Poisson’s ratio
𝜂1 - Lowest positive root of (1+𝜎E)⋅J1𝜂 = 𝜂J0(𝜂)
Fr - Resonance frequency (Hz)
Fa - Anti-resonance frequency (Hz)
75
ΔF =Fa −Fr (Hz)
Assuming that 𝜎E = 0.31 for PZT ceramics and 𝜂1 = 2.05, the following
simplified equations holds:
Mechanical Quality Factor

The mechanical Qm (also referred to as Q) is the ratio of the reactance to
the resistance in the series equivalent circuit representing the
piezoelectric resonator, which is related to the sharpness of the
resonance frequency. The mechanical Qm can be calculated using the
equation:
𝑓𝑟
𝑄𝑚 =
𝑓2 − 𝑓1
where fr is the resonance frequency, f1 and f2 are frequencies at −3 dB of

the maximum admittance. The mechanical Qm is also related to the
electromechanical coupling factor k, following the equation:
1 𝐹𝑎2
𝑄𝑚 = ( 2 2)
2𝜋𝐹𝑟 𝑍𝑚 𝐶0 𝐹𝑎 𝐹𝑟
Where,
Fr - Resonance frequency (Hz)
Fa - Anti-resonance frequency (Hz)

Zm - Impedance at Fr (ohm)
C0 - Static capacitance (Farad)
76
6.6 PIEZOELECTRIC MATERIALS
The most commonly known piezoelectric material is quartz. But

piezoelectric materials are numerous, the most used are
Quartz (SiO2): Quartz shows a strong piezoelectricity due to its crystalline

structure, meaning that when a pressure is applied on a quartz crystal an
electrical polarization can be observed along the pressure direction.
Gallium orthophosphate (GaPO4): Gallium orthophosphate has almost

the same crystalline structure as quartz, that is why it has the same
characteristics. However, its piezoelectric effect is almost twice as
important as the one for the quartz, making it a valuable asset for
mechanical application. It is not a natural element, it has to be
synthesised.
Tourmaline: crystal commonly black but can range from violet to green
and pink.
Barium Titanate (BaTiO3): This element is an electrical ceramic; it is
usually replaced by lead zirconate titanate (PZT) for piezoelectricity. It is
used for microphones and transducers.
Lead Zirconate Titanate (PbBO3 - PZT): PZT is one of the most used
piezoelectric in a variety of applications due to its excellent properties and
high enough transition temperatures. It has a perovskite structure with B
sites randomly occupied by either of isovalent Ti and Zr ions.
Berlinite (AlPO4)
Zinc oxide (ZnO)
Aluminum Nitride (AiN)
Polyvinylidene Fluoride (PVDF)
LET US SUM UP
• A material is referred to as antiferroelectric if it can be field-forced

to a ferroelectric state (i.e. the free energies of the ferroelectric and
antiferroelectric states must be similar).
• In a ferroelectric crystal, the alignment of dipoles in one of the polar
directions extends only over a region of the crystal and it is called
ferroelectric domain.
• Piezoelectric effect in quartz (SiO2) and other single crystals,
which generates an electric charge proportional to a mechanical
77
stress. The converse piezoelectric effect is a geometric strain
proportional to an applied voltage.
1. Define ferroelectric domain.

2. What is piezoelectric effect?
3. What are piezoelectric parameters?
1. Regions of uniform polarization are called ferroelectric domains.

2. Piezoelectric effect in quartz (SiO2) and other single crystals,
which generates an electric charge proportional to a mechanical
stress.
3. Piezoelectric charge (strain) constant, piezoelectric voltage
coefficient, piezoelectric coupling coefficient, and mechanical
quality factor
UNIT END EXERCISES
1. Explain in detail about antiferroelectricity.

2. Discuss in detail about ferroelectric domain.
3. Lis the piezoelectric parameters and explain them.
SUGGESTED READINGS

Delhi
Ltd., New Delhi.
Web Resources
1. https://www.youtube.com/watch?v=gq3TrxfkwAg
2. https://www.youtube.com/watch?v=MSf3KLtoaJI
3. https://www.youtube.com/watch?v=U9l9hp9KlN0
4. https://www.youtube.com/watch?v=Y11DCZRvWjM
5. https://www.youtube.com/watch?v=9i5_09ZHT0I
78
6. https://onscale.com/piezoelectricity/what-is-piezoelectricity/
7. https://onscale.com/piezoelectricity/history-of-piezoelectricity/
8. https://www.youtube.com/watch?v=HyuhtnQiOx4
9. https://www.youtube.com/watch?v=_KdWxyWHsqk
79
BLOCK III: MAGNETIC PROPERTIES
Unit 7: Classification of Magnetic Materials
Unit 8: Diamagnetism and Paramagnetism
Unit 9: Ferromagnetism, Antiferromagnetism and
Ferrimagnetism
80
UNIT 7
CLASSIFICATION OF MAGNETIC MATERIALS
Structure
Overview
Objectives
7.1 Terms and Definitions
7.2 Classification of magnetic materials
7.3 Atomic theory of magnetism
7.4 The quantum numbers
7.5 The origin of permanent magnetic moments
Let Us Sum Up
Check Your Progress

Unit end exercises
Suggested readings
OVERVIEW
Magnetism is perhaps the aspect of solid-state physics, which has been

familiar for the longest period of time. It is the phenomenon through which
materials assert an attractive or repulsive force on other materials.
Macroscopic properties of magnetic materials can be explained in terms
of the motion of electrons inside an atom and the interactions amongst
electrons. Based on the sign of susceptibility materials are classified into
different types. In the present unit you will learn about the various types
of magnetic materials and their characteristics also the classical theory of
diamagnetism is discussed.
81
OBJECTIVES
After studying this unit, you will be able to:

➢ Know the magnetic susceptibility, permeability and difference
between magnetic and non-magnetic materials
➢ Distinguish various types of magnetic materials
➢ Explain basic characteristics of different types of magnetic
materials
➢ Learn the Langevin’s classical theory of diamagnetism
TERMS AND DEFINITIONS
Magnetic Induction and magnetization

When a magnetic field, 𝐻, is applied to a material, the response of the
material is called its magnetic induction, 𝐵. The relationship between 𝐵
and 𝐻 is a property of the material. The equation relating 𝐵 and 𝐻 is (in
cgs units)
𝐵 = 𝐻 + 4𝜋𝑀 (1)
where M is the magnetization of the medium. The magnetization is defined

as the magnetic moment per unit volume,
𝑚 𝑒𝑚𝑢
𝑀 = = (2)
𝑉 𝑐𝑚3
The cgs unit of magnetization is the emu/cm3. Since B = H in free space

(where M = 0), the unit of magnetic induction should be the same as that
of magnetic field, that is, the Oersted. In SI units the relationship between
B, H, and M is
𝐵 = 𝜇0 (𝐻 + 𝑀) (3)
where 𝜇0 is the permeability of free space (𝜇0 = 4𝜋 × 10−7 𝐻𝑚−1 ). The

units of M are obviously the same as those of H (A/m), and those of 𝜇0
are weber/(A m), also known as henry/m. So the units of 𝐵 are weber/m2,
or tesla (T); 1 gauss = 10−4 tesla.
For an isotropic medium M and H are parallel vectors and are relation
between them can be expressed as,
𝑀 = 𝜒𝐻 (4)
82
Where 𝜒 is the susceptibility of the medium and is a scalar quantity.
Substituting Eq. 4 into 3, then we have,
𝐵 = 𝜇0 (1 + 𝜒)𝐻 = 𝜇𝐻 (5)
Where
𝜇 = 𝜇0 (1 + 𝜒) (6)
Is known as the permeability of the medium. It is often more convenient

to use the relative permeability 𝜇𝑟 , which is defined as,
𝜇
𝜇𝑟 = 𝜇 = (1 + 𝜒) (7)
0
7.2 CLASSIFICATION OF MAGNETIC MATERIALS
Magnetic materials can be classified into different categories according to

their 𝜒 values and based on how they vary with magnetic field strength
and temperature. They are,
1. Diamagnetic
2. Paramagnetic
3. Ferromagnetic
4. Antiferromagnetic
5. Ferromagnetic
Diamagnetic materials
• The motion of orbital electrons of the atom in a diamagnetic
material gets modified in such a way that a weak magnetic
moment opposing the field is induced.
• When a diamagnetic material is placed in an external magnetic
field it has a tendency to repel the magnetic lines of force.
Superconductors are an example of perfect diamagnetic material.
• Diamagnetic materials have negative susceptibility(χ).
• For these materials 𝜇𝑟 𝑎𝑛𝑑 χ are independent of temperature.
• Ex: inert gases, Cu, Zn, Ag, Au, Bi, mercury, water, glass etc.
Paramagnetic materials
• Para magnetism is the result of intrinsic magnetic moment
possessed by the atoms and ions
83
• In the absence of an external field these moments are randomly
oriented with respect to one other because of thermal fluctuations,
so they exhibit no net magnetic moment.
• When these materials are subjected to external magnetic field, the
moments tend to align along the magnetic field, which results in
net magnetization.
• When atoms and ions have no mutual interaction between them
and they acted upon individually, the effect is called Para
magnetism
• χ is positive for these materials and it is greater than zero
• χ of paramagnetic materials decreases with increasing
temperature
• Ex: Aluminum, platinum, potassium, the rare earth elements, alkali
and alkaline earth metals etc.
Ferromagnetic materials
• Ferromagnetic substances possess permanent (spontaneous)

magnetic moments even in the absence of an external magnetic
field
• χ of ferromagnetic substance is very large and positive, hence they
strongly attract the lines of force
• Ferromagnetism exists only below a certain temperature TC,
above which the substance becomes paramagnetic
• when a ferromagnetic material is fully magnetized, all the dipoles
in it are aligns exactly in the same direction
• Ex: Iron, cobalt and nickel etc.
Antiferromagnetic materials
• An antiferromagnetic material has the dipoles with equal
magnitude aligned exactly opposite to each other, as a result the
moments balance each other and result in a zero net
magnetization
Ferrimagnetic materials
• In ferrimagnetic material the magnetic moments of neighboring
dipoles point in opposite directions but they are unequal. As a
result, they do not completely balance each other and possess
finite net magnetization
84
7.3 ATOMIC THEORY OF MAGNETISM
In an atom, we know that the electrons revolve round the nucleus in

different circular orbits. Analogous to this situation let us consider an
electron of mass m, having an electronic charge (-e) moving in a circular
orbit of radius r with a velocity v (angular velocity ω) as shown in Fig. From
the basic knowledge of current electricity, w.k.t a moving electron
constitutes an electric current,
𝑑𝑞
𝐼=
𝑑𝑡
𝑑𝑞
𝐼. 𝑑𝑠 = . 𝑑𝑠
𝑑𝑡
𝑑𝑠
𝐼. 𝑑𝑠 = 𝑑𝑞. = −𝑒𝑣
𝑑𝑡
𝑑𝑠
Where, 𝑑𝑞 = −𝑒 and 𝑣 = 𝑑𝑡, the linear velocity. But for a circular orbit,
𝑑𝑠 = 2𝜋𝑟 and 𝑣 = 𝜔𝑟, so that
𝐼. 2𝜋𝑟 = −𝑒𝜔𝑟
𝑒𝜔
𝐼 = − 2𝜋 (8)
From electromagnetic theory, the magnetic field produced by a current I

flowing in a stationary loop of cross sectional area A at right angles to the
plane of the current loop is identical with that produced by a magnetic
dipole when measured at large distance. The magnetic moment produced
by the dipole is
𝜇𝑚 = 𝐼. 𝐴 (9)
For a circular motion of orbit 𝐴 = 𝜋𝑟 2 also substituting the value of I from

the eq.8 into eq.9, we obtain
𝑒𝜔 𝑒𝑚𝜔𝑟 2 𝑒
𝜇𝑚 = − 2𝜋 . 𝜋𝑟 2 = − = − (2𝑚) 𝐿 (10)
2𝑚
85
• Where 𝐿 = 𝑚𝜔𝑟 2 is the angular momentum of e -. The equation is
valid for only for motion of e- in the orbit. Not for spinning motion
of e- and nucleus.
• To understand the origin of magnetic moments of an atom, we

have to take into account of spinning motion of e- and nucleus.
• For the purpose, let us introduce the quantum theory of atom,
according to which the state of electrons in an atom can be
completely specified by four quantum numbers.
7.4 THE QUANTUM NUMBERS
These are integral or half-integral numbers used to specify the state of a

system in quantum mechanics. The four quantum numbers are:
1. Principle quantum numbers, n
The principle quantum number determines the energy level of the electron
in an atom. It can accept only integer values, i.e n = 1, 2, 3,….. The
corresponding electronic levels are called the K, L, M, N….. orbits.
2. Orbital quantum number. L

The orbital quantum number, also known as the (angular momentum
quantum number or orbital quantum number), describes the subshell, and
gives the magnitude of the orbital angular momentum through the
relation.
L2 = ħ2 ℓ (ℓ + 1) (11)
In chemistry and spectroscopy, ℓ = 0 is called s orbital, ℓ = 1, p orbital, ℓ =

2, d orbital, and ℓ = 3, f orbital.
The value of ℓ ranges from 0 to n − 1, so the first p orbital (ℓ = 1) appears
in the second electron shell (n = 2), the first d orbital (ℓ = 2) appears in the
third shell (n = 3), and so on:
ℓ = 0, 1, 2,..., n − 1
A quantum number beginning in n = 3, ℓ = 0, describes an electron in the

s orbital of the third electron shell of an atom. In chemistry, this quantum
number is very important, since it specifies the shape of an atomic
orbital and strongly influences chemical bonds and bond angles. The
azimuthal quantum number can also denote the number of angular nodes
86
present in an orbital. For example, for p orbitals, ℓ = 1 and thus the amount
of angular nodes in a p orbital is 1.
Shape of orbital is also given by azimuthal quantum number.
3. Magnetic quantum number, ml

The magnetic quantum number describes the specific orbital (or "cloud")
within that subshell, and yields the projection of the orbital angular
momentum along a specified axis:
Lz = mℓ ħ (12)
The values of mℓ range from −ℓ to ℓ, with integer intervals.
The s subshell (ℓ = 0) contains only one orbital, and therefore the mℓ of an

electron in an s orbital will always be 0. The p subshell (ℓ = 1) contains
three orbitals (in some systems, depicted as three "dumbbell-shaped"
clouds), so the mℓ of an electron in a p orbital will be −1, 0, or 1. The d
subshell (ℓ = 2) contains five orbitals, with mℓ values of −2, −1, 0, 1, and 2.
4. Spin quantum number, ms

The spin quantum number describes the intrinsic spin angular
momentum of the electron within each orbital and gives the projection of
the spin angular momentum S along the specified axis:
Sz = ms ħ. (13)
In general, the values of ms range from −s to s, where s is the spin

quantum number, associated with the particle's intrinsic spin angular
momentum:[4]
ms = −s, −s + 1, −s + 2, ..., s − 2, s − 1, s.
An electron has spin number s = 1/2, consequently ms will be ±1/2,

referring to "spin up" and "spin down" states. Each electron in any
individual orbital must have different quantum numbers because of
the Pauli exclusion principle, therefore an orbital never contains more
than two electrons.
87
7.5 THE ORIGIN OF PERAMANENT MAGNETIC MOMENTS
Permanent magnetic moments can arise from the following three different
sources:
1. The orbital magnetic moment of the electron

2. The spin magnetic moment of the electron
3. The spin magnetic moment of the nucleus
1. The orbital magnetic moment of the electron

Based on the atomic theory of magnetism we obtained an expression
(eq.10) of magnetic moment. However, in quantum consideration, the
angular momentum vector can take only specific orientation (eq.12) in
space when the atom is placed in an applied magnetic field. Therefore,
with the help of eq.10 and 12
𝑒 𝑒 𝑒ℎ
𝜇𝑚 = − (2𝑚) 𝐿𝑧 = − (2𝑚) 𝑚𝑙 ℏ = − (4𝜋𝑚) 𝑚𝑙
𝜇𝑚 = −𝑚𝑙 𝜇𝐵 (14)
𝑒ℎ
Where 𝜇𝑚 = (4𝜋𝑚) = 9.27 × 10−24 𝐴. 𝑚2 and is called Bohr magneton.
In a complex atoms whose shells have many electrons, the total orbital
magnetic moment is determined by taking the algebraic sum of the
magnetic moments of individual electrons in compliance with rules. The
moment of completely filled shells is zero and hence an atom with partially
filled have a nonzero orbital magnetic moment.
2. The spin magnetic moment of the electron

Similar to orbital motion, magnetic moment due to spin of the electron can
be determined by substituting the value of magnetic spin angular
momentum S from eq.13 into eq.10, we obtain,
𝜇𝐵
𝜇𝑠 = (15)
2
That is the spin magnetic moment is half of the Bohr magneton. This is
only approximately correct because eq.10 is not valid for electron spin. In
fact, the magnetic moment component 𝜇𝑠𝑧 along the field direction is given
by,
88
𝑒 𝑒ℎ
𝜇𝑠𝑧 = 𝑔 (2𝑚) 𝑚𝑠 ℏ = 𝑔 (4𝜋𝑚) 𝑚𝑠 (16)
Where 𝑔 is called the spectroscopic splitting factor or Lande’s 𝑔 factor.

For the electron spin g=2.0023, i.e the electron spin gives rise very nearly
one Bohr magneton in the direction of an external field. The Lande’s 𝑔
factor is given by,
𝐽(𝐽+1)+𝑆(𝑆+1)−𝐿(𝐿+1)
𝑔 =1+ (17)
2𝐽(𝐽+1)
3. The spin magnetic moment of the nucleus

Just like electron, the atomic nucleus possesses intrinsic spin and thus a
magnetic moment is associated with this. Since the nucleus mass is about
103 times greater than the mass of the electron, therefor the nuclear
magnetic moment is approximately three orders of the magnitude smaller
than the magnetic moment associated with the electron. Hence it is
negligible.
LET US SUM UP
• The magnetic induction B and the magnetic field H in a material

medium are related by the equation.
𝐵 = 𝜇0 𝐻 + 𝜇0 𝑀
Where M is the magnetization vector and is proportional to the field
𝑀 ∝ 𝐻 → 𝑀 = 𝜒𝐻
The constant 𝜒 is known as magnetic susceptibility.

• The different sources of permanent magnetic moment are the
orbital magnetic moment, the spin magnetic moment of the
electrons and spin magnetic moment of nucleus
1. What is magnetization?
2. What are the sources for the magnetic dipole moment?
89
1. Magnetization is defined as the magnetic moment per unit volume.

2. The orbital magnetic moment of the electron, The spin magnetic
moment of the electron and the spin magnetic moment of the
nucleus
UNIT END EXERCISES
1. Distinguish clearly between diamagnetism, paramagnetism and

ferromagnetism
2. discuss in detail about the origin of magnetism in magnetic
materials
SUGGESTED READINGS

Delhi
Web Resources
1. https://www.youtube.com/watch?v=6QUFuZpCgGw
2. https://www.youtube.com/watch?v=QQZ6EGf0Ju8
3. https://www.youtube.com/watch?v=DDLljK1ODeg
4. https://www.youtube.com/watch?v=IMlc8Fz5k0Y
5. https://www.youtube.com/watch?v=r_gBQ_qhg8U
6. https://www.youtube.com/watch?v=aNb6Ta-3U7A
7. https://www.youtube.com/watch?v=DW6NN4XwYzI
8. https://www.youtube.com/watch?v=yUU8Vavsr88
9. https://www.youtube.com/watch?v=-SzxrzZrJCM
90
UNIT 8
DIAMAGNETISM AND PARAMAGNETISM
Structure
Overview
Objectives
8.1 Langevin’s classical theory of diamagnetism
8.2 Sources of paramagnetism
8.3 Langevin’s classical theory of paramagnetism
8.4 Quantum theory of paramagnetism
Let Us Sum Up
Check Your Progress
Unit End Exercises
Suggested Readings
OVERVIEW
In the previous unit you have learnt that paramagnetic materials posses
positive susceptibility. Paramagnetism is the magnnetic analogue of
electrical orientational polarizability and is due to the permanent magnetic
moment of the atoms. In this unit you will learn about the Langevin’s
classical theory and Weiss theory of paramagnetism. Also you will learn
about special magnetic phenomeon, i.e. antiferromagnetism and
ferrimagnetism, which have found important technological applications
OBJECTIVES
➢ learn the Langevin’s classical theory of diamagnetism

➢ learn the Langevin’s classical theory of paramagnetism
➢ learn the quantum theory of paramagnetism
91
8.1 LANGEVIN’S CLASSICAL THEORY OF DIAMAGNETISM
Consider an electron, which revolves round a central nucleus as shown in

Fig. 2.1. If m is the mass of an electron, -e is the charge of an electron
and r is the radius of the orbit then the centripetal force acting on the
electron due to the nucleus, when the external field is absent is given by,
𝑚𝑣 2
𝐹0 = = 𝑚𝜔02 𝑟 (1)
𝑟
Where 𝑣 = 𝜔02 𝑟. When a magnetic field is applied along the z-axis

(perpendicular to the xy-plane), an additional force 𝐹𝐿 equal to the Lorentz
force starts acting on the electron in a direction away from the center. The
Lorentz force is given by,
𝐹𝐿 = −𝑒(𝑣 × 𝐵) = −𝑒𝐵𝑟𝜔 (2)
Where the magnetic field B is perpendicular to r. Angular frequency

changes from 𝜔0 𝑡𝑜 𝜔, because of the change in net force. The resulting
equation can be given by,
𝐹0 − 𝑒𝐵𝑟𝜔 = 𝑚𝜔2 𝑟 (3)
Fig. 2.1. Electron motion in a plane
Substituting equation, 1 into 3,

𝑒𝐵𝜔
𝜔2 + = 𝜔02 (4)
𝑚
So that
92
1
𝑒𝐵 2 2 𝑒𝐵
𝜔 = ± [(2𝑚) + 𝜔02 ] − 2𝑚
𝑒𝐵 𝑒𝐵 2
If 𝜔0 ≫ 2𝑚 then (2𝑚) term can be neglected, therefore,
𝑒𝐵
𝜔 = ±𝜔0 − 2𝑚 = ±𝜔0 − 𝜔𝐿 (5)
Where 𝜔𝐿 is called the Larmour frequency. The ± sign on 𝜔0 indicates the

parallel and antiparallel respective orientation of orbital moments with
respect to the field.
In the absence of magnetic field electron motion is spherically symmetric
and produces no net current or flux but when the field is present, electron
precesses about the field and produces a net current 𝐼. Due to the change
in frequency 𝜔𝐿 , the current for each electron can be written as,
𝑒𝜔𝐿 𝐵𝑒 2
𝐼 = 𝑐ℎ𝑎𝑟𝑔𝑒 × 𝑟𝑒𝑣𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑝𝑒𝑟 𝑢𝑛𝑖𝑡 𝑡𝑖𝑚𝑒 = − = − 4𝜋𝑚 (6)
2𝜋
Then the magnetic moment can be written as,
𝑍𝑒 2 𝐵
𝜇𝑚 = 𝐼 × 𝐴 = − 4𝜋𝑚 𝜋𝜌̅ 2 (7)
Where Z is the number of electrons in an atom and 𝜌̅ 2 is the mean square

radius of the projection of the orbit on a plane perpendicular to the Z-axis,
therefore
𝜌̅ 2 = 𝑥̅ 2 + 𝑦̅ 2 (8)
Mean square distance of the electron from the nucleus is,
𝑟̅ 2 = 𝑥̅ 2 + 𝑦̅ 2 + 𝑧̅ 2 (9)
For spherically symmetric charge distribution 𝑥̅ 2 = 𝑦̅ 2 = 𝑧̅ 2 , therefore

2 2
𝜌̅ 2 = 𝑟̅ (10)
3
Substituting Eq. 17 into 14,
𝑍𝑒 2 𝐵 2 𝑍𝑒 2 𝐵𝑟̅ 2
𝜇𝑚 = 𝐼 × 𝐴 = − 4𝜋𝑚 𝜋 (3 𝑟̅ 2 ) = − (11)
6𝑚
93
If N is the number of atoms per unit volume, then M and B are given by
𝑀 = 𝑁𝜇𝑚 𝑎𝑛𝑑 𝐵 = 𝜇0 𝐻. The diamagnetic susceptibility per unit volume
is,
𝑀 𝜇0 𝑍𝑒 2 𝑁𝑟̅ 2
𝜒𝑑𝑖𝑎 = =− (12)
𝐻 6𝑚
This is the classical Langevin equation for diamagnetism. From the above
equation it can be concluded that 𝜒𝑑𝑖𝑎 is proportional to 𝑍 𝑎𝑛𝑑 𝑟̅ 2 , which
indicates that 𝜒𝑑𝑖𝑎 depends on the outer electron and size of the atom.
And also, it shows the temperature invariance of diamagnetic
susceptibility.
8.2 SOURCES OF PARAMAGNETISM
Paramagnetism is a case of positive magnetic susceptibility.

Paramagnetism is found in:
Atoms molecules and lattice defects have an odd number of
electrons; that is there should be at least one electron which does
not pair. The atoms of the group I, III, V and VII of the periodic
Table, gaseous nitric oxide (NO); organic free radicals such as
triphenylmethyl C(C6H5)3 and F-centres in alkali halides, satisfy
this criterion.
Free atoms with unfilled inner shell : transition elements (Z = 57 -
72) and (Z = 91 - 102), rare earth and actinide elements have
atoms with unfilled inner shells.
A few compounds with an even number of electrons including
molecular oxygen and organic biradicals.
Metals: The electrons in a metal are considered to be free like
molecules in a gas. They tend to pair up but there are always a
few unpaired electrons to produce a weak temperature
independent paramagnetism known as Pauli paramagnetism.
8.3 LANGEVIN’S CLASSICAL THEORY OF PARAMAGNETISM
Curie’s measurements on paramagnetics are theoretically explained by

Langevin. Qualitatively in this theorem it is assumed that paramagnet
consists of atoms, each of which has the net magnetic moment μ. In the
94
absence of magnetic field net magnetization is zero due to the random
orientation of atomic moments. When a field is applied all atomic moments
tend to align in the direction of applied field and would acquire a large
moment. But thermal agitation of the atoms opposes this tendency, as a
result atomic moments get randomized and therefore decreases the
susceptibility.
In quantitative aspects of theory, consider a unit volume of material

containing n atoms, each having a magnetic moment μ. Let the direction
of each moment be represented by a vector, and let all the vectors be
drawn through the center of a sphere of unit radius (Fig. 2.2).
Fig. 2.2. Effect of applied field on magnetic dipole of moment μ

Let 𝑑n be the number of moments inclined at an angle between 𝜃 𝑎𝑛𝑑 𝜃 +
𝑑𝜃 to the field H. In the absence of field the number of μ vectors passing
through unit area at any point on the sphere surface is same, and 𝑑𝑛 is
given by 2π 𝑠𝑖𝑛𝜃 𝑑𝜃 for a sphere of unit radius. But when a field is applied,
the vectors shift toward the direction of the field then each atomic moment
has a certain potential energy 𝑈, given by Equation 1,
𝑈 = −𝜇𝐻𝑐𝑜𝑠𝜃 13
At thermal equilibrium temperature T, the probability of an atom having an

𝑈
energy U is proportional to 𝑒 −𝑘𝑇 , where k is Boltzmann constant. 𝑑𝑛 is
given by,
𝑈 𝜇𝐻𝑐𝑜𝑠𝜃
𝑑𝑛 = 𝐾𝑑𝐴𝑒 −𝑘𝑇 = 2𝜋𝐾𝑒 𝑘𝑇 𝑠𝑖𝑛𝜃𝑑𝜃 14
K is a proportionality factor and is determined by,

𝑛
∫0 𝑑𝑛 = 𝑛 (15)
95
Substituting Eq. 14 in 15,
𝜇𝐻𝑐𝑜𝑠𝜃
𝜋
∫0 2𝜋𝐾𝑒 𝑘𝑇 𝑠𝑖𝑛𝜃𝑑𝜃 = 𝑛 (16)
𝜇𝐻
Let 𝑎 = 𝑘𝑇
then Eq. iv becomes
𝜋
2𝜋𝐾 ∫0 𝑒 𝑎𝑐𝑜𝑠𝜃 𝑠𝑖𝑛𝜃𝑑𝜃 = 𝑛 (17)
The total magnetic moment in the direction of the field acquired by the unit
volume under consideration, that is, the magnetization M, is given by
𝑛
𝑀 = ∫0 𝜇𝑐𝑜𝑠𝜃 𝑑𝑛 (18)
Substituting 4 and 2 in 6,
𝜋 𝜋
𝑀 = ∫ 𝜇𝑐𝑜𝑠𝜃 2𝜋𝐾𝑒 𝑎𝑐𝑜𝑠𝜃 𝑠𝑖𝑛𝜃𝑑𝜃 = 2𝜋𝐾𝜇 ∫ 𝑐𝑜𝑠𝜃 𝑒 𝑎𝑐𝑜𝑠𝜃 𝑠𝑖𝑛𝜃𝑑𝜃
0 0
𝜋
𝑛𝜇 ∫0 𝑐𝑜𝑠𝜃 𝑒 𝑎𝑐𝑜𝑠𝜃 𝑠𝑖𝑛𝜃𝑑𝜃
𝑀= 𝜋 (19)
∫0 𝑒 𝑎𝑐𝑜𝑠𝜃 𝑠𝑖𝑛𝜃𝑑𝜃
To solve the above the equation put 𝑥 = 𝑐𝑜𝑠𝜃 and 𝑑𝑥 = 𝑠𝑖𝑛𝜃 𝑑𝜃 then
−1
𝑛𝜇 ∫1 𝑥 𝑒 𝑎𝑥 𝑑𝑥
𝑀= 𝜋 (20)
∫0 𝑒 𝑎𝑥 𝑑𝑥
𝑒 𝑎 +𝑒 −𝑎 1 1
= 𝑛𝜇 (𝑒 𝑎−𝑒 −𝑎 − 𝑎) = 𝑛𝜇(𝑐𝑜𝑡ℎ𝑎 − 𝑎) (21)
But 𝑛𝜇 corresponds to perfect alignment of all the atomic magnets parallel

to the field, which is a state of complete saturation. Say this quantity M 0,
then
𝑀 1
= 𝑐𝑜𝑡ℎ𝑎 − 𝑎 (22)
𝑀0
The expression on the right is called the Langevin function L(a).

Expressed as a series,
𝑎 𝑎3 2𝑎5
𝐿(𝑎) = 3 − 45 + 945 −….. (23)
which is valid only for 𝑎 ≤ 1. For small a, 𝐿(𝑎)=a/3.
96
From Eq. 21,
𝑛𝜇𝑎 𝑛𝜇 2 𝐻
𝑀= = (24)
3 3𝑘𝑇
Therefore,
𝑀 𝑛𝜇 2
𝜒𝑉 = = 3𝑘𝑇 (25)
𝐻
𝜒𝑉 𝑛𝜇 2
𝜒𝑚 = = 3𝜌𝑘𝑇 (26)
𝜌
But n is the number of atoms per unit volume, is equal to 𝑁/ 𝜌𝐴, where
N is atoms/mol (Avogadro’s number), 𝜌 is density, and A is atomic
weight. Therefore,
𝑁𝜇 2 𝐶 𝑒𝑚𝑢 𝐴𝑚2
𝜒𝑉 = = (𝑐𝑔𝑠)𝑜𝑟 (𝑆𝐼)
3𝐴𝑘𝑇 𝑇 𝑐𝑚3 𝑂𝑒 𝑚3 𝐴𝑚−1
𝑁𝜇 2 𝐶 𝑒𝑚𝑢 𝐴𝑚2
𝜒𝑚 = 3𝜌𝐴𝑘𝑇 = 𝜌𝑇 (𝑐𝑔𝑠)𝑜𝑟 (𝑆𝐼) (27)
𝑔 𝑂𝑒 𝑘𝑔 𝐴𝑚−1
which is Curie’s law, with the Curie constant given by
𝑁𝜇 2
𝐶=
3𝐴𝑘
8.4QUANTUM THEORY OF PARAMAGNETISM
The Langevin’s classical theory of paramagnetism is incapable of

providing a consistent explanation of the magnetic phenomena resulting
from the motion of electric charges. The very basis of the classical theory
that all orientations of magnetic moments with respect to B are possible,
is wrong according to quantum considerations. To overcome various
difficulties, let us discuss the essence of quantum theory of
paramagnetism based on the following basic facts:
• For each unit of orbital angular momentum, an electron in an atom

𝑒ℎ
has one Bohr magneton (𝜇𝐵 = 4𝜋𝑚) of magnetic moment
associated with it. The magnetic moment is antiparallel to the
angular momentum.
97
• For each unit of spin angular momentum (ℏ⁄2), there is also
associated one half Bohr magneton (𝜇𝐵 ⁄2) of magnetic moment
to an electron
• The total effective angular momentum of an electron is described
as the vector sum of orbital and spin contributions, i.e.
J=L+S (28)
• The effective magnetic moment is given by 𝑔𝜇𝐵 𝐽.

• According to quantum mechanics, the magnitude of the angular
1
momentum vector is given by [𝐽(𝐽 + 1)] ⁄2 and not by J. Also there
are 2J+1 ways in which the atomic dipoles may orient relative to
the magnetic field. The probability of such orientation is
determined by the Boltzman factor 𝑒𝑥𝑝 (∆𝑈⁄𝑘𝑇) .
For simplicity. Let us consider the atoms with L = 0. This gives g = 2 and
J = S = ½ which in turn provide only two possible states. The lower level
(𝑚𝑠 = 𝑚𝑗 = −1/2) corresponds to the moment parallel to the field, while
the upper level corresponds to the moment opposite to the field.
Let N1 and N2 be the concentration of atoms in the lower and upper levels,
respectively and that N1+N2 =N the total number of atoms. The difference
of these concentrations produces a magnetization
𝑀 = 𝑔𝜇𝐵 (𝑁1 − 𝑁2 ) (29)
Where 𝑔𝜇𝐵 is the z-component of the magnetic moment when it is fully

aligned with the field. These two concentrations are related by the
expression
𝑁1 exp(+∆𝑈⁄𝑘𝑇 )
= exp(−∆𝑈⁄𝑘𝑇) (30)
𝑁2
Where ∆𝑈 = 𝑔𝜇𝐵 𝐵. Now assuming 𝑥 = 𝑔𝜇𝐵 𝐵/𝑘𝑇, we obtain
𝑒 𝑥 − 𝑒 −𝑥
𝑁1 − 𝑁2 = 𝑁 ( ) = 𝑁 tan ℎ(𝑥)
𝑒 𝑥 + 𝑒 −𝑥
So that
𝑀 = 𝑔𝜇𝐵 (𝑁1 − 𝑁2 ) = 𝑁𝑔𝜇𝐵 tan ℎ(𝑥) (31)
For low field x << 1, and hence tan ℎ(𝑥) ~𝑥 so that eq. 31 becomes
98
𝑁(𝑔𝜇𝐵 )2 𝐵 𝜇0 𝑁(𝑔𝜇𝐵 )2 𝐻
𝑀 = 𝑁𝑔𝜇𝐵 𝑥 = = (32)
𝑘𝑇 𝑘𝑇
Therefore, the paramagnetic susceptibility is given by,
𝑀 𝜇0 𝑁(𝑔𝜇𝐵 )2
𝜒= = (33)
𝐻 𝑘𝑇
Now in a magnetic field, for a system of atoms with L = 0 and J = S = ½,

the projection of magnetic moment is similar to that of spin momentum. In
eq. 33 𝜇𝐵 is projected value of moment whereas the magnitude of the
effective moment of the atom is given by
1⁄
𝜇𝑒𝑓𝑓 = 2𝑔𝜇𝐵 [𝐽(𝐽 + 1)] 2 = √3𝑔𝜇𝐵
for S = J = ½
Or
2
𝜇𝑒𝑓𝑓 = 3𝑔2 𝜇𝐵2
2
𝜇𝑒𝑓𝑓
𝑔2 𝜇𝐵2 =
3
Substituting this eq. in 33,

2
𝜇0 𝑁𝜇𝑒𝑓𝑓
𝜒= (34)
3𝑘𝑇
Which is in agreement with classical result. However, for J > ½ an atom

with angular momentum quantum number J has (2J+1) equally spaced
energy levels. The magnetization is then
𝑔𝐽𝜇𝐵 𝐵
𝑀 = 𝑁𝑔𝐽𝜇𝐵 𝐵𝐽 (𝑥), with 𝑥 ≡ (35)
𝑘𝑇
Where the Brillouin function BJ is defined as

(2𝐽+1) (2𝐽+1)𝑥 1 𝑥
𝐵𝐽 (𝑥) = 𝑐𝑜𝑡ℎ ( ) − 2𝐽 𝑐𝑜𝑡ℎ (2𝐽) (36)
2𝐽 2𝐽
When J becomes very large, the Brillouin function becomes identical to

the Langevin function i.e
1 𝑥
𝐿(𝑥) = coth 𝑥 − ≡
𝑥 3
99
Therefore from eq. 35 the susceptibility becomes
2 2 2
𝜇0 𝑁𝐽(𝐽+1)𝑔2 𝜇𝐵 𝜇0 𝑁𝑝2 𝜇𝐵 𝜇0 𝑁𝜇𝑒𝑓𝑓
𝜒= = = (37)
3𝑘𝑇 3𝑘𝑇 3𝑘𝑇
where the effective moment of the atom, is now defined as 𝜇𝑒𝑓𝑓 = 𝑝𝜇𝐵
and 𝑝 = 𝑔𝐽(𝐽 + 1)1⁄2 is called the effective number of Bohr magneton for
the atom. The eq. 37 indicates that the quantum mechanical treatment
leads to the same conclusions as the classical treatment.
LET US SUM UP
• Diamagnetism is very weak magnetic effect. It is observed in those

solid, which do not have permanent magnetic moment
• When an atom is placed in magnetic field, the motion of the
electron does no longer remain in spherically symmetric but starts
precessing about the field. The resultant diamagnetic susceptibility
is given by the equation
𝑀 𝜇0 𝑍𝑒 2 𝑁𝑟̅ 2
𝜒𝑑𝑖𝑎 = =−
𝐻 6𝑚
Which depends on the size of the atom

• The small non zero magnetic moment is due to the orbital motion
of electrons and this magnetic moment is always directed opposite
to the applied magnetic field
• Paramagnetism found in all atoms/molecules possessing odd
number of electrons and in all free atoms/ions with an unfilled inner
shell
• Considering the atom has a net magnetic moment. Langevin
showed that the alignment of the moments with the field leads to
a Classical Paramagnetic Susceptibility
1. What are the sources of paramagneism?
100
1. Atoms molecules and lattice defects having an odd number of

electrons; that is there should be at least one electron which does
not pair. The atoms of the group I, III, V and VII of the periodic
Table, gaseous nitric oxide (NO)
UNIT END EXERCISES
1. Derive an expression of diamagnetic susceptibility on the basis of

classical theory
2. Obtain an expression for paramagnetic susceptibility on the basis
of classical laws
3. Discuss in detail about the quantum theory of paramagneitsm
SUGGESTED READINGS

Delhi
Web Resources
1. https://www.youtube.com/watch?v=CYdtTtLrURw
2. https://www.youtube.com/watch?v=DDLljK1ODeg
3. https://www.youtube.com/watch?v=CwECg-NxF6A
4. https://www.youtube.com/watch?v=yIOA1qHorWs
5. https://www.youtube.com/watch?v=SK1TN5pjHfg
6. https://www.youtube.com/watch?v=Jq14-AjJ1y4
7. https://www.youtube.com/watch?v=PEUKZ5UJG9Y
8. https://www.youtube.com/watch?v=KLUrOy-KSlI
courses/physics/SolidStatePhysics-IIT-Kharagpur/lecture-61.html
101
UNIT 9
FERROMAGNETISM, ANTIFERROMAGNETISM AND

FERRIMAGNETISM
Structure
Overview
Objectives
9.1 Ferromagnetism
9.2 The Weiss molecular field theory
9.3 Temperature dependence of spontaneous magnetization
9.4 The physical origin of Weiss molecular field theory
9.5 Ferromagnetic domains
9.6 Domain theory
9.7 Antiferromagnetism
9.8 Ferrimagnetism
9.9 Structure of ferrite
Let Us Sum Up
Check Your Progress
Unit End Exercises
Suggested Readings
OVERVIEW
In general, when we speak of a magnet we actually mean a ferromagnet.

For example, consider a piece of iron, which has the ability to pick up other
pieces of iron towards it, possesses permanent magnetic moments and is
said to be a permanent magnet. In this chapter we will discuss about the
physical origin and properties of the saturation magnetization in
ferromagnetics. You will also learn about the ferromagnetism theory
proposed by Weiss and temperature dependence of magnetization in
ferromagnetics.
102
OBJECTIVES

➢ Explain the domain structure in ferromagnets.
➢ Describe the process involved at the microscopic level when a
ferromagnetic substance is magnetized.
➢ Understand the antifrromagnetism and ferrimagnetism.
9.1 FERROMAGNETISM
In general, when we speak of a magnet, we actually mean a ferromagnet.

For example, consider a piece of iron, which has the ability to pick up other
pieces of iron towards it possesses permanent magnetic moments and is
said to be a permanent magnet. Thus, ferromagnetism is the existence of
magnetization even in the absence of the external magnetic field.
Some of the experimentally observed facts are:
• Magnetization M increases when an external field is applied to the
specimen. Moreover, the relationship between magnetization M
and applied field H is nonlinear and shows hysteresis effect similar
to that shown by polarization P and the electric field E.
• The strong magnetism is found to disappear at a critical
temperature (Tc), the specimen becomes demagnetized, behaves
like a paramagnet and shows magnetic effects only when an
external field is applied.
In order to explain these experimental facts, Weiss put forward a theory
of ferromagnetism based on the following hypothesis.
➢ Ferromagnetic materials are made up of large number of
‘domains’ (each domain contains about 109 - 1015 atoms), which
are spontaneously magnetized. The magnitude of spontaneous
magnetization (refers to a single domain) of the specimen is
determined by the vector sum of the magnetic moments of the
individual domains.
➢ Within a given domain, all the dipoles (spins) are aligned in the
same direction, so that magnetization is the maximum possible
value for a given material and temperature.
103
Fig 9.1 Ferromagnetic domain
9.2 THE WEISS MOLECULAR FIELD THEORY
The spontaneous magnetization of each domain is due to the presence of

an exchange field Hex (internal molecular field), which tend to produce a
parallel alignment of dipoles.
𝐻𝑒𝑥 = 𝐻 + 𝜆 (1)
Where 𝜆 is called the Weiss constant and H is applied field
In a ferromagnetic material Curie law holds for Hex as well. Therefore,

𝑀 𝐶
=𝑇 (2)
𝐻𝑒𝑥
Substituting 1 into 2,
𝐶𝐻
𝑀 = 𝑇−𝐶𝜆 (3)
Then the ferromagnetic susceptibility is given by
𝑀 𝐶 𝐶
𝜒= = 𝑇−𝐶𝜆 = 𝑇−𝑇 (4)
𝐻 𝑐
Where T = Cλ is known as the Curie temperature and the above equation

is known as Curie-Weiss law.
When 𝑇 ≥ 𝑇𝑐 ferromagnetic material behaves like paramagnetic. As 𝑇 →
𝑇𝑐 , susceptibility tends to infinity and for 𝑇 ≤ 𝑇𝑐 , there exists a
spontaneous magnetization even in the absence of an external field.
104
9.3 TEMPERATURE DEPENDENCE OF SPONTANEOUS
MAGNETIZATION
Magnetic behavior of ferromagnetic material below the Curie temperature

can be determined by assuming the contribution of magnetic moment
from orbital motion is negligible compared to spin moments. In the
absence of an external field (H = 0) Hex reduces to,
Hex = 𝜆𝑀 (5)
Where 𝑀 = 𝑁𝜇̅ is the spontaneous magnetization at some temperature T

less than TC.
The Magnetization M for spin half is given by,
𝑀 = 𝑁𝑔𝜇𝐵 tan ℎ(𝑥) (6)
𝑔𝜇𝐵 𝐵
Where 𝑥 = 𝑘𝑇
. By replacing B by Hex,
𝑔𝜇𝐵 𝜇0 𝐻𝑒𝑥 𝜇0 𝑔𝜇𝐵 𝜆𝑀

𝑥= =
𝑘𝑇 𝑘𝑇
𝑘𝑇𝑥
𝑀=𝜇 (7)
0 𝑔𝜇𝐵 𝜆
By plotting 𝑀 𝑣𝑠 𝑥, Eq. 6 and 7 can be solved. The value of M at any given

temperature is obtained from the point of intersection of the two cures, as
shown in Fig. 9.2.
From Eq. 6 it is observed that as T increase the slope of the straight
increases. For 𝑇 < 𝑇𝑐 , the two cures intersect at a point, which gives a
non-vanishing spontaneous magnetization. At T = 0K maximum
spontaneous magnetization occurs, is given by
𝑀𝑠 (0) = 𝑁𝑔𝜇𝐵 (8)
At 𝑇 = 𝑇𝑐 , the straight line is tangential to the hyperbolic curve at the origin,

where the spontaneous magnetization reduces to zero and remains zero
for all temperatures above the critical value ( 𝑇 > 𝑇𝑐 ). Further, at 𝑇 = 𝑇𝑐 ,
for 𝑥 ≪ 1, the hyperbolic function can be written as,
tanh (𝑥) ≅ 𝑥
by equating Eq. 6 and 7 we get
105
𝑘𝑇𝑐
𝜆=𝜇 2
(9)
0 𝑁(𝑔𝜇𝐵 )
to describe the temperature dependence of spontaneous magnetization

in simple manner Eq. 6 can be expressed by making use of Eq. 8 and 9,
𝑀𝑠 (𝑇) 𝑇
= 𝑡𝑎𝑛ℎ ( )
𝑀𝑠 (0) 𝑇𝑐
Fig. 9.2. M vs x and M vs tan kx curves. Point of intersection

represents the spontaneous magnetization
𝑀𝑠 (𝑇) 𝑇
𝑀𝑠 (0)
is the normalized magnetization and 𝑇𝑐
is the normalized
temperature. The above equation is called as the thermomagnetic
equation of state for ferromagnetic phase of materials.
9.4 THE PHYSICAL ORIGIN OF WEISS MOLECULAR FIELD
The introduction of Weiss molecular field made it possible to explain a

wide range of phenomena observed in ferromagnetism. However, the
nature of the field itself remained a mystery for a long time. At first, it was
supposed to be due to a simple nearest neighbor dipole-dipole interaction.
Such an interaction would give rise to a field of the order of
𝜇𝐵
= 103 𝑔𝑎𝑢𝑠𝑠𝑒𝑠
𝑎3
106
Where a is the interatomic distance in a ferromagnetic crystal. On the
other hand, for a Curie temperature Tc = 1000 K, the exchange field is
approximately found to be
𝐻𝑒𝑥 ≃ 𝜆𝑀𝑠 (0) ≃ 104 × 103 ≃ 107 𝑔𝑎𝑢𝑠𝑠𝑒𝑠
This discrepancy shows that a simple model based on dipole-dipole

interaction cannot account for ferromagnetism. Actually, a much stronger
type interaction is needed.
This first attempt to solve the problem was made by Heisenberg in 1982.
According to him the large Weiss molecular field can be explained in terms
of the so-called exchange interaction between the electron spins. The
energy of the interaction for ions i, j bearing spins Si, Sj can be expressed
as
𝑖𝑗
𝐸𝑒𝑥 = −2𝐽𝑆𝑖 . 𝑆𝑗 (10)
And the total exchange energy of spin i with its neighbors J1, J2, …… may
be expressed as
𝑖𝑗
𝐸𝑒𝑥 = −2𝐽 ∑𝑛𝑗=1 𝑆𝑖 . 𝑆𝑗 (11)
Where J is called exchange integral and is a measure of the strength of

interaction.
In general, the exchange integral is negative and hence a non-
ferromagnetic state is favoured However, for a ferromagnet it must be
positive. In the above equations, the dot product is used because the
exchange energy is governed by the relative orientation of the spins. In
ferromagnetism, where parallel orientation of spins is favoured, Eex is
minimum and 𝑆𝑖 . 𝑆𝑗 = 𝑆 2 . Similarly, Eex is maximum when spins are
antiparallel and therefore 𝑆𝑖 . 𝑆𝑗 = 𝑆 2 .
It is possible to determine the exchange integral experimentally as a

function of the ratio of the interatomic spacing “a" to the unfilled shell of
radius r. For transition metals this is represented by the curve shown in
Fig.9.3.
107
Fig. 9.3
The ratio a/r for transition element of the iron group if found to be
Elements Fe Co Ni Cr Mg Gd
a/r ration 3.26 3.64 3.94 2.60 2.94 3.10
According to Slater, the ratio (a/r) ≥ 3, but not very large, must be satisfied
for the occurrence of ferromagnetism. The substance viz. Fe, Co, Ni and
Cd and Gd satisfy the above criterion and are found to be ferromagnetic.
On the other hand Mn and Cr fail to satisfy the above criterion and not
ferromagnetic.
9.5 FERROMAGNETIC DOMAINS
Ferromagnetic materials exhibit hysteresis under the influence of an

external magnetic field. This behavior can be explained by Weiss domain
hypothesis, according to which ferromagnetics contain small domains.
Fig. 9.4. Role of domains in magnetization of ferromagnetics (a)

Unmagnetized (b) domain movement (c) domain rotation
Each of these domains magnetized to saturation but the net varies from
zero to saturation. A ferromagnetic material in demagnetized state is
108
represented schematically in Fig. 9.4. by four equal domains. When the
magnetic field is applied in an arbitrary direction, the domains which have
magnetic moments along the direction of the applied field will grow at the
expense of others. And this process occurs through the domain wall
motion. As the field increased further, the magnetization increases to
saturation and it occurs due to the rotation of domains from easy to hard
direction. In this stage the whole specimen becomes single domain whose
moment is directed parallel to the applied field.
Fig. 9.5. (a) Hysteresis loop of a ferromagnetic material (b)

Schematic representation of a bloch wall
At low temperatures the dependence of M on H is shown in Fig. 9.5(a).

formation of hysteresis has three distinct regions and are may be
described as follows:
• When the applied field is small, the induced magnetization varies

linearly with the field and is also reversible. This region is called
as reversible region
• When the field gradually increases the magnetization shows a
non-linear variation and also becomes irreversible. This is the
region of irreversible wall motion.
• As the field increased further, the magnetization also increases
gradually and ultimately attains a saturation value (MS). This is the
region where the rotation of domains takes place. A further
increase in field produces no change in magnetization.
• On the other hand, when the field is gradually decreased, the
decrease in magnetization follows a different path and for a zero
field, the specimen continues to retain a certain amount of
magnetization, called the remnant magnetization (Mr).
• A finite field equal to the coercive field (-HC) is required to bring
the magnetization back to zero.
109
• A further increase in the reverse field results in a complete
reversal of MS. A second reversal of the field completes the
hysteresis curve.
Block wall
In a crystal specimen, the domains are separated from one
another by boundaries. These are the regions within which the moments
(spins) changes their spatial directions. The transition layer between two
domains is called a “domain wall” or “block wall” (Fig. 9.5(b)).
9.6 DOMAIN THEORY
This theory was proposed by Weiss in 1907. It explains the hysteresis

and the properties of ferromagnetic materials.
Postulates of domain theory:
1. A ferromagnetic material is divided into a large number of small

region called domains (0.1 to 1 of area)
2. In each domain the magnetic moments are in same direction.
3. But the magnetic moment varies from domain to domain and the
net magnetization is zero,
4. In the absence external magnetic field all the magnetic moments
are in different direction.
5. When a magnetic field is applied there are two process takes
place
• By the motion of domain walls.
• By the rotation of domains.
By the motion of Domain walls

When a small amount of magnetic field is applied, the dipoles in the
domains are aligned parallel to the applied magnetic field. It increases
domain area by the motion of domain walls.
By the rotation of Domains
If the applied magnetic field is further increased, the domains are rotated
parallel to the field direction by the rotation of domains.
110
Fig. 9.6 Domain theory of ferromagnetism
Energies involved in the domain growth (or) Origin of Domain theory

of Ferromagnetism
The total internal energy of the domain structure in a ferromagnetic
material is made up from the following
1. Exchange energy (or) Magnetic field energy.
2. Crystalline energy (or) Anisotropy energy.
3. Domain wall energy (or) Bloch wall energy.
4. Magnetostriction energy
1. Exchange energy (or) Magnetic Field energy

“The interaction energy which makes the adjacent dipoles align
themselves” is the called exchange energy (or) magnetic field energy.
It arises from an interaction of electron spins. It depends upon the inter
atomic distance. This exchange energy also called magnetic field energy.
Whose energy is required in assembling the atomic magnets into a single
domain and this work done is stored as potential energy. The volume of
the domain may very between 10-2 to 10-6 cm3.
Fig. 9.7 (a) Single domain (b) multi domain

2. Anisotropy energy
The excess of energies required to magnetize a specimen along the hard
direction is called the crystalline anisotropy energy. In ferromagnetic
materials there are two types of directions of magnetization namely,
111
• Easy direction and
• Hard directions
In easy direction of magnetization, weak field can be applied and in hard

direction of magnetization, strong field should be applied.
Crystalline anisotropy energy is energy of magnetization which is the

function of crystal orientation. As shown in figure magnetization curves for
iron with the applied field along different crystallographic direction
crystallographic directions have been drawn. For example, in BCC iron
the easy direction is [100], the medium direction is [110], and the hard
direction [111]. This energy is very important in determining the
characteristic domain boundaries.
3. Domain wall energy or Bloch wall energy
A thin boundary or region that separates adjacent domains in different

directions is called domain wall or Bloch wall. The size of the Bloch walls
is about 200 to 300 lattice constant thickness. The energy of domain wall
is due to both exchange energy and anisotropic energy. Based on the spin
alignments, two types of Bloch walls may arise, namely
Thick wall: When the spins at the boundary are misaligned and if the
direction of the spin changes gradually as shown in below figure, it leads
to a thick Bloch wall. Here the misalignments of spins are associated with
exchange energy.
Thin wall: When the spins at the boundaries changes abruptly, then the
anisotropic energy becomes very less. Since the anisotropic energy is
112
directly proportional to the thickness of the wall, this leads to a thin Bloch
wall.
4. Magetostriction energy
When a material is magnetized, it is found that it suffers a change in
dimensions. This phenomenon is known as Magnetostriction. This
deformation is different along different crystal directions. So, if the
domains are magnetized in different directions, they will either expand or
shrink. This means that work must be done against the elastic restoring
forces. The work done by the magnetic field against these elastic restoring
forces is called magneto-elastic energy or Magnetostrictive energy.
9.7 ANTIFERROMAGNETISM
Ferromagnetic and antiferromagnetic materials have small exchange

energy Hex, but the exchange integral is positive for ferromagnetics and it
is negative for antiferromagnetic due to the balanced antiparallel
arrangement of spins.
Antiferromagnetic materials have small positive susceptibility.
Temperature dependence of susceptibility is shown in Fig. 3.3 (a). As the
temperature increases susceptibility of antiferromagnetic material
increases and reaches a maximum value at a certain temperature called
Neel temperature (TN). above the Neel temperature susceptibility is
observed to follow the below given equation,
𝐶
𝜒=
𝑇 + 𝑇𝑐
Where C is the Curie constant and TC is the paramagnetic Curie

temperature.
113
Fig. 9.8. (a) Magnetic susceptibility of an antiferromagnetic material
(b) two interpenetrating cubic lattices with anti-parallel spins
The Characteristic features of Antiferromagnetic materials are explained
on the basis of two sub lattice model, which is shown in Fig. 9.3 (b). In this
model it is assumed that the magnetic structure of lattice system contains
two interpenetrating simple cubic lattices, in which the spin moments of
atoms in one sub lattice array are antiparallel with the spin moments of
atoms in another sub lattice array.
At absolute zero, spin moments of both the sub lattice arrays are ordered
and mutually compensated so that the net magnetization zero. As the
temperature is raised, antiparallel arrangement is gradually disturbed and
the magnetization raises and becomes maximum at the Neel point, above
which the material behaves like paramagnetic.
9.8 FERRIMAGNETISM
Ferrimagnetism is similar to the antiferromagnetism, in which the

moments are arranged antiparallel, but they are not compensated
completely. Such an uncompensated antiferromagnetism is known as
ferrimagnetism and the corresponding materials are said to be ferrites.
They exhibit spontaneous magnetization below the ferrimagnetic Neel
temperature (TFN).
9.9 STRUCTURE OF FERRITES
Ferrite crystals are those that have the inverted spinel structure rather
than the normal spinel structure: The B cations occupy one-eighth of the
tetrahedral holes, whereas the A cations occupy one-fourth of the
octahedral sites. The remaining one-fourth is taken care of by the B cation.
114
Fig. 9.9 Structure of Ferrite
The natural ferrite is Magnetite, Fe3O4. The corresponding general

chemical formula is written as 𝑀𝑒 +2 𝐹𝑒2+3 𝑂4 . Ferrites have spinel structure
and spinel has two forms, normal and inverse. Normal spinel ferrites
(AB2O4) can be considered to contain two sub lattices A (tetrahedral) and
B (octahedral). all the divalent and trivalent metal ions in normal spinel
structure occupy A- and B-sub lattices, respectively. Ex:
(Zn+2)AO(Fe+3)BO3 in inverse spiel structure all the divalent metal ions
occupy B-sites and Trivalent ions are equally distributed over the A- and
B- sub lattices. Ex: (Fe+3)A(Fe+3Ni+2)BO4.
Application of ferrite in computer memories

Ferrites were used as the memory device of the computer. A memory core
is a memory device, in which the ferrite cores are arranged in a grid
structure and through which signal wires for reading and writing are
passed. When a current flow through the signal wire, the ring core
becomes magnetized due to the current’s magnetic action. But the
orientation of the magnetization reverses depending on the current
direction, it can be used as zero or one digital information. Since the
magnetization remains semi-permanent, magnetic cores are used as
highly reliable non-volatile memories, for memory devices of computers.
LET US SUM UP
❖ Ferrornagnets have a very high positive value of magnetic

susceptibility. In spite of this, these materials do not exhibit
magnetism in the absence of a magnetic field
due to domain structure. By application of external field, the
domains reorientthemselves to give magnetic property to the
ferromagnetic materials
115
❖ Due to irreversible reorientation of magnetic domains, ferromagnets
exhibit hysteresis loss
❖ Ferromagnetism is the existence of the spontaneous
magnetization below a critical temperature TC, known as Curie
Temperature. Above this temperature substance becomes
paramagnetic and obeys Curie-Weiss law
❖ According to Weiss, ferromagnetic materials are made up of large
number of domains.
❖ Like ferromagnetism, antiferromagnetism and ferrimagnetism also
owe their existence to exchange interaction between magnetic
moments. The characteristic features of antiferromagnetic
materials can be qualitatively explained on the basis of two sub
lattice model.
❖ Ferrimagnetic materials exhibit spontaneous magnetization below
ferrimagnetic Neel temperature (TFN)
1. Define Ferromagnetism. What is Weiss field?

2. What is domain?
3. Define antiferromagnetism and ferrimagnetism.
4. What is Neel temperature?
1. The appearance of a very large magnetization due to the parallel

alignment of neighboring magnetic moments by an exchange
interaction. Weiss field is a hypothetical internal magnetic field,
strong enough to line up the spin moments despite the thermal
energy
2. A region in ferromagnetic material, where all the moments are
aligned.
3. Antiferromagnetism: the opposite alignment of adjacent magnetic
moments in a solid produced by the exchange interaction.
Ferrimagnetism: A special case of antiferromagnetism, where the
opposite moments are of different magnitude, as a result of large
amount of magnetization appears
4. The temperature above which a ferromagnetic and
antiferromagnetic material becomes paramagnetic.
116
UNIT END EXERCISES
1. Give an account of Weiss theory of ferromagnetism. Based on this

theory how will you explain hysteresis effect and curie point
2. Draw a typical M-H curve for a ferromagnetic material and explain
the different stages of magnetization process on the basis of
domain theory
SUGGESTED READINGS

Delhi
Web Resources
1. https://www.youtube.com/watch?v=FwtmQ_nk-es
2. https://archive.nptel.ac.in/courses/115/106/115106061/
3. https://www.youtube.com/watch?v=d8q6DzQ7CpU
4. https://www.youtube.com/watch?v=3iDfBT_0_OE
5. https://www.youtube.com/watch?v=ix0oe-LVddA
6. https://cosmolearning.org/video-lectures/lecture-29-ferroelectric-
moment-spontaneous-magnetization-landau-theory-9751/
7. https://www.youtube.com/watch?v=YgrGrQxw4eU
8. https://www.youtube.com/watch?v=l_Og5qlqv-Y
9. https://www.youtube.com/watch?v=sJYoLiDbjmQ
10. https://www.youtube.com/watch?v=wQ2_Jm1Yf7o
11. https://www.youtube.com/watch?v=g2DkG86yB4w
12. https://www.youtube.com/watch?v=RGP-3wrKSwQ
13. https://www.youtube.com/watch?v=93iXn9VF0ls
14. https://www.youtube.com/watch?v=HBtGtGG34Rs
117
BLOCK IV: SUPERCONDUCTIVITY
Unit 10: Introduction to Superconductivity
Unit 11: BCS Theory
Unit 12: Applications of Superconductivity
118
UNIT 10
INTRODUCTION TO SUPERCONDUCTIVITY
Structure
Overview
Objectives
10.1 Occurrence of superconductivity
10.2 Destruction of superconductivity by magnetic field
10.3 Meissner effect

10.4 Type I and Type II superconductors
10.5 Heat capacity
10.6 Energy gap
10.7 Microwave and infrared properties
Let Us Sum Up
Check Your Progress
Unit End Exercises
Suggested readings
OVERVIEW
Superconductivity is the phenomenon of zero electrical resistance and

repulsion of magnetic fields at very low temperatures.
It was discovered by Dutch physicist Hike Kamerlingh Onnes in 1911.
When Onnes and his team members were doing research on various
properties of mercury, interestingly they found sudden drop of
electrical resistance to zero. When studying the resistance of solid
mercury at cryogenic temperatures by using liquid helium they
observed at 4.2 K, the electrical resistance dropped to zero. Repeated
resistivity measurements indicated zero resistance at the liquid-helium
temperatures. Short circuit was assumed during the initial trial.
119
During one repetitive experimental run, a young technician fell asleep.
The helium pressure (kept below atmospheric one) slowly rose and,
therefore, the boiling temperature. As it passed above 4.2 K, suddenly
resistance appeared.
“Mercury has passed into a new state, which on account of its
extraordinary electrical properties may be called the superconducting
state“ H. Kamerlingh Onnes 1913 (Nobel prize -1913)
Fig. 10.1 (a) Temperature vs resistance graph for Mercury (b)

Photograph of H.K. Onnes,
The phenomenon of zero resistivity in metals led to lot of new

applications. In subsequent decades, superconductivity was found in
several other materials. In 1913, lead (Pb) was found to behave as a
superconductor at 7 K, and in 1941, it was found that niobium nitride
became a superconductor at 16 K in the recent few years, near to room
temperature superconductors are being developed with the
advancements in the field of materials science and physics.
OBJECTIVES

➢ Understand the Occurrence of superconductivity.
➢ Distinguish Type I and Type II Superconductors
➢ Explain basic characteristics of Superconducting Materials
120
10.1 OCCURRENCE OF SUPERCONDUCTIVITY
The phenomenon of superconductivity is not common to all but yet it

is observed in many substances including metallic elements, alloys,
and compounds whose transition temperature vary widely. In 1957, B.
Mathias proposed certain empirical rules on the basis of which he
discovered a number of new superconductors. The rules are:
1. Superconductivity is found to occur in metallic elements in

which the number of valence electrons Z lies between 2 and 8.
In general, superconducting elements lie in the inner columns
of the periodic table.
2. Transition metals having odd valence electrons (Z) such as 3.5
or 7 have higher Tc and are favourable to exhibit superconductivity
while metals having even numbers of valence electrons arc
particularly unfavourable (Fig. 2).
3. For elements lying along a given row of the periodic Table. T,
versus Z2 gives straight line.
4. A small atomic volume, accompanied by a small atomic mass
favours superconductivity.
5. Materials having high normal resistivities exhibit
superconductivity.
6. Materials with the product of number of valence electrons and the
resistivity (in electrostatic units at 20°), nρ > 106 show
superconductivity.
Fig.10.2 Variation of transition temperature with number of

valence electrons (Z)
121
Fig. 10.3 An empirical correlation between transition
temperature and Z2.
10.2DESTRUCTION OF SUPERCONDUCTIVITY BY MAGNETIC FIELD
The magnetic field and the superconductivity are found to be mutually

exclusive. When a weak magnetic field is applied to a superconducting
specimen, below transition temperature it expels the magnetic flux (i.e
lines of force) initially held and acts as an ideal diamagnet. This
phenomenon is called the Meissner effect and is shown in Fig. 4. When
the applied field is gradually increased to a critical or threshold value, Hc,
the superconductivity is destroyed (Fig. 5). However, this transition is
reversible. The critical field Hc is a function of temperature, and for a given
substance decreases gradually with increase in temperature from T = 0 K
to T = Tc. further this variation is empirically found to be represented by
the expression,
𝑇 2
𝐻𝑐 = 𝐻𝑐 (0) [1 − (𝑇 ) ] (1)
𝑐
Where 𝐻𝑐 (0) is the maximum value of the field at T = 0 K and
𝐻𝑐 (𝑇𝑐 ) = 0
at T = Tc are constant s and characteristics of the material.
122
Fig. 10.4 The Meissner effect
Fig.10.5 Critical magnetic field as a function of temperature
10.3 THE MEISSNER EFFECT
In 1933, Walter Meissner and Robert Ochsenfeld discovered a magnetic

phenomenon that showed that superconductors are not just perfect
conductors. Fig. 10.3 illustrates a thought experiment that highlights this
123
difference. Imagine that both the ideal conductor and superconductor are
above their critical temperature, Tc. That is, they both are in a normal
conducting state and have electrical resistance. A magnetic field, B, is
then applied. This results in the field penetrating both materials. Both
samples are then cooled so that the ideal conductor now has zero
resistance. It is found that the superconductor expels the magnetic field
from inside it, while the ideal conductor maintains its interior field. Note
that energy is needed by the superconductor to expel the magnetic field.
This energy comes from the exothermic superconducting transition.
Switching off the field induces currents in the ideal conductor that prevent
changes in the magnetic field inside it – by Lenz’s law. However, the
superconductor returns to its initial state, i.e. no magnetic field inside or
outside it.
Since superconductor exhibits perfect diamagnetism below the critical
temperature Tc, magnetic flux density inside the material is zero.
Therefore B = 0, for T < Tc

Relationship between flux density and the strength of the magnetizing
field is given by
B = µo(M + H)
µo = Absolute permeability of free space

M = Intensity of magnetization of the material and
H = Strength of the magnetizing
B = µ0 (H + M)
0 = µ0 (H + M)
or
M=–H
or magnetic susceptibility,
M
χ = 𝐻 = –1 (2)
124
10.4 TYPE I AND TYPE II SUPERCONDUCTORS
Depending on the mechanism of transition from the superconducting state

to the normal state on the application of a field that exceeds the critical
field, the superconductors are divided into two groups:Type I and Type II
superconductors
(a (b
Fig .10.6 Type I and type II variation of magnetization behavior of

superconductors
Type I Superconductors
The superconductors which never allow a magnetic flux density inside
the superconductor, i.e., those which are perfectly diamagnetic, are
classified as Type I or soft superconductors. These superconductors
exhibit complete Meissner effect. In these superconductors, the
transition from the superconducting state to the normal state occurs
sharply in the presence of magnetic field at Hc [Fig. 7 (a)]. It is also
clear from the magnetization curve of Type I superconductors [Fig. 7
(b)] that they are perfectly diamagnetic materials below Hc because
they do not have any magnetic field inside. However, up to Hc, the
magnetization varies linearly with the applied field and suddenly drops
to zero at the transition to the normal conducting state. They are poor
conductors of electric current as the current flows only at the outer
surface of the conductor [Fig. 7 (c]. Some examples of Type
superconductors are Pb, Al, Sn, and so on. The value of critical field
(Hc) for Type I superconductors is relatively low and is in the range of
100 G.
125
Fig .10.7 Behavior of magnetic field for type I superconductor
Type II Superconductors
The superconductors which exhibit incomplete Meissner effect or admit
partial magnetic flux density and have zero resistivity are called Type II or
hard superconductors. The behavior of magnetization and the variation of
resistivity with the external field are shown in Figs. 8 (a) and (b),
respectively It is clear from the magnetization curve that for the applied
field below a certain lower critical field Hc1(H < Hc), the specimen is
perfectly diamagnetic like Type I superconductor and there is no
penetration of field, and hence, no magnetic flux density is found in the
interior of the specimen (Meissner effect). The magnetization increases
linearly up to Hc till the upper critical field Hc is reached. In the region
between H1and H2, the specimen passes through the normal as well as
through the superconducting states. This mixed state is known as the
vortex state. Above the upper critical field Hc2, the magnetization
vanishes completely and the external magnetic field penetrates so as to
destroy the superconductivity. This indicates that above the critical field
H, a superconductor becomes a normal conductor. Thus, a
superconductor in the region Hc to H can conduct electric current within
the specimen, such that the magnetic field region can be used for high-
current and high-field superconductors like NiTi and Ni3Sb, which are
Type II superconductors.
Fig 10.8 Behavior of external magnetic field for type II

superconductor
126
10.5 HEAT CAPACITY
At low temperatures, the specific heat of a normal metal is given by an

expression
C= Ce + Cl - (3)
where Ce = γT and Cl = αT3are the electronic and lattice contributions,
respectively. The coefficient of electronic specific heat γ is defined by
an expression
2
𝛾 = 3 𝜋𝑟 2 𝑘𝐵2 𝑁(0) - (4)
Here, N(0) is the electronic density at the Fermi surface at 0 K and kB is

the Boltzmann constant. The coefficient α is related to the Debye
temperature θD through the relation
12 𝜋4 𝑁 𝑘𝐵
𝛼= 3 - (5)
5 𝜃𝐷
For the superconducting state Cl remains essentially unchanged but Ce

rises rapidly and discontinuously when the temperature is lowered
through TC, consequently the electronic specific heat in the
superconducting state becomes smaller than the normal state value.
Fig. 9 Variation of specific heat of a superconductor depicting a

jump at Tc
It depicts an exponential behavior proportional to -1/T, which suggests
excitation of electrons across an energy gap. This feature is quite
characteristic of the superconducting state. The argument of the
exponential factor is found to be -Eg/2kBT and not -Eg/kBT through optical
and electronic tunnelling experiments of the energy gap. Such an energy
gap in the superconductors is of entirely different origin from the energy
gap in semiconductors or insulators.
127
Fig. 10.10 Variation of superconducting energy gap with
temperature
While electron – lattice interactions are responsible for energy gap in

insulators, electron - electron interactions are the most important in
superconductors. The energy gap of a superconductors decreases
continuously to zero as the temperature is increased to the critical value
TC (fig 10.10).
10.6 ENERGY GAP
Experiments have shown that in superconductors, for temperatures in the

vicinity of absolute zero, a forbidden energy gap just above the Fermi level
is observed. Fig. 11a Shows the conduction band in the normal state. Fig.
11b depicts an energy gap equal to 2Eg at the Fermi level in the
superconducting state. Thus, the Fermi level in a superconductor is
midway between the ground state and the first excited state so that each
lies an energy distance = Eg away from the Fermi level.
Electrons in excited states above the gap behave as normal electrons. At
absolute zero, there are no electrons above the gap. Eg is typically of the
order of 10-4 eV
128
Fig. 10.11 depicts an energy gap equal to 2Eg at the Fermi level in
the superconducting state
Eg is found to be a function of temperature T. Fig. 10 shows reduced

values of observed energy gap Eg (T) / Eg (0) as a function of the
reduced temperature T/Tc . We observe that the energy gap
decreases continuously to zero as the temperature is increased to Tc
. The transition from the superconducting state to the normal state is
observed to be a second-order phase transition. In such a transition,
there is no latent heat, but there is a discontinuity in the heat capacity.
10.7 MICROWAVE AND INFRARED PROPERTIES
The existence of an energy gap means that photons of energy less than
the gap energy are not absorbed. Nearly all the photons incident are
reflected as for any metal because of the impedance mismatch at the
boundary between vacuum and metal, but for a very thin (-20 Å film more
photons are transmitted in the superconducting state than in the normal
state.
For photon energies less than the energy gap, the resistivity of a
superconductor vanishes at absolute zero. At T << Tc, the resistance in
the superconducting state has a sharp threshold at the gap energy.
Photons of lower energy see a resistance less surface. Photons of higher
energy than the energy gap see a resistance that approaches that of the
normal state because such photons cause transitions to unoccupied
normal energy levels above the gap.
As the temperature is increased not only does the gap decrease in energy,
but the resistivity for photons with energy below the gap energy no longer
129
vanishes, except at zero frequency. At zero frequency the
superconducting electrons short-circuit any normal electrons that have
been thermally excited above the gap. At finite frequencies the inertia of
the superconducting electrons prevents them from completely screening
the electric field, so that thermally excited normal electrons now can
absorb energy.
10.8 ISOTOPE EFFECT
It has been observed that the critical temperature of superconductors

varies with isotopic mass. In mercury, Tc varies from 4.185 K to 4.146 K
as the average atomic mass M varies from 199.5 to 203.4 atomic mass
units. The experimental results within each series of isotopes may be ftted
by a relation of the form
Mα Tc = constant. - (8)
Here α is a number usually 0.5. From the dependence of Tc on the

isotopic mass M, it is therefore evident that the lattice vibrations and
hence electron-lattice interactions are deeply involved in
superconductivity which will be deeply discussed in
Tc  θD  M -1/2 - (9)
Such a value of α=1/2, however, has not been found to be universal
and some elements have shown α = 0 for eg Ru and Zr.
LET US SUM UP
❖ Superconductivity is the phenomenon of zero electrical resistance

and repulsion of magnetic fields at very low temperatures. It was
discovered by Dutch physicist Hike Kamerlingh Onnes in 1911.
❖ The temperature at which a substance changes its state from
normal to superconducting in the absence of a magnetic feld is
known as critical temperature (Tc).
❖ There are two types of superconductors: Type I (soft) and Type II
(hard).
❖ No interior magnetic field is found in Type I superconductors. Type
II superconductors, on the other hand, have it completely only at
small magnetic fields, but partially at higher external fields.
130
1. What is Meissner effect?

2. Define Type I superconductor.
3. Define Type II superconductor
1. When a weak magnetic field is applied to a superconducting

specimen, below transition temperature it expels the magnetic flux
(i.e lines of force) initially held and acts as an ideal diamagnet. This
phenomenon is called the Meissner effect.
2. The superconductors which never allow a magnetic flux density
inside the superconductor, i.e., those which are perfectly
diamagnetic, are classified as Type I or soft superconductors
3. The superconductors which exhibit incomplete Meissner effect or
admit partial magnetic flux density and have zero resistivity are
called Type II or hard superconductors.
UNIT END EXERCISES
1. Give an account of destruction of superconductivity by magnetic

field.
2. Discuss in detail about Type I and Type II superconductors.
SUGGESTED READINGS

Delhi
Web Resources
1. https://www.youtube.com/watch?v=GglT1RoBPzg
2. https://www.youtube.com/watch?v=VHp2Ff5N_bs
3. https://www.youtube.com/watch?v=3hB1pSjZa6c
4. https://www.youtube.com/watch?v=DwkKnUqosLM
131
UNIT 11
BCS THEORY
Structure
Overview
Objectives
11.1 Thermodynamics of the superconducting transition
11.2 London equation
11.3 Coherence length

11.4 BCS theory of superconductivity
Let Us Sum Up
Check Your Progress
Unit end exercises
Suggested readings
OVERVIEW
At sufficiently low temperatures, electrons near the Fermi surface become

unstable against the formation of Cooper pairs. Cooper showed such
binding will occur in the presence of an attractive potential, no matter how
weak. In conventional superconductors, an attraction is generally
attributed to an electron-lattice interaction. The BCS theory, however,
requires only that the potential be attractive, regardless of its origin. In the
BCS framework, superconductivity is a macroscopic effect which results
from the condensation of Cooper pairs. These have some bosonic
properties, and bosons, at sufficiently low temperature, can form a
large Bose–Einstein condensate. Superconductivity was simultaneously
explained by Nikolay Bogolyubov, by means of the Bogoliubov
transformations.
In many superconductors, the attractive interaction between electrons

(necessary for pairing) is brought about indirectly by the interaction
132
between the electrons and the vibrating crystal lattice (the phonons).
Roughly speaking the picture is the following:
An electron moving through a conductor will attract nearby positive
charges in the lattice. This deformation of the lattice causes another
electron, with opposite spin, to move into the region of higher positive
charge density. The two electrons then become correlated. Because there
are a lot of such electron pairs in a superconductor, these pairs overlap
very strongly and form a highly collective condensate. In this "condensed"
state, the breaking of one pair will change the energy of the entire
condensate - not just a single electron, or a single pair. Thus, the energy
required to break any single pair is related to the energy required to
break all of the pairs (or more than just two electrons). Because the
pairing increases this energy barrier, kicks from oscillating atoms in the
conductor (which are small at sufficiently low temperatures) are not
enough to affect the condensate as a whole, or any individual "member
pair" within the condensate. Thus the electrons stay paired together and
resist all kicks, and the electron flow as a whole (the current through the
superconductor) will not experience resistance. Thus, the collective
behavior of the condensate is a crucial ingredient necessary for
superconductivity.
OBJECTIVES
➢ Describe the Thermodynamics of the superconducting

transition.
➢ Explain London Equation and Coherence length
➢ Discuss BCS theory of superconductivity
11.1THERMODYNAMICS OF SUPERCONDUCTING TRANSITION
In order to increase our understanding of the temperature dependence of

the specific heat of superconductors and the nature of the normal-
superconducting phase transition, we consider in this section a simple
model for the thermodynamics of a metal in the normal state and in the
superconducting state.
The Gibbs free energy per unit volume of a superconductor in a magnetic
field can be written as
133
𝐺 = 𝑈 − 𝑇𝑆 − 𝐻𝑀 (1)
where M is the magnetization, S is the entropy and the usual pV term is

neglected. We may verify Eq. 1 by observing that the changes in internal
energy density in the presence of a magnetic field is given by
𝑑𝑈 = 𝑇𝑑𝑆 + 𝐻𝑑𝑀 (2)
Then, from Eqs. 1 and 2, we obtain

𝑑𝐺 = −𝑆𝑑𝑇 − 𝑀𝑑𝐻 (3)
Substituting M = -H/4π for a perfect diamagnet (B = 0) and integrating Eq.

3, we obtain the following important relation for the superconducting state
at a given temperature
1
𝐺𝑠 = 𝐺𝑠 (0) + 8𝜋 𝐻2 (4)
From thermodynamic theory we know that for two phases to be in

equilibrium (at constant T; P; H), it is necessary that the Gibbs free
energies be equal. Thus, along the critical field curve where the
superconducting and normal states are in equilibrium,
1
𝐺𝑛 = 𝐺𝑠 (0) + 8𝜋 𝐻𝑐2 (5)
where Gn is the Gibbs free energy density of the normal state and is
essentially independent of the magnetic field. From Eq. 3, we obtain
𝜕𝐺
(𝜕𝑇 ) = −𝑆 (6)
𝐻
so that Eqs. 4 and 5 give the important result that in equilibrium

𝐻 𝑑𝐻𝑐
𝑆𝑛 − 𝑆𝑠 = − 4𝜋𝑐 (7)
𝑑𝑇
where Ss denotes the entropy in the superconducting phase in zero field.

Since dHc=dT is always found to be negative, the entropy of the normal
state is always greater than that of the superconducting state.
Finally, the difference in heat capacity per unit volume in the
superconducting and normal states is given by
𝑑 𝑇𝐻𝑐 𝑑2 𝐻𝑐 𝑇 𝑑𝐻 2
∆𝐶 = 𝐶𝑠 − 𝐶𝑛 = 𝑇 𝑑𝑇 (𝑆𝑠 − 𝑆𝑛 ) = + 4𝜋 [ 𝑑𝑇𝑐 ] (8)
4𝜋 𝑑𝑇 2
At T = Tc; where Hc = 0, we thus have
134
𝑇 𝑑𝐻 2
∆𝐶 = 4𝜋𝑐 [ 𝑑𝑇𝑐 ] (9)
We note from Eq. 7 that at the critical temperature Hc = 0 so that there is

no latent heat of transition (ΔS = 0), but there is, according to Eq. 9, a
discontinuity in the heat capacity. For this reason, the phase transition at
T = Tc (where Hc = 0) is of second order, but away from Tc, the phase
transition has a latent heat and is a first order phase transition.
11.2 LONDON EQUATIONS
A simple but useful description of the electrodynamics of

superconductivity was put forward by the brothers Fritz and Heinz London
in 1935, shortly after the discovery that magnetic fields are expelled from
superconductors. Their proposed equations are consistent with the
Meissner effect and can be used with Maxwell's equations to predict how
the magnetic field and surface current vary with distance from the surface
of a superconductor.
According to two fluid model, a superconductor is supposed to be
composed of two distinct types of electrons, i.e. normal electrons and
superelectrons. The normal electron behaves in a usual manner.
However, the superelectrons behave in a much different way, such as
they experience no scattering have zero entropy (perfect order), have a
long coherence length (~104Å), and so on. At T = Tc, all the electrons are
normal and as the temperature decreases an increasing proportion
becomes superelectrons until at T = OK all are superelectrons. Therefore,
based on this model, London brothers put forward the idea that at any
temperature the total sum of superelectrons and normal electrons is equal
to the conduction electron density in the material in the normal state. So
that if nn and ns respectively are the densities of normal electrons and
superelectrons, the conduction electron n becomes,
𝑛 = 𝑛𝑛 + 𝑛𝑠 (9)
Let us suppose that a small transient electric field E arises within a

superconductor which freely accelerates the super electrons. If vs is the
average velocity, m is the mass and e is the charge of a superelectron,
then the equation of motion can be written as
𝑑𝑣𝑠
𝑚 = −𝑒𝐸 (10)
𝑑𝑡
135
And the current density of superelectron is
𝐽𝑠 = −𝑒𝑛𝑠 𝑣𝑠 (11)
From eq. 2 and 3, we obtain
𝑑𝐽𝑠 𝑛𝑠 𝑒 2
=− 𝐸 (12)
𝑑𝑡 𝑚
This is called the first London equation. This shows that it is possible to
have steady state current in a superconductor in the absence of an electric
field, because in eq. 12, for E = 0. J is finite and constant or vice-versa.
The corresponding expression for normal current density is
𝐽𝑛 = 𝜎𝐸
which shows that no current is possible in the absence of an electric field,

a usual behaviour of materials in the normal state.
The conclusion E = 0 leads to another important result when combined
with the Maxwell’s equation
𝜕𝐵
∇ × 𝐸 = − ( 𝜕𝑡 ) (13)
That is
𝜕𝐵
( 𝜕𝑡 ) = 0 or B = constant (14)
Eq. 14 tells us that in steady state B is constant inside a superconductor

irrespective of its temperature. This result is not in agreement with the
Meissner effect, according to which a superconductor expels magnetic
flux completely for all temperatures below Tc. In order to remove this
discrepancy, London suggested some modifications in the above
formalism. For the purpose let us curl the eq. 12 and then substitute the
value of curl E from eq., we obtain
𝑑𝐽𝑠 𝑛𝑠 𝑒 2 𝑑𝐵
∇× =− (15)
𝑑𝑡 𝑚 𝑑𝑡
Integrating eq. 15 w.r.t and putting the constant of integration equal to

zero, we have
𝑛𝑠 𝑒 2
∇ × 𝐽𝑠 == − 𝐵 (16)
𝑚
136
London penetration depth
According to F. London and H. London (London theory), the magnetic field
at the surface of a superconductor does not vanish suddenly, it decays
exponentially to zero according to the following equation (Fig. 11.1),
−𝑥
𝐵 = 𝐵𝑜 𝑒 𝜆 (17)
Where B0 is the field at the surface, x is the distance from the surface and
λ is the characteristic length known as London penetration depth.
Fig. 11.1 Penetration depth

Penetration depth
Temperature (K)
Fig. 2 Variation of λ with T
137
The penetration depth varies with temperature. At low temperatures it is
almost constant, but higher temperatures the penetration depth increases
rapidly and tends to infinity as the temperature approaches the transition
temperature Tc (Fig. 2). This change is given by the relation,
𝜆 2 1
(𝜆𝑇 ) = 𝑇 4
(18)
𝑜 [1−( ) ]
𝑇𝑐
𝑚𝑜
𝜆𝑜 = (𝜇 2
) (19)
𝑜 𝑛𝑠 𝑒
Penetration depth at 0 K. m0 and e are the mass and charge of electron

respectively, ns is the number of superelectrons.
11.3 COHERENCE LENGTH
Pippard (1953) was the first to recognise the idea of a transition length
associated with the order parameter w. It is a distance within which the
order parameter w changes from its maximum value in the bulk
superconducting region to zero in the normal region (Fig. 3). This distance
is known as coherence length (ξ) and depends on the purity of the sample.
For a pure superconductor, the intrinsic coherence length ξ0 is obtained
as follows:
Fig. 11.3 Variation of magnetic field H and order parameter w

through an interface between the normal and superconducting
region
138
The electron states which are responsible for superconductivity lie within
kTc of the Fermi surface. From uncertainty principle, their lifetime τ is given
by
𝑘𝑇𝑐 ≃ ℏ
If vF is the electron velocity at the Fermi surface, then the wave function
must extend over a distance ξ0= vFτ. Therefore,
ℏ𝑣𝐹 ℏ𝑣𝐹
𝜉0 ≅ ≅ (20)
𝑘𝑇𝑐 2∆
However, a more refined form of this equation is

2ℏ𝑣𝐹
𝜉0 = ≅ 10−6 𝑚 (21)
𝜋∆
Like London penetration depth λ, the coherence length ξ is also a function

of temperature and also vary in the same manner.
11.4 BCS THEORY OF SUPERCONDUCTIVITY
According to classical physics, part of the resistance of a metal is due to

collisions between free electrons and the crystal lattice’s vibrations,
known as phonons. In addition, part of the resistance is due to scattering
of electrons from impurities or defects in the conductor.
A microscopic theory of superconductivity was developed in 1957 by John
Bardeen, Leon Cooper and J. Robert Schrieffer, which is known as the
BCS theory. The central feature of the BCS theory is that two electrons in
the superconductor are able to form a bound pair called a Cooper pair if
they somehow experience an attractive interaction between them. This
notion at first sight seems counterintuitive since electrons normally repel
one another because of their like charges. This may be thought of in the
following way and is illustrated in Fig.11. 4
An electron passes through the lattice and the positive ions are attracted
to it, causing a distortion in their nominal positions. The second electron
(the Cooper pair partner) comes along and is attracted by the displaced
ions. Note that this second electron can only be attracted to the lattice
distortion if it comes close enough before the ions have had a chance to
return to their equilibrium positions. The net effect is a weak delayed
attractive force between the two electrons. This short-lived distortion of
the lattice is sometimes called a virtual phonon because its lifetime is too
139
short to propagate through the lattice like a wave as a normal phonon
would.
Fig. 4 Classical description of the coupling of a Cooper pair
From the BCS theory, the total linear momentum of a Cooper pair must
be zero. This means that they travel in opposite directions as shown in
Figure 8. In addition, the nominal separation between the Cooper pair
(called the coherence length) ranges from hundreds to thousands of ions
separating them! This is quite a large distance and has been represented
incorrectly in many textbooks on this subject. If electrons in a Cooper pair
were too close, such as a couple of atomic spacings apart; the
electrostatic (coulomb) repulsion will be much larger than the attraction
from the lattice deformation and so they will repel each other. Thus, there
will be no superconductivity. A current flowing in the superconductor just
shifts the total moment slightly from zero so that, on average, one electron
in a cooper pair has a slightly larger momentum magnitude that its pair.
They do, however, still travel in opposite directions.
The interaction between a Cooper pair is transient. Each electron in the

pair goes on to form a Cooper pair with other electrons, and this process
continues with the newly formed Cooper pair so that each electron goes
140
on to form a Cooper pair with other electrons. The end result is that each
electron in the solid is attracted to every other electron forming a large
network of interactions. Causing just one of these electrons to collide and
scatter from atoms in the lattice means the whole network of electrons
must be made to collide into the lattice, which is energetically too costly.
The collective behaviour of all the electrons in the solid prevents any
further collisions with the lattice. Nature prefers situations that spend a
minimum of energy. In this case, the minimum energy situation is to have
no collisions with the lattice. A small amount of energy is needed to
destroy the superconducting state and make it normal. This energy is
called the energy gap.
Although a classical description of Cooper pairs has been given here, the
formal treatment from the BCS theory is quantum mechanical. The
electrons have wave-like behaviour and are described by a wave function
that extends throughout the solid and overlaps with other electron wave
functions. As a result, the whole network of electrons behaves line one
wave function so that their collective motion is coherent.
In addition to having a linear momentum, each electron behaves as if it is
spinning. This property, surprisingly, is called spin. This does not mean
that the electron is actually spinning, but behaves as though it is spinning.
The requirement from the BCS theory is that spins of a Cooper pair be in
opposite directions.
Note that the explanation and pictorial representation of a Cooper pair
presented here comes directly from BCS theory. However, current HSC
textbooks tend to distort this picture with unphysical situations such as the
Cooper pair being within one or two atomic spacings and traveling in the
same direction – each of these situations is false.
LET US SUM UP
✓ Transition between the normal and superconducting states is

thermodynamically reversible.
✓ According to London equations, the flux does not drop to zero
abruptly at the surface of a Type I superconductor but decreases
exponentially.
✓ According to BCS theory, super electrons exist as Cooper pairs.
They form a bound state, and their motions are highly correlated.
141
1. Define London penetration depth.

2. What is coherence length?
3. Define Cooper pair.
1. The London penetration depth refers to the exponentially decaying

magnetic field at the interior surface of a superconductor.
2. The superconducting coherence length is a measure of the size of
a Cooper pair (distance between the two electrons) and is of the
order of cm
3. Cooper pairs are a pair of electrons with opposite spins that are
loosely bound at absolute temperatures due to electron-lattice
interactions.
UNIT END EXERCISES
1. Obtain an expression for the London penetration depth of

magnetic field for a superconductor.
2. Give an elementary treatment of BCS theory of superconductivity.
SUGGESTED READINGS

Delhi
Web Resources
1. https://www.youtube.com/watch?v=2aSlKff0YYE
2. https://www.youtube.com/watch?v=WETC7HgOgHo
3. https://www.youtube.com/watch?v=RiqMTYVMg6M
4. https://www.digimat.in/nptel/courses/video/115103108/L01.html
142
UNIT 12
APPLICATIONS OF SUPERCONDUCTIVITY
Structure
Overview
Objectives
12. 1 Flux quantization in a superconducting ring
12.2 Single particle tunneling
12.3 DC Josephson effect

12.4 AC Josephson effect
12.5 Macroscopic quantum interface
12.6 High temperature superconductors
12.7 Applications
Let Us Sum Up
Check Your Progress
Unit end exercises
Suggested readings
OVERVIEW
Superconductors are noted for their zero DC electrical resistance. Hence,

most of the applications of the superconductor examples are because of
their properties which provide advantages such as low power loss
because of less dissipation of energy, high-speed operations because of
zero resistance and continuous flowing electrical current, and high
sensitivity. The usual and well-known superconductor examples are
mercury superconductors, niobium-tin superconductors, lanthanum-
barium-copper oxide superconductors, and yttrium-barium copper oxide
superconductors. Examples of applications of superconductors include
medical MRI/NMR devices, magnetic-energy storage systems, motors,
143
generators, transformers, computer parts and sensitive devices for the
measurement of magnetic fields, electrical currents, etc. Future possible
applications involve high-performance smart grids, electric power
transmission, transformers, electric motors (in vehicles like maglev trains),
magnetic levitation devices, superconducting magnetic refrigerators, etc.
Superconducting materials have come to be used experimentally to speed
up connections in computer chips. Superconducting coils are used as
electromagnets in MRI machines.
OBJECTIVES
➢ Understand the Flux quantization in a superconducting ring.

➢ Distinguish AC and DC Josephson effects.
➢ Explain basic characteristics of High temperature
superconductors and their applications.
12.1 FLUX QUANTIZATION IN A SUPERCONDUCTING RING
In 1950 Ginzburg and Landau developed a macroscopic theory for

superconducting phase transition based on general thermodynamical
approach to the theory of phase transition. They considered the long-
range order as fundamental and introduced a complex wave function ψ
as an order parameter to describe the superconducting state, where the
density of the superconducting electrons 𝑛𝑠 = |𝜓|2 . For a given
temperature, the order parameter ψ is a position in the materials i.e it is
not constant and vanishes above Tc. Since all Cooper pairs are in the
same two-electron state, a single wave function is sufficient.
If we write the wave function explicitly in terms of the magnitude and a
phase as ψ=|ψ| exp (iϕ), then the current density can be written as
2𝑒 2 𝑒ℏ
𝐽 = − ( 𝑚𝑐 𝐴 + 𝑚 ∇𝜑) |𝜓|2 (1)
Where A is the vector potential.

Let us consider a superconducting material in the shape of a ring as
shown in Fig. 12.1 and take a closed path, we find
144
Fig. 12.1 A ring shaped superconducting material showing the path
of integration C through its interior.
2𝑒 2 𝑒ℏ
∮ 𝐽. 𝑑𝑙 = |𝜓|2 ∮ ( 𝑚𝑐 𝐴 + 𝑚 ∇𝜑) . 𝑑𝑙 = 0 (2)
Whereas Stokes theorem gives us
∫ 𝐽. 𝑑𝑙 = ∫ ∇ × A . 𝑑𝑠 = ∫ 𝐵. 𝑑𝑠 = Φ (3)
Where Φ is the flux enclosed by the ring. Further, since the order
parameter is single valued, its phase change around the closed path must
be zero or an integral multiple of 2π. Therefore,
∮ ∇ϕ. 𝑑𝑙 = 2𝜋𝑛 (4)
Where n is an integer.
Substituting eq. 3 and 4 in 2 and solving for Φ, we find that the magnetic
flux enclosed by a ring must be quantized, i.e.
𝑛ℎ𝑐
Φ= = 𝑛Φ0 (5)
2𝑒
ℎ𝑐
Where Φ0 = 2𝑒 = 2.07 × 10−7 𝑔𝑎𝑢𝑠𝑠 − 𝑐𝑚2 is known as fluxoid or flux
quantum. The eq. 5 does not hold if the flux penetrates the ring itself
(partially when the material of the ring is thin).
Actually, the flux through the ring is the sum of the flux due to the external
source and the flux due to the supercurrent flowing through the ring i.e.
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Φ = Φ𝑒𝑥𝑡 + Φ𝑠𝑐 (6)
It is the flux Φ which is quantized. Normally, the flux due to the external
source is not quantized, therefore, Φ𝑠𝑐 must adjust itself such that Φ
assumes a quantized value.
12.2 SINGLE PARTICLE TUNNELING
Consider two metals separated by an insulator, as shown in Fig. 12. 2.

The insulator normally acts as a barrier to the flow of conduction electrons
from one end metal to the other. If the barrier is sufficiently thin less than
10 or 20 Å) there is a significant probability that an electron which
impinges on the barrier will pass from one metal to the other: this is called
tunneling. In many experiments the insulating layer is simply a thin oxide
layer formed on one of two evaporated metal films.
Fig.12. 2 Two metals, A and B separated by a thin layer of an

insulator C.
When both metals are normal conductors, the current-voltage relation of

the sandwich or tunneling junction is ohmic at low voltages, with the
current directly proportional to the applied voltage. Giaever discovered
that if one of the metals becomes superconducting the current-voltage
characteristic changes from straight line of Fig. 12.3 a to the curve shown
in Fig. 12.3 b
146
Fig. 12.3 (a) Linear current-voltage relation for junction of normal
metals separated by oxide layer; (b) current-voltage relation with
one metal normal and the other metal superconducting.
12.3 DC JOSEPHSON EFFECT
A dc current flows across the junction in the absence of any electric or

magnetic field.
The discussion of Josephson junction phenomena follows the discussion

of flux quantization. Let ψ1 be the probability amplitude of electron pairs
on one side of a junction and let ψ2 be the amplitude on the other side.
For simplicity, let both superconductors be identical. They are at zero
potential.
The time-dependent Schrodinger equation applied to the two amplitudes
gives
𝜕𝜓1 𝜕𝜓2
𝑖ℏ = ℏ𝑇𝜓2 ; 𝑖ℏ = ℏ𝑇𝜓1 (7)
𝜕𝑡 𝜕𝑡
Here ℏ𝑇 represents the effect of the electron pair coupling or transfer

interaction across the insulator; T has the dimensions of a rate or
frequency. It is a measure of the leakage of ψ1 into the region 2, and of ψ2
into the region 1. If the insulator is very thick, T is zero and there is no pair
tunneling.
⁄ ⁄
Let 𝜓1 = 𝑛11 2 𝑒 𝑖𝜃1 and 𝜓2 = 𝑛21 2 𝑒 𝑖𝜃2 then,
𝜕𝜓1 1 ⁄ 𝜕𝑛1 𝜕𝜃1

= 2 𝑛1−1 2 𝑒 𝑖𝜃1 + 𝑖𝜓1 = −𝑖𝑇𝜓2 (8)
𝜕𝑡 𝜕𝑡 𝜕𝑡
147
𝜕𝜓2 1 ⁄ 𝜕𝑛2 𝜕𝜃2
= 2 𝑛2−1 2 𝑒 𝑖𝜃2 + 𝑖𝜓2 = −𝑖𝑇𝜓1 (9)
𝜕𝑡 𝜕𝑡 𝜕𝑡
⁄
Multiply eq. 8 by 𝑛11 2 𝑒 −𝑖𝜃1 to obtain, with 𝛿 = 𝜃2 − 𝜃1
1 𝜕𝑛1 𝜕𝜃1
+ 𝑖𝑛1 = −𝑖𝑇〈𝑛1 𝑛2 〉1⁄2 𝑒 𝑖𝛿 (10)
2 𝜕𝑡 𝜕𝑡
⁄
Multiply eq. 8 by 𝑛21 2 𝑒 −𝑖𝜃2 to obtain
1 𝜕𝑛2 𝜕𝜃1
+ 𝑖𝑛2 = −𝑖𝑇〈𝑛1 𝑛2 〉1⁄2 𝑒 −𝑖𝛿 (11)
2 𝜕𝑡 𝜕𝑡
Now equate the real and imaginary parts of eq. 10 and similarly 11
𝜕𝑛1 𝜕𝑛2
= 2𝑇〈𝑛1 𝑛2 〉1⁄2 sin 𝛿 ; = −2𝑇〈𝑛1 𝑛2 〉1⁄2 sin 𝛿 ; (12)
𝜕𝑡 𝜕𝑡
𝜕𝜃1 𝑛 1⁄2 𝜕𝜃2 𝑛 1⁄2

= −𝑇 (𝑛2 ) cos 𝛿 ; = −𝑇 (𝑛1 ) cos 𝛿 ; (13)
𝜕𝑡 1 𝜕𝑡 2
If 𝑛1 ≅ 𝑛2 as for identical superconductors 1 and 2, we have from eq. 13

that
𝜕𝜃1 𝜕𝜃2 𝜕
= ; (𝜃2 − 𝜃1 ) = 0 (14)
𝜕𝑡 𝜕𝑡 𝜕𝑡
From eq. 12 we see that

𝜕𝑛2 𝜕𝑛1
=− (15)
𝜕𝑡 𝜕𝑡
𝜕𝑛2 𝜕𝑛1
The current flow from 1 to 2 is proportional to 𝜕𝑡
or the same thing, − 𝜕𝑡
.
We therefore conclude from eq. 12 that the current J of superconductor
pairs across the junction depends on the phase difference 𝛿 as
𝐽 = 𝐽0 sin 𝛿 = 𝐽0 sin(𝜃2 − 𝜃1 ) (16)
Where J0 is proportional to the transfer interaction T. the current J0 is the

maximum zero—voltage current that can be passed by the junction. With
no applied voltage a dc current will flow across the junction, with a value
between J0 and - J0 according to the value of the phase difference
(𝜃2 − 𝜃1 ). This is the dc Josephson effect.
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12.4 AC JOSEPHSON EFFECT
A dc voltage applied across the junction causes rf current oscillations

across the junction. This effect has been utilized in a precision
determination of the value ℏ/𝑒 of. Further, an rf voltage applied with the
dc voltage can then cause a dc current across the junction.
Let a dc voltage V be applied across the junction. We can do this because
the junction is an insulator. An electron pair experiences a potential
energy difference qV on passing across the junction, where q = -2e. We
can say that a pair on one side is at potential energy -eV and a pair on the
other side is at eV. The equations of motion are
𝜕𝜓1 𝜕𝜓2
𝑖ℏ = ℏ𝑇𝜓2 − 𝑒𝑉𝜓1 ; 𝑖ℏ = ℏ𝑇𝜓1 + 𝑒𝑉𝜓2 (17)
𝜕𝑡 𝜕𝑡
We proceed as above to find in place of (10) the equation
1 𝜕𝑛1 𝜕𝜃1
+ 𝑖𝑛1 = 𝑖𝑒𝑉𝑛1 ℏ−1 − 𝑖𝑇〈𝑛1 𝑛2 〉1⁄2 𝑒 𝑖𝛿 (18)
2 𝜕𝑡 𝜕𝑡
This equation breaks up into the real part
𝜕𝑛1
= 2𝑇〈𝑛1 𝑛2 〉1⁄2 𝑒 𝑖𝛿 (19)
𝜕𝑡
exactly as without the voltage V, and the imaginary part
𝜕𝜃1 𝑛 1⁄2
𝜕𝑡
= (𝑒𝑉 ⁄ℏ) − 𝑇 (𝑛2 ) cos 𝛿 (20)
1
Which differs from eq. 13 by the term 𝑒𝑉⁄ℏ.
Further, by extension of eq. 11
1 𝜕𝑛2 𝜕𝜃2
+ 𝑖𝑛2 = 𝑖𝑒𝑉𝑛2 ℏ−1 − 𝑖𝑇〈𝑛1 𝑛2 〉1⁄2 𝑒 −𝑖𝛿 (21)
2 𝜕𝑡 𝜕𝑡
Whence
𝜕𝑛2
= −2𝑇〈𝑛1 𝑛2 〉1⁄2 sin 𝛿 (22)
𝜕𝑡
𝜕𝜃2 𝑛 1⁄2
= −(𝑒𝑉 ⁄ℏ) − 𝑇 (𝑛1 ) cos 𝛿 (23)
𝜕𝑡 2
From eq. 20 and 23 with 𝑛1 ≅ 𝑛2 we have
149
𝜕 𝜕𝛿
(𝜃2 − 𝜃1 ) = = − 2𝑒𝑉 ⁄ℏ (24)
𝜕𝑡 𝜕𝑡
We see by integration of eq. 24 that with a dc voltage across the junction

the relative phase of the probability amplitudes varies as
𝛿(𝑡) = 𝛿(0) − (2𝑒𝑉𝑡⁄ℏ) (25)
The superconducting current is given by eq. 16 with eq. 25 for the phase
𝐽 = 𝐽0 sin[𝛿(0) − (2𝑒𝑉𝑡⁄ℏ)] (26)
The current oscillates with frequency
𝜔 = 2𝑒𝑉 ⁄ℏ (27)
This is the ac Josephson effect.
12.5 MACROSCOPIC QUANTUM INTERFACE
The phase difference 𝜃2 − 𝜃1 around a closed circuit which encompasses

a total magnetic flux Φ is given by
2𝑒
𝜃2 − 𝜃1 = (ℏ𝑐 ) Φ (28)
The flux is the sum of that due to external fields and that due to currents
in the circuit itself.
Fig.12. 4 The arrangement for experiment on macroscopic quantum

interference. A magnetic flux 𝚽 passes through the interior of the
loop.
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We consider two Josephson junctions in parallel, as in Fig. 4. No voltage
is applied. Let the phase difference between points 1 and 2 taken on a
path through junction a be 𝛿𝑎 . When taken on a path through junction b,
the phase difference is 𝛿𝑏 . In the absence of a magnetic field these two
phases must be equal.
Now let the flux Φ pass through the interior of the circuit. We do this with
a straight solenoid normal to the plane of the paper and lying inside the
circuit. By eq. 28
2𝑒
𝛿𝑏 − 𝛿𝑎 = (ℏ𝑐 ) Φ
or
𝑒 𝑒
𝛿𝑏 = 𝛿0 + ℏ𝑐 Φ; 𝛿𝑎 = 𝛿0 − ℏ𝑐 Φ (29)
The total current is the sum of Ja and Jb. The current through each junction
is of the form (16), so that
𝑒 𝑒 𝑒Φ
𝐽𝑇𝑜𝑡 = 𝐽0 {sin (𝛿0 + Φ) + sin (𝛿0 − Φ)} = 2(𝐽0 sin 𝛿0 ) cos
ℏ𝑐 ℏ𝑐 ℏ𝑐
The current varies with Φ and has maxima when

𝑒Φ
= 𝑠𝜋, s = integer (30)
ℏ𝑐
The short period variation is produced by interference from the two

junctions, as predicted by eq. 30. The longer period variation is a
diffraction effect and arises from the finite dimensions of each junction-
this causes to depend on the particular path of integration.
12.6 HIGH TEMPERATURE SUPERCONDUCTORS
It has long been a dream of scientists working in the field of

superconductivity to find a material that becomes a superconductor at
room temperature. A discovery of this type will revolutionize every aspect
of modern-day technology such as power transmission and storage,
communication, transport and even the type of computers we make. All of
these advances will be faster, cheaper and more energy efficient. This
151
has not been achieved to date. However, in 1986 a class of materials was
discovered by Bednorz and Müller that led to superconductors that we use
today on a bench-top with liquid nitrogen to cool them. Not surprisingly,
Bednorz and Müller received the Nobel Prize in 1987 (the fastest-ever
recognition by the Nobel committee). The material we mostly use on
bench-tops is Yttrium – Barium – Copper Oxide, or YBa2Cu3O7, otherwise
known as the 1-2-3 superconductor, and are classified as high
temperature (Tc) superconductors. High-temperature
superconductors (abbreviated high-Tc or HTS) are defined as materials
that behave as superconductors at temperatures above 77 K (−196.2 °C;
−321.1 °F), the boiling point of liquid nitrogen.
The critical temperature of some high-Tc superconductors is given above.

Critical temperatures as high as 135 K have been achieved. Whilst this is
not room temperature, it has made experiments on superconductivity
accessible to more people since these need only be cooled by liquid
nitrogen (with a boiling point of liquid nitrogen is 77 K), which is cheap and
readily available. This is in contrast to the expensive and bulky equipment
that used liquid helium for cooling the traditional types of superconductors.
Moreover, the superconductors are calculated to have an upper critical
magnetic field, Bc2, of about 200 Tesla – huge!
The crystal lattice structure of YBa2Cu3O7 is shown in Fig. 5. Unlike
traditional superconductors, conduction mostly occurs in the planes
containing the copper oxide. It has been found that the critical temperature
is very sensitive to the average number of oxygen atoms present, which
can vary. For this reason the formula for 1-2-3 superconductor is
sometimes given as YBa2Cu3O7-δ where δ is a number between 0 and 1.
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Fig. 5 Crystal lattice structure of the High – Tc superconductor,
YBa2Cu3O7
The nominal distance between cooper pairs (coherence length) in these

superconductors can be as short as one or two atomic spacings. As a
result, the coulomb repulsion force will generally dominate at these
distances causing electrons to be repelled rather than coupled. For this
reason, it is widely accepted that Cooper pairs, in these materials, are not
caused by a lattice deformation, but may be associated with the type of
magnetism present (known as antiferromagnetism) in the copper oxide
layers. So high–Tc superconductors cannot be explained by the BCS
theory since that mainly deals with a lattice deformation mediating the
coupling of electron pairs. The research continues into the actual
mechanism responsible for superconductivity in these materials.
12.7 APPLICATIONS OF SUPERCONDUCTORS
The first large scale commercial application of superconductivity was in

magnetic resonance imaging (MRI). This is a non-intrusive medical
imaging technique that creates a two-dimensional picture of say tumors
153
and other abnormalities within the body or brain. This requires a person
to be placed inside a large and uniform electromagnet with a high
magnetic field. Although normal electromagnets can be used for this
purpose, because of resistance they would dissipate a great deal of heat
and have large power requirements. Superconducting magnets on the
other hand have almost no power requirements apart from operating the
cooling. Once electrical current flows in the superconducting wire, the
power supply can be switched off because the wires can be formed into a
loop and the current will persist indefinitely as long as the temperature is
kept below the transition temperature of the superconductor.
Superconductors can also be used to make a device known as a
superconducting quantum interference device (SQUID). This is incredibly
sensitive to small magnetic fields so that it can detect the magnetic fields
from the heart (10-10 Tesla) and even the brain (10-13 Tesla). For
comparison, the Earth’s magnetic field is about 10-4 Tesla. As a result,
SQUIDs are used in non-intrusive medical diagnostics on the brain.
The traditional use of superconductors has been in scientific research
where high magnetic field electromagnets are required. The cost of
keeping the superconductor cool is much smaller than the cost of
operating normal electromagnets, which dissipate heat and have high
power requirements. One such application of powerful electromagnets is
in high energy physics where beams of protons and other particles are
accelerated to almost light speeds and collided with each other so that
more fundamental particles are produced. It is expected that this research
will answer fundamental questions such as those about the origin of the
mass of particles that make up the Universe.
Levitating trains have been built that use powerful electromagnets made
from superconductors. The superconducting electromagnets are mounted
on the train. Normal electromagnets, on a guideway beneath the train,
repel (or attract) the superconducting electromagnets to levitate the train
while pulling it forwards.
A use of large and powerful superconducting electromagnets is in a
possible future energy source known as nuclear fusion. When two light
nuclei combine to form a heavier nucleus, the process is called nuclear
fusion. This results in the release of large amounts of energy without any
harmful waste. Two isotopes of hydrogen, deuterium and tritium, will fuse
to release energy and helium. Deuterium is available in ordinary water
and tritium can be made during the nuclear fusion reactions from another
abundantly available element – lithium. For this reason, it is called clean
nuclear energy. For this reaction to occur, the deuterium and tritium gases
154
must be heated to millions of degrees so that they become fully ionized.
As a result, they must be confined in space so that they do not escape
while being heated. Powerful and large electromagnets made from
superconductors are capable of confining these energetic ions. An
international fusion energy project, known as the International
Thermonuclear Experimental Reactor (ITER) is currently being built in the
south of France that will use large superconducting magnets and is due
for completion in 2017. It is expected that this will demonstrate energy
production using nuclear fusion.
LET US SUM UP
❖ When a thin insulating layer is sandwiched between a metal and

a superconductor or two superconductors, electrons can tunnel
through the junction. The current-voltage characteristics of the
junction help in determining the energy gap of a superconductor.
❖ For a thin insulating layer, Cooper electrons can tunnel even at
zero potential difference, leading to the Josephson effect. A static
voltage across the junction produces an alternating current of
frequency 𝜔 = 2𝑒𝑉⁄ℏ.
1. What is dc Josephson effect?

2. What is ac Josephson effect?
3. What are high temperature superconductors?
1. A dc current flows across the junction in the absence of any

electric or magnetic field.
2. A dc voltage applied across the junction causes rf current
oscillations across the junction. This effect has been utilized in a
precision determination of the value ℏ/𝑒 of. Further, an rf voltage
applied with the dc voltage can then cause a dc current across the
junction
3. High-temperature superconductors (abbreviated high-Tc or HTS)
are defined as materials that behave as superconductors at
temperatures above 77 K (−196.2 °C; −321.1 °F), the boiling point
of liquid nitrogen
155
UNIT END EXERCISES
1. Explain dc Josephson effect. Show that the supercurrent of

superconducting pairs across the junction depends on the phase
difference.
2. Discuss ac Josephson effect. Show that the current oscillates with
the frequency 𝜔 = 2𝑒𝑉⁄ℏ
SUGGESTED READINGS

Delhi
Web Resources
1. https://www.youtube.com/watch?v=D-9M3GWoBrw
3. https://www.youtube.com/watch?v=hob6CCbpNAE
4. https://www.youtube.com/watch?v=Uf6HAF6Qa0w
5. https://www.youtube.com/watch?v=WETC7HgOgHo
6. https://www.youtube.com/watch?v=RiqMTYVMg6M&t=20s
7. https://www.youtube.com/watch?v=rxhjgrJL6tU
9. https://www.youtube.com/watch?v=au3nwl_MRNY
156
BLOCK V: PHYSICS OF NANOSOLIDS
Unit 13: Physics of Nanosolids
Unit 14: Carbon Nanotechnology
Unit 15: Nanoelectronics
157
UNIT 13
PHYSICS OF NANOSOLIDS
Structure
Overview
Objectives
13.1 Definition of nanoscience and nanotechnology
13.2 Preparation of nanomaterials
13.3 Surface to volume ratio

13.4 Quantum confinement - Qualitative and Quantitative description
13.5 Density of states of nanostructures
13.6 Excitons in Nano semiconductors
Let Us Sum Up
Check Your Progress
Unit End Exercises
Suggested readings
OVERVIEW
Nanoscience is a phenomenon of manipulation of materials at the atomic,

molecular and macromolecular scales, where properties differ
significantly from those at larger scales. Nanotechnology is the design,
characterisation, production and application of structures, devices and
systems by controlling shape and size at the nanometre scale.
Nanomaterials are defined as particles in the form of crystals, rods, or
spheres having size between 1 nm and 100 nm at least in one dimension.
A nanometre is one billionth of a meter, or 10-9 m. Materials in this range
of size exhibit some remarkable specific properties. For example, crystals
in the nanometre scale have a low melting point and reduced lattice
constants. Nanosystems display electronic, photochemical,
electrochemical, optical, magnetic, mechanical or catalytic properties that
158
differ significantly not only from those of molecular units, but also from
those of macroscopic systems.
Physical properties that make nanomaterials different from bulk

(macroscale) materials
1. Due to smallness of nanomaterials, their mass is extremely small
and gravitational forces become negligible, instead
electromagnetic forces are dominant in determining the behaviour
of atoms and molecules.
2. For objects of very small mass, such as electrons, (wave – particle

duality of matter) wave like nature has more pronounced effect.
The position of electrons are represented by wave function.
Quantum mechanics is used to describe motion and energy
instead of classical mechanics.
3. The consequence of this is the tunnelling. It is the penetration of
an electron into an energy region that is classically forbidden. For
a particle having less energy than the energy required to overcome
a potential barrier, there is no probability of finding the particle on
the other side of the barrier according to classical theory. But
quantum mechanically, there is a finite probability of the particle
tunnelling through the barrier. The condition for this to happen is
that the thickness (energy potential) of the barrier must be
comparable to the wavelength of the particle. This is observed at
nanometre scale.
4. Quantum confinement – In a nanomaterial, such as a metal,
electrons are confined in space rather than free to move in the bulk
of the material.
5. Quantisation of energy – Electrons in a nanomaterial can exist at
discrete energy levels.
6. At nanoscale, the random motions are of same scale as the size
of the material. This has an influence on how particle behave.
7. Increased surface to volume ratio – One of the distinguishing
properties of nanomaterials is that they have increased surface
area. This leads to unique properties of materials at nanoscale.
OBJECTIVES
159
➢ Understand the Definition of nanoscience and nanotechnology.
➢ Describe the preparation of nanomaterials.
➢ Explain Surface to volume ratio and Quantum confinement.
➢ Discuss Excitons in Nano semiconductors.
➢ Explain basic characteristics of nanomaterials.
13..1 DEFINITION OF NANOSCIENCE AND NANOTECHNOLOGY
Nanomaterials are those which have at least one dimension in the

range of 1-100 nm. The term “Nano” originates from the Greek word
“nanos” and Latin word “nanus” which means “Dwarf”. The
nanomaterials are of interest as they have unique properties (optical,
magnetic and electrical and thermal) that are size dependent critically
in the nanoscale, which makes them the game changers of Physics of
Material Science. In the 4th century articles made of nanomaterials
were under use like: The Lycurgus Cup is a Roman glass cage cup
made of a dichroic glass, which shows different colours in transmission
and reflection Fig.1 (a) & (b). Today's scientists and engineers are
finding a wide variety of ways to deliberately make materials at the
nanoscale to take advantage of their enhanced properties such as
higher strength, lighter weight, increased control of light spectrum, and
greater chemical reactivity than their bulk counterparts.
If we look into the history, it was Feynman Fig:1(b), during his talk
entitled “There is a Plenty of Room at the Bottom” at CalTech on 29th
December 1959, to introduce the ideas and concepts of nanoscience
and nanotechnology, long before the term nanotechnology was used.
After a decade, it is Prof. Norio Taniguchi Fig: 1(c) who first actually
coined the term “Nanotechnology”. The study of the properties and
applications of nanomaterials are called as Nanoscience and
Nanotechnology resp., and which enable to see and control the
individual atoms and molecules. The microscopes needed to see
nanoparticles were invented in 1980s. So once the scientists had the
right tools such as Scanning tunneling microscope and Atomic force
microscope, the era of Nanotechnology began.
160
Fig.13.1 (a) Lycurgus cup in transmitted (red) & (b) reflected
(green) light (c) Richard Feynman & (d) Norio Taniguchi
13.2 PREPARATION OF NANOMATERIALS
There are 2 basic approaches in the synthesis of nanomaterials.

1. Top-down and
2. Bottom-up approach (simply saying from small to big).
161
In the “top-down” synthesis, the corresponding material is
reconstructed or deformed, ablated to form different structures, akin to
a sculptor chiseling a block of marble to create a statute of definite
shape and size. It involves breaking down of large size bulk material
into Nano size particles.
Eg:1. Milling, 2. Attrition process and 3. Electro explosion wire (EEW)

technique.
Drawbacks
1. It is a quick manufacturing process but requires more energy,
so it is not suitable for large scale production.
2. Another drawback of top down approach is imperfections of

surface structure & such defects have a significant impact on
the physical and other properties of nanoparticles.
3. A high degree of deformation of material occurs in mechanical
milling process due to repeated impact between the ball and
particles which is unwanted.
4. There may be generation of heat and also particle
agglomeration and this can be avoided by milling under wet
conditions.
Bottom–up approach
In “bottom-up” synthesis, the material is constructed from atom or
molecules to the cluster until the designed shape is achieved, akin to
building a house from bricks. During the assembling process physical
forces acting on the Nano structure used to combine the particles in to
a larger one. Most of the complex nanostructures can be synthesized
by this approach and hence this is mostly preferred because of the
advantage of precise control of particle size.
Eg:1. Sol-gel method, 2. Co-precipitation, 3. Inert gas condensation
162
Fig.13.2 Schematics of Top down & Bottom up approaches
13.2 SURFACE TO VOLUME RATIO
The surface area to volume ratio for a material or substance made of

nanoparticles has a significant effect on the properties of the material.
Firstly, materials made up of nanoparticles have a relative larger surface
area when compared to the same volume of material made up of bigger
particles.
For example, let us consider a sphere of radius r. The surface area of the
sphere will be 4πr2. The volume of the sphere = 4/3πr3. Therefore, the
surface area to the volume ratio will be 4πr2/(4/3πr3) = 3/r. It means that
the surface area to volume ratio increases as the radius of the sphere
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decreases and vice versa. It also means that when a given volume of
material is made up of smaller particles, the surface area of the material
increases. Therefore, as particle size decreases, a greater proportion of
the particles are found at the surface of the material. For example, a
particle of size 3 nm has 50% of its particles on the surface; at 10 nm,
20% of its particles are on the surface; and at 30 nm, 5% of its particles
are on the surface. Therefore, materials made of nanoparticles have a
much greater surface area per unit volume ratio compared with the
materials made up of bigger particles. This leads to nanoparticles being
more chemically reactive. As chemical reactions occur between particles
that are on the surface, a given mass of nanomaterial will be much more
reactive than the same mass of material made up of large particles. This
means that materials that are inert in their bulk form are reactive when
produced in their nanoparticle form.
13.4 QUANTUM CONFINEMENT - QUALITATIVE AND QUANTITATIVE

DESCRIPTION
Quantum confinement is the restricted motion of randomly moving

electrons in specific energy levels if one or more of the dimensions of a
crystal approach the Bohr exciton radius or de Brogile wavelength of the
electron. The length scale corresponding to quantum confinement regime
usually ranges from 1-25 nm. Low-dimensional systems exhibit
nanometric size in one (2D systems), two (1D systems) or three (0D
systems) spatial dimensions. To avoid the confusion about how the low
dimensional systems are defined, we consider that the charge carriers
have degree of freedom directions and confinement directions.
For bulk materials, there are three degrees of freedom directions and zero
confined directions. Thus, bulk materials are called three-dimensional
systems.
Quantum wells are considered two-dimensional systems, which mean
that the charge carriers have two degrees of freedom directions and one
confined direction. In this case, the growth direction is the confined
direction.
Quantum wires, on the other hand, have one degree of freedom direction
and two confined directions. Thus, quantum wires are considered one-
dimensional systems. When the charge carriers are confined in three
directions, the structure is called zero-dimensional system. We refer to
this system as quantum dots.
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Quantum Well — flat thin layer of semiconductor material (typically
between 1 and 10 nm thick) within which the potential energy of an
electron is less than outside the layer, therefore the motion of the electron
is limited in one dimension. The motion of the electron perpendicular to
the quantum well plane is quantised, and its energy can take on only
discrete values.
Design:
Quantum wells are real-world implementation of the “particle in the
box” problem; they act as potential wells for charge carriers and are
typically experimentally realized by epitaxial growth of a sequence
of ultrathin layers consisting of semiconducting materials of varying
composition.
The main differentiating characteristic among the three structures

was the size of the structure in each coordinate, with respect to a
particle’s de Brogile wavelength at the fermi energy(𝜆F). Assuming the
electron E-K relation
ℏ𝑘 2
𝐸=
2𝑚𝑒∗
Which, for instance, typically holds near the bottom of the

conduction band in a semiconductor, we have
ℎ
𝜆𝐹 =
√2𝑚𝑒∗ 𝐸𝐹
If the electron’s environment is large compared to 𝜆F then the electron

will behave approximately as if it is free. If the electron’s wavelength is on
the order of, or is large compared to with, its environment, then it will
behave in a confined fashion.
To appreciate the size involved, consider that in three dimensions

the Fermi wavelength
2𝜋
𝜆𝐹 = 1⁄3
(3𝑁𝑒 𝜋2 )
In typical metals, 𝜆F is approximately in the range 0.5nm to 1 nm.
In typical semiconductors, 𝜆F is approximately in the range 10 nm to 100

nm.
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If Lx ≤ F << Ly, Lz, then we have an effectively two-dimensional system-a
quantum well. The Fermi wavelength (𝜆F) is nothing but the de Broglie
wavelength of electrons near the Fermi energy.
Fig. 13.3 In quantum wells, electrons are confined only in one

dimension. Quantum wells are usually implemented by burying the
confining material within a barrier material.
Fabrication:
The simplest quantum structure in which electron motion is restricted in
one direction is a thin film or a sufficiently thin layer of a semiconductor. It
was in thin films of semimetal bismuth and InSb semiconductor that size
quantisation effects were first observed. Today quantum structures are
manufactured differently. Their production is based on so-called
heterostructures, which are obtained by creating semiconductor contacts
with different band gaps. A thin layer of a semiconductor with a narrow
band gap is placed between two layers of a material with a wider band
gap. As a result, the electron is trapped in one dimension, while in the
other two dimensions the electron can move freely.
Several sophisticated processes have been developed for manufacturing
such structures, but the best results in the formation of quantum
heterostructures have been achieved by the method of molecular beam
epitaxy. Heterostructures can be grown using different materials, but the
best pair for growing quantum wells is gallium arsenide GaAs and the solid
solution of AlxGa1-xAs (x = 0.15-0.35).
Characterization techniques:
The width of the quantum well will be characterized using Field emission
scanning electron microscope. Optical characterization of QDs is usually
provided by UV-VIS and photoluminescence spectroscopy.
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Applications:
Quantum wells are used widely in diode lasers, including red lasers for
DVDs and laser pointers, infra-red lasers in fiber optic transmitters, or in
blue lasers. They are also used to make HEMTs (high electron mobility
transistors), which are used in low-noise electronics. Quantum well
infrared photodetectors are also based on quantum wells and are used
for infrared imaging. The theory surrounding quantum well devices has
led to significant advancements in the production and efficiency of many
modern components such as light-emitting diodes, transistors for
example. Today, such devices are ubiquitous in modern cell phones,
computers, and many other computing devices.
Fig.4 Schematic representation of a quantum well. The vertical axis

represents the quantum particle energy, and the horizontal line - its
coordinate; a is the width of quantum well; E1,..., En is the set of
discrete values of quantum particle's energy.
Quantum wire - a filamentary object, whose cross-sectional dimensions
satisfy the condition of size quantisation. The potential energy of the
electron in this object is lower than outside of it, and the electron motion
is restricted to two dimensions due to small cross size (usually 1-10 nm).
Movement along the filament axis remains free, while movement in other
directions is quantised, and its energy can only take discrete values.
Properties of quantum wires:

Quantum wires are light weight, high electrical conductivity, small
diameter, low chemical reactivity and high tensile strength.
Design:
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If Lx, Ly ≤ F <<Lz, then we have an effectively one-dimensional system-a
Quantum wire. The Fermi wavelength (𝜆F) is nothing but the de Broglie
wavelength of electrons near the Fermi energy.
Fig.12.5 Quantum wires confine electrons in two dimensions. The

electron is not confined along the wire.
Fabrication:
Quantum wires are one-dimensional electronic systems, the most
outstanding representatives of which are carbon nanotubes and
semiconductor heterostructures. The latter are manufactured using
lithographic technology by etching a narrow strip in a heterostructure as
shown in figure.
Fig. 6 Quantum wire produced by submicron lithography through

etching of a thin strip from a heterostructure [1]: 1 – semiconductor
with a wide band gap (e.g., AlGaAs), 2 – semiconductor with a
narrow band gap (e.g., GaAs).
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The width of the quantum wire will be characterized using Field emission
scanning electron microscope and transmission electron microscope.
Optical characterization of QDs is usually provided by UV-VIS and
photoluminescence spectroscopy.
Applications:
❖ Electronic devices
❖ Sensing using semiconductor nanowires
❖ In high density data storage
❖ Batteries
Quantum dots (QDs): Quantum dots are zero dimensional materials with
three dimensional confined carriers. They are very small semiconductor
crystals on the order of nanometre size, containing merely a hundred to a
thousand atoms. As a result, they tightly confine electrons or electron-hole
pairs called “excitons” in all three dimensions. QDs can be made from
single-element materials, such as silicon or germanium, or from
compound semiconductors, such as CdSe, PbSe, CdTe, and PbS. QDs
are also sometimes referred to as “artificial atoms,” as these materials
exhibit discrete electronic states as seen in atoms and molecules.
Quantum dots are artificial nanostructures that can possess many varied
properties, depending on their material and shape. For instance, due to
their particular electronic properties they can be used as active materials
in single-electron transistors. The properties of a quantum dot are not only
determined by its size but also by its shape, composition, and structure,
for instance if it's solid or hollow.
Design:
If Lx, Ly, Lz ≤ 𝜆F, then we have an effectively zero-dimensional system-a
quantum dot
The Fermi wavelength (𝜆F) is nothing but the de Broglie wavelength of
electrons near the Fermi energy.
169
Lz
Ly
Lx
Fig. 13. 7 In a quantum dot, an electron is confined in three
dimensions.
QDs' size is generally calculated using conventional techniques like
scanning electron microscopy (SEM), transmission electron microscopy
(TEM), and dynamic light scattering (DLS) studies. Optical
characterization of QDs is usually provided by UV-VIS and
photoluminescence spectroscopy The quantum confinement effect is
usually studied using photoluminescence (PL) and magneto-PL.
170
Fig. 8 Quantum dots are nanoscale man-made crystals that have
the ability to convert a spectrum of light into different colors. Each
dot emits a different color depending on its size.
How Quantum Dots Work

When energy is applied to an atom, electrons are energized and move to
a higher level. When the electron returns to its lower and stable state, this
additional energy is emitted as light corresponding to a particular
frequency. Quantum dots work in much the same way but a quantum dot
crystal act as one very large atom. The energy source used to stimulate
a quantum dot is commonly ultraviolet light. The frequency or colour of
light given off is not related to the material used in the quantum dot, but
by the size of the quantum dot.
Quantum Dot Size and Color Relationship
If semiconductor particles are made small enough, quantum effects come
into play, which limit the energies at which electrons and holes (the
absence of an electron) can exist in the particles. As energy is related to
wavelength (or color), this means that the optical properties of the particle
can be finely tuned depending on its size. Thus, particles can be made to
emit or absorb specific wavelengths (colors) of light, merely by controlling
their size.
Large quantum dots produce light with a long wavelength and small
quantum dots produce light with small wavelengths. In terms of colour in
the visible spectrum, this means large quantum dots produce red light and
small quantum dots produce blue light – sizes in between account for all
the other colours in the spectrum. By combining a range of sizes of
quantum dots in the same sample, the entire light spectrum can be
produced simultaneously and appears as white light.
Fabrication Methods
Quantum dots can be manufactured by a number of processes from
colloidal synthesis to chemical vapour deposition (CVD). The cheapest
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and simplest method is benchtop colloidal synthesis. Electrochemical
techniques and CVD can be used to create ordered arrays of quantum
dots on a substrate material.
Applications:
Blue-laser diodes, single electron transistor, light-emitting devices, solar
cells, LEDs, transistors, displays, laser diodes, quantum computing, and
medical imaging etc
13.5 DENSITY OF STATES OF NANOSTRUCTURES
Density of states (DOS) is defined as the number of available states per

unit energy per unit volume. The density of states function will change
upon changing the dimensionality of the solid. For electrons in a bulk
semiconductor, density of states is zero at the bottom of the conduction
band and increases as the energy of the electrons in the conduction band
increases, given by E1/2. This behaviour is shown in figure, which
compares the density of states for electron in a quantum well (and also in
quantum wire and dot), where the density of states is a step function
because of the discreteness of the energy levels along the confinement
direction
Fig. 13.9 Density of states in (a) bulk semiconductor (3D), (b)

quantum well (2D), (c) quantum wire (1D), and (d) quantum dot (0D).
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13.6 EXCITONS IN NANO SEMICONDUCTORS
❖ The concept of excitons was first proposed by Yakov Frenkel in

1931.
❖ The absorption of a photon by an inter band transition in a
semiconductor creates an electron in conduction band and a hole
in valence band.
❖ These oppositely charged particles attract each other through
Coulomb interaction and there may be a probability of formation of
a neutral electron hole pair called exciton.
❖ “An exciton is a bound state of an electron and hole which are
attracted to each other by an electrostatic force.”
❖ When the photon is absorbed by a semiconductor, an electron
hole pair is created as shown in Fig. 3.7.
❖ The electron in the conduction band is now attracted to the
localized hole by repulsive Coulomb forces from the large number
of electrons surrounding the hole and excited electrons.
❖ This attraction provides a stabilizing energy balance
Fig. 13.10 Electron-hole pair
Frenkel exciton:
❖ “When there is a strong electron hole attraction, like in ionic
crystals, the electrons and holes are tightly bound to each other,
this type of exciton is called Frenkel exciton.”
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❖ They are also called tight bound excitons. They are found
molecular crystals.
❖ They are bound to specific atoms or molecules and they move by
hopping from one atom to another. Their binding energy is of a
range 0.1 eV to 1 eV. They are stable at room temperature.
Fig. 13.11 Frenkel exciton
Wannier – Mott excitons:

❖ “When the electron hole separation is much larger to the lattice
constant, then the exciton is called Wannier-Mott exciton.”
❖ In this, the electron hole pair is weakly bound. They are also called
free excitons. They mainly exist in semiconductor. They have large
radius.
❖ They are delocalized state that can move freely throughout the
crystal. They have a binding energy of around 0.01 eV.
Fig. 13.12 Wannier – Mott excitons
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LET US SUM UP
Nanomaterials are defined as particles in the form of crystals, rods,

or spheres having size between 1 nm and 100 nm at least in one
dimension.
There are 2 basic approaches in the synthesis of
nanomaterials. Top-down and Bottom-up approach (simply
saying from small to big).
Quantum confinement is the restricted motion of randomly moving
electrons in specific energy levels if one or more of the dimensions
of a crystal approach the Bohr exciton radius or de Brogile
wavelength of the electron. The length scale corresponding to
quantum confinement regime usually ranges from 1-25 nm. Low-
dimensional systems exhibit nanometric size in one (2D systems),
two (1D systems) or three (0D systems) spatial dimensions.
An exciton is a bound state of an electron and hole which are
attracted to each other by an electrostatic force
1. What do you mean by Quantum Dot, Wire, Well?

2. Define Quantum Confinement.
3. Define Density of Sates
1. Density of States: Density of states (DOS) is defined as the

number of available states per unit energy per unit volume.
2. Quantum confinement: Quantum confinement is change of
electronic and optical properties when the material sampled is of
sufficiently small size - typically 10 nanometers or less.
3. Quantum Well: A quantum well is a potential well with only
discrete energy values
Quantum Wire: A filamentary object, whose cross-sectional
dimensions satisfy the condition of size quantisation. The potential
energy of the electron in this object is lower than outside of it, and
the electron motion is restricted to two dimensions due to small
cross size (usually 1-10 nm). Movement along the filament axis
remains free, while movement in other directions is quantised, and
its energy can only take discrete values.
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Quantum Dot: Quantum dots (QDs) are zero dimensional
materials with three
dimensional confined carriers. They are very small semiconductor
crystals on the order of nanometre size, containing merely a
hundred to a thousand atoms.
UNIT END EXERCISES
1. What are the methods to prepare nanomaterials and discuss in

detail.
2. Discuss about Quantum well in detail
3. Discuss about Quantum Wire in detail.
4. Discuss about Quantum Dots
5. Explain the density of states in 2D, 1D and 0D.
SUGGESTED READINGS
1. Hanson, G.W. “Fundamentals of Nanoelectronics”. Pearson

Education, 2009
2. Rogers, B., Adams, J. & Pennathur, S. “Nanotechnology:
Understanding Small Systems”. CRC Press, 2014
3. T. Pradeep, A textbook of Nanoscience and Nanotechnology,
Tata McGraw Hill education Pvt. Ltd., New Delhi
4. K.K.Chattopadhyay, A.N.Banerjee, Introduction to Nanoscience
and Nanotechnolog, PHI Learning private Ltd., Delhi 2014
Web Resources
1. https://www.youtube.com/watch?v=ebO38bbq0_4
3. https://www.youtube.com/watch?v=qUEbxTkPIWI
4. https://www.youtube.com/watch?v=jY2p7LpXAao
5. https://www.youtube.com/watch?v=b_BA7kymfg4
6. https://www.youtube.com/watch?v=YynCBmtUO1c
7. https://www.youtube.com/watch?v=evE08ycZfnM
8. https://www.youtube.com/watch?v=WYCoXpxsqj4
9. https://www.youtube.com/watch?v=t-m-NwJa4lY
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UNIT 14
CARBON NANOTECHNOLOGY
Structure
Overview
Objectives
14.1 Buckminsterfullerene
14.2 Carbon nanotubes
14.3 Nano diamond

14.4 BN nanotubes
Let Us Sum Up
Check Your Progress
Unit End Exercises
Suggested readings
OVERVIEW
Carbon also plays a vital role in nanotechnology research and

nanotechnology applications. Carbon is a non-metallic element present in
the cells of organisms. Its atomic number is 6 and atomic weight is 12.
Carbon is found in abundance in living things and materials that are
derived from living things. Due to the existence of diverse allotropes of
carbon, from renowned allotropic phases such as amorphous carbon,
graphite and diamonds to newly discovered auspicious carbon nanotubes
(CNTs), graphene oxide (GO), graphene quantum dots (GQDs) and
fullerene, carbon-based materials have recently become prized.
177
OBJECTIVES

➢ Understand the structure of Buckminsterfullerene.
➢ Distinguish Types Carbon nanotubes.
➢ Explain basic characteristics of CNTs
14.1 BUCKMINSTERFULLERENE
The 1996 Nobel Prize in Chemistry was awarded to Richard Smalley,

Robert Curl, and Harold Kroto for their discovery of a new allotrope of
carbon, C60 called buckminsterfullerene.
Buckminsterfullerene (C60) is a spherical carbon allotrope where 60 atoms
are assembled in pentagons and hexagons, in a geometry similar to
a soccer ball. All the carbon atoms are connected by single and double
bonds, these are often called BuckyBalls. Their cage structure and poly
aromaticity cause the formation of a displaced electron cloud that allows
these molecules to act as charge-transfer complexes.
Structure of Buckminsterfullerene
The fullerene, C60, consists of fused five and six-membered carbon rings.
Each six membered rings is surrounded, alternately, by hexagons and
pentagons of carbons; each pentagon is fused to five hexagons. The
consequence of this structural motif is that each hexagon is like the base
of a bowl; the three pentagons fused to this ring, linked by hexagons, force
the structure to curve resulting in a dome-like structure that eventually
curves around itself to give a structure resembling a sphere. The shape
of fullerene,C60 resembles a soccer ball. All the 60 carbon atoms are
equivalent and give rise to a single 13C NMR resonance.
Fig. 14.1 Structure of buckminsterfullerene
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Preparations of Buckminsterfullerene
When an electric spark is struck between graphite electrodes, soot is
produced. This soot is mainly carbon black but contains a significant
amount of C60 carbon cluster compound, in this process smaller amounts
of other fullerenes C32, C50, C70, C76 and C84 may also be produced.
The following are easily extracted from the soot by dissolving them in
benzene or hydrocarbon solvents, giving a red solution and finally
mustard colour crystals. The different compounds are separated by
chromatographically.
Physical Properties of Buckminsterfullerene

Buckminsterfullerene is stable at high temperatures and high
pressures.
Fullerenes are covalent; hence they are soluble in organic
solvents but insoluble in water.
Solutions of pure C60 have a deep purple color which leaves a
brown residue on evaporation.
In solid state buckminsterfullerene C60 molecules adopt
the fcc arrangement.
Buckminsterfullerene(C60) is used as a superconductor below
18K, which means that it carries an electric current with zero
resistance.
crystallization of C60 in benzene solution yields triclinic crystals
with the formula C60·4C6H6.
Chemical Properties of Buckminsterfullerene

❖ Buckminsterfullerene can easily be reduced electrochemically to
form fulleride ion, It reacts with group-1 metals forming solid K3C60,
which acts as a superconductor below 18K.
❖ Hydrogenation: C60 addition with hydrogen to give
polyhydrofullerenes. Buckminsterfullerene exhibits a small
degree of aromatic character so it also undergoes Birch
reduction.
❖ Halogenation: Halogens undergo addition reaction with
C60 produces the following compounds such as C60Br8 and
C60Br24.
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❖ Addition of oxygen: Ozonation of C60 in 1,2-xylene at 257K gives
an intermediate ozonide C60O3, which can be decomposed to form
epoxide C60O.
❖ Formation of metal complexes: Fullerenes act as ligands in
transition metal complexes due to the immense π system.
Osmium tetroxide, a powerful oxidizing agent. When OsO4 is
reacted with C60 and 4-tert-butylpyridine, it produceing
C60(OsO4)(4-t-butylpyridine)2.
❖ Compounds containing encapsulated metals. These may
contain one, two, or three metals inside the fullerene sphere.
Examples: UC60.
Application of Buckminsterfullerene
➢ Fullerene in its pure state acts as insulators but can be converted
to semiconductors and superconductors under suitable conditions.
➢ Buckminsterfullerene’s ability to trap different atoms or molecules
makes them useful in the medical field. For example, radioactive
C60O can be used in cancer as well as AIDS therapy.
➢ Fullerenes help in improving antiwear and anti-friction properties
of lubricating oils.
➢ It can catalyse photochemical refining in industry.
➢ It has a high electron affinity; hence it is used as common electron
acceptor in donor/acceptor based solar cells.
➢ Buckminsterfullerene may be used to store hydrogen, possibly as
a fuel tank for fuel cell powered cars.
14.2 CARBON NANOTUBE (CNT)
A carbon nanotube is a carbon allotrope that resembles a tube of carbon

atoms. Carbon nanotubes are extremely robust and difficult to break, but
they are still light. Because of their exceptional mechanical, electrical, and
thermal properties, carbon nanotubes are one of the most investigated
nanomaterials. Multiwall carbon nanotubes feature several concentric
cylindrical lattices of carbon atoms, whereas single wall carbon nanotubes
have only one cylinder of carbon atoms. Buckytube is another name for
carbon nanotubes. Two-dimensional graphite is folded or rolled into a
cylindrical shape structure to create nanotubes. Inside, nanotubes are
hollow. The nanotube has a diameter of 1-3 nanometers.
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Properties of CNTs
❖ Light weight
❖ High aspect ratio
❖ Remarkably high mechanical strength and the Young’s modulus
ranges from 270-950 GP.
❖ Tensile strength of CNTs is 11-63 GP which is 100 times greater
than that of steel,
❖ The excellent thermal properties (low temperature specific heat
and high thermal conductivity) Electrical conductivity approaches
to that of copper
Types of CNTs
CNTs can be divided into two categories on the basis of the number
of tubes present in the CNTs. They are a) Single-walled CNTs b) Multi-
walled CNTs
a) Single-walled CNTs (SWCNTs):- SWCNTs are made up of a single

graphene sheet rolled upon itself with a diameter of 1–2 nm (Fig. 1.2 c).
The length of the tube can vary million times depending on the preparation
methods. They can be formed in three different forms fig. 1.2 b on the
basis of rolling of grapheme sheet in to a seamless cylinder viz,. –
Armchair, Zigzag, Chiral forms
Fig. 14.2 Geometry of CNTs

b) Multi-walled CNTs:- MWNTs consist of multiple layers of graphene
rolled upon itself with diameters ranging from 2 to 50 nm depending
181
on the number of graphene tubes Fig 1.2 c). These tubes have an
approximate inter-layer distance of 0.34 nm.
Fig. 3 a) SWCNT b) MWCNT
Synthesis of CNTs
CNTs can be prepared by various methods, such as the
➢ Arcdischarge
➢ Chemical vapor deposition (CVD)
➢ Laser ablation
➢ Sol-gel
Carbon Nanotubes Uses & Applications

❖ Carbon nanotubes are utilized in energy storage, device
modelling, automotive parts, boat hulls, sporting goods, water
filters, thin-film electronics, coatings, actuators, and
electromagnetic shields.
❖ Because of their large surface area, CNTs have been successfully
used in pharmacy and medicine to adsorb or conjugate a wide
range of medicinal and diagnostic substances.
182
❖ CNTs have a number of unique chemical, size, optical, electrical,
and structural properties that make them appealing as drug
delivery and biosensing platforms for the treatment of a variety of
diseases and noninvasive monitoring of blood levels and other
chemical properties of the human body, respectively.
❖ Carbon nanotubes (CNTs) have unique qualities, such as high
surface-to-volume ratios, increased conductivity and strength,
biocompatibility, ease of functionalization, optical properties, and
so on.
14.3 NANO DIAMOND
Nanodiamond is the term used to describe diamond particles so small that

they are measured in nanometers, or billionths of a meter. Nanodiamonds
are very, very small and diamond is pure carbon in its hardest state.
Nanodiamonds were discovered over the course of 19 years, with initial
research taking place between 1963 – 1982. Scientists noticed the
presence of nanodiamonds where explosives with carbon-based triggers
were used in nuclear explosions. Since then, nanodiamonds have gained
worldwide interest.
These tiny diamonds can be created through several methods including

the explosive detonation of a carbon producing explosive. Their size
typically ranges from 3-5 nm to 100 nm. Explosive nanodiamond
synthesis is achieved in one of two ways. One method involves adding
graphite to an explosives system and subjecting the graphite (carbon) to
the shock wave of an explosive detonation. The other method is to
detonate a carbon producing explosive inside of a thick pipe. In both
cases, a portion of the carbon is converted into diamond and some
remains as graphite, which can be burned off with strong acids. Diamond
material created from the detonation of an explosive is referred to as
“detonation nanodiamond”.
Applications
Nanodiamonds have unique structures with unique physicochemical
properties that confer advantages over other commonly used materials.
They are very sensitive to environmental chemical changes, have poor
water solubility, low fluorescence, and useful thermal and chemical
consistency.
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Nanodiamonds are used as antimicrobial agents and delivery vehicles for
vaccines and drugs because they are biocompatible and small in size and
shape, enabling them to penetrate cells without causing damage.
Nanodiamonds also possess many desirable mechanical properties.
Compared to other nanomaterials, their properties include superior
hardness, better chemical stability, and thermal conductivity.
Nanodiamonds can also resist harsh environments and have a lower
friction coefficient. Such characteristics facilitate nanodiamond use in
batteries, metal plating, chromatography, proteomics, magnetic
resonance imaging, mass spectroscopy, capacitors, surgical implants,
lubricants, nanocomposites, nanocoatings, and nanosensors.
14.4 BN NANOTUBES
Boron nitride nanotube (BNNT) has similar tubular nanostructure as

carbon nanotube (CNT) in which boron and nitrogen atoms arranged in a
hexagonal network. Owing to the unique atomic structure, BNNT has
numerous excellent intrinsic properties such as superior mechanical
strength, high thermal conductivity, electrically insulating behavior,
piezoelectric property, neutron shielding capability, and oxidation
resistance. Since BNNT was first synthesized in 1995, developing efficient
BNNT production route has been a significant issue due to low yield and
poor quality in comparison with CNT, thus limiting its practical uses.
Fig. 4 Structural model of (a) CNT and (b) BNNT. The alternating B
and N atoms are shown in blue and red, respectively, on the BNNT
model
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BNNT synthesis methods
BNNT has been synthesized mainly by methods that have been well
documented earlier for CNT fabrication including arc discharge, chemical
vapor deposition (CVD) laser ablation etc.
LET US SUM UP
❖ Buckminsterfullerene (C60) is a spherical carbon allotrope where

60 atoms are assembled in pentagons and hexagons, in a
geometry similar to a soccer ball. All the carbon atoms are
connected by single and double bonds, these are often
called BuckyBalls.
❖ Carbon nanotubes are extremely robust and difficult to break, but
they are still light. Because of their exceptional mechanical,
electrical, and thermal properties, carbon nanotubes are one of the
most investigated nanomaterials.
❖ Nanodiamonds are very, very small and diamond is pure carbon
in its hardest state. Their size typically ranges from 3-5 nm to 100
nm.
❖ Boron nitride nanotube (BNNT) has similar tubular nanostructure
as carbon nanotube (CNT) in which boron and nitrogen atoms
arranged in a hexagonal network. Owing to the unique atomic
structure, BNNT has numerous excellent intrinsic properties such
as superior mechanical strength, high thermal conductivity,
electrically insulating behavior, piezoelectric property, neutron
shielding capability, and oxidation resistance
1. What is Buckminsterfullerene?
2. What are the types of CNTs?
3. Define BN nanotube.
1. Buckminsterfullerene (C60) is a spherical carbon allotrope where

60 atoms are assembled in pentagons and hexagons, in a
geometry similar to a soccer ball.
2. CNTs can be divided into two categories on the basis of the
number of tubes present in the CNTs. They are a) Single-
walled CNTs b) Multi-walled CNTs
185
3. Boron nitride nanotube (BNNT) has similar tubular nanostructure
as carbon nanotube (CNT) in which boron and nitrogen atoms
arranged in a hexagonal network.
UNIT END EXERCISES
1. Discuss in detail about Buckminsterfullerene.

2. What are carbon nanotubes? With neat diagram discuss the types,
properties and applications of CNTs
3. Explain in detail about BN nanotubes.
SUGGESTED READINGS

Education, 2009
Web Resources
3. https://www.youtube.com/watch?v=nYZyQ7etgc8
4. https://www.youtube.com/watch?v=c6WGu3xVzpc
5. https://www.youtube.com/watch?v=9EKqNBvz4cA
6. https://www.youtube.com/watch?v=J-uaI0EHz7U
7. https://www.youtube.com/watch?v=U1QDH_8_hu0
8. http://www.digimat.in/nptel/courses/video/113102080/L30.html
9. https://www.youtube.com/watch?v=ZaeK0k9fsuc
186
UNIT 15
NANOELECTRONICS
Structure
Overview
Objectives
15.1 Nanoelectronics
15.2 Single electron transistor
15.3 Molecular machine

15.4 Nano biometrics
Let Us Sum Up
Check Your Progress
Unit End Exercises
Suggested readings
OVERVIEW
Nanoelectronics refer to the use of nanotechnology on electronic

components, especially transistors. Although the term nanotechnology is
generally defined as utilizing technology less than 100nm in size,
nanoelectronics often refer to transistor devices that are so small that
inter-atomic interactions and quantum mechanical properties need to be
studied extensively. As a result, present transistors (such as CMOS90
from TSMC or Pentium 4 Processors from Intel) do not fall under this
category, even though these devices are manufactured under 90 nm or
65 nm technology.
187
OBJECTIVES

❖ Understand the concepts of Nanoelectronics.
❖ Distinguish Single electron transistor Molecular machine
❖ Explain basics of Nano biometrics
15.1 NANOELECTRONICS
Nanoelectronics are sometimes considered as disruptive technology

because present candidates are significantly different from traditional
transistors. Some of these candidates include: hybrid
molecular/semiconductor electronics, one dimensional
nanotubes/nanowires, or advanced molecular electronics. The sub-
voltage and deep-sub-voltage nanoelectronics are specific and important
fields of R&D, and the appearance of new ICs operating near theoretical
limit (fundamental, technological, design methodological, architectural,
algorithmic) on energy consumption per 1 bit processing is inevitably.
Nanofabrication
For example, single electron transistors, which involve transistor
operation based on a single electron. Nanoelectromechanical systems
also falls under this category.
Nanofabrication can be used to construct ultra-dense parallel arrays of
nanowires, as an alternative to synthesizing nanowires individually.
Nanomaterials electronics
Besides being small and allowing more transistors to be packed into a
single chip, the uniform and symmetrical structure of nanotubes allows a
higher electron mobility (faster electron movement in the material), a
higher dielectric constant (faster frequency), and a symmetrical
electron/hole characteristic. Also, nanoparticles can be used as quantum
dots.
Molecular electronics
Single molecule devices are another possibility. These schemes would

make heavy use of molecular self-assembly, designing the device
components to construct a larger structure or even a complete system on
their own. This can be very useful for reconfigurable computing, and may
even completely replace present FPGA technology.
188
Molecular electronics is a new technology which is still in its infancy, but
also brings hope for truly atomic scale electronic systems in the future.
One of the more promising applications of molecular electronics was
proposed by the IBM researcher Ari Aviram and the theoretical chemist
Mark Ratner in their 1974 and 1988 papers Molecules for Memory, Logic
and Amplification, (see Unimolecular rectifier). This is one of many
possible ways in which a molecular level diode / transistor might be
synthesized by organic chemistry. A model system was proposed with a
spiro carbon structure giving a molecular diode about half a nanometre
across which could be connected by polythiophene molecular wires.
Theoretical calculations showed the design to be sound in principle and
there is still hope that such a system can be made to work.
Nanoelectronic devices
Computers
Nanoelectronics holds the promise of making computer processors more
powerful than are possible with conventional semiconductor fabrication
techniques. A number of approaches are currently being researched,
including new forms of nanolithography, as well as the use of
nanomaterials such as nanowires or small molecules in place of traditional
CMOS components. Field effect transistors have been made using both
semiconducting carbon nanotubes and with heterostructured
semiconductor nanowires.
Energy production
Research is ongoing to use nanowires and other nanostructured materials
with the hope of to create cheaper and more efficient solar cells than are
possible with conventional planar silicon solar cells. It is believed that the
invention of more efficient solar energy would have a great effect on
satisfying global energy needs. There is also research into energy
production for devices that would operate in vivo, called bio-nano
generators.
Medical diagnostics
There is great interest in constructing nanoelectronic devices that could
detect the concentrations of biomolecules in real time for use as medical
diagnostics, thus falling into the category of nanomedicine. A parallel line
of research seeks to create nanoelectronic devices which could interact
with single cells for use in basic biological research. These devices are
called nanosensors.
189
15.2 SINGLE ELECTRON TRANSISTOR
Definition:
SET is three-dimensional switching devices which can transfer electrons
from source to drain one by one. That is the purpose of the SET is to
individually control the tunnelling of electrons into and out of the quantum
dot.
Construction & Working:

The structure of SET is shown in the below figure. It has the similar
structure of a conventional Field Effect Transistor (FET). It has tunnelling
junctions in place of the channel region of the FET.
Fig. 15.1 A single-electron transistor (SET) (a) SET in “OFF” mode.

(b) SET in “ON” mode.
To control tunneling, a voltage bias to the gate electrode is applied. A
separate voltage bias is applied between source and drain electrodes for
the current direction. For current to flow, gate bias voltage must be large
enough to overcome the coulomb blockade energy.
The energy E needed to move a charge Q, across a potential difference
V is given by
190
E = VQ.
Presently, the charge of an electron (Q=e). So, the voltage that will move
an electron onto or off the quantum dot is given by,
𝐸 𝑊𝑐
𝑉= =
𝑒 𝑒
Since E = Wc,
Where Wc – Charging Energy
𝑒2
𝑒 𝑒2
𝑉= 2𝐶
= ……… (1) [ Wc = ]
𝑒 2𝐶 2𝐶
With this voltage applied to the quantum dot, an electron can tunnel
through Coulomb blockade of the quantum dot. The gate voltage as given
in eqn. (1) can be used to tune the number of electrons on the dot at a
time. At the lowest setting, electrons tunnel one at a time, from source to
𝑒2
drain through the dot. At the proper gate voltage, V = 2𝐶
the potential
energy of the dot is low enough to allow an electron to tunnel through
Coulomb blockade energy barrier to the quantum dot.
Once the quantum dot gets an electron, its potential energy rises. Then
the electron tunnels through the Coulomb blockade on the other side to
reach the lower potential energy at the drain. Since, the dot is empty and
potential lower again, the process repeats. Thus, when the gate voltage
Vg is zero, no current flows. The first gate voltage large enough to move
an electron through the Coulomb blockade is called VCoulomb.
For single-electron tunneling, Vg = VCoulomb.

𝑒
If the gate voltage equals Vcoulomb + 2𝐶
, then two electrons can be moved
on the quantum dot at a time. If the gate voltage equals
𝑒 𝑒 𝑒
Vcoulomb + 2𝐶 + = Vcoulomb + 2𝐶 ,
2𝐶
Then three electrons can be moved on the quantum dot at a time and so
on. Thus, number of electrons in the quantum dot is controlled using the
gate voltage.
The ON and OFF states can be utilized to make an effective switch out of
a SET. The gate voltages for a SET are a few millivolts and source-to-
drain currents are in the Pico ampere range.
191
Advantages:
The fast information transfer velocity between cells (almost near
optical optic velocity) is carried out via electrostatic interactions
only.
No wire is needed between arrays. The size of each cell can be as
small as 2.5nm. This made them very suitable for high density
memory.
This can be used for next generation quantum computer.
Limitations:
In order to operate SET circuit at room temperature, the size of the

quantum dot should be smaller than 10nm.
It is very hard to fabricate by traditional optical lithography and
semiconductor process.
The methods must be developed for connecting the individual
structures into logic circuits and these circuits must be arranged
into larger 2D patterns.
Applications:
Sensor technology and Digital electronic circuits.
It is used for mass data storage.
It is used in highly sensitive electrometer.
SET can be used as a temperature probe, particularly in very low
temperature.
15.3 MOLECULAR MACHINE
A molecular machine, nanite, or nanomachine is a molecular component

that produces quasi-mechanical movements (output) in response to
specific stimuli (input). In cellular biology, macromolecular
machines frequently perform tasks essential for life, such as DNA
replication and ATP synthesis. The expression is often more generally
applied to molecules that simply mimic functions that occur at the
macroscopic level. The term is also common in nanotechnology where a
number of highly complex molecular machines have been proposed that
are aimed at the goal of constructing a molecular assembler.
Types
Molecular machines can be divided into two broad categories; 1. artificial
and 2. biological. In general, artificial molecular machines (AMMs) refer to
molecules that are artificially designed and synthesized whereas
192
biological molecular machines can commonly be found in nature and have
evolved into their forms after abiogenesis on Earth.
1. Artificial
A wide variety of artificial molecular machines (AMMs) have been
synthesized by chemists which are rather simple and small compared to
biological molecular machines. The first AMM, a molecular shuttle, was
synthesized by Sir J. Fraser Stoddart. A molecular shuttle is
a rotaxane molecule where a ring is mechanically interlocked onto an axle
with two bulky stoppers. The ring can move between two binding sites
with various stimuli such as light, pH, solvents, and ions. As the authors
of this 1991 JACS paper noted: "Insofar as it becomes possible to control
the movement of one molecular component with respect to the other in a
rotaxane, the technology for building molecular machines will
emerge", mechanically interlocked molecular architectures spearheaded
AMM design and synthesis as they provide directed molecular
motion. Today a wide variety of AMMs exists as listed below.
Molecular motors
Molecular motors are molecules that are capable of directional rotary
motion around a single or double bond. Single bond rotary motors are
generally activated by chemical reactions whereas double bond rotary
motors are generally fueled by light. The rotation speed of the motor can
also be tuned by careful molecular design. Carbon nanotube
nanomotors have also been produced.
Molecular propeller
A molecular propeller is a molecule that can propel fluids when rotated,
due to its special shape that is designed in analogy to macroscopic
propellers. It has several molecular-scale blades attached at a certain
pitch angle around the circumference of a nanoscale shaft. Also
see molecular gyroscope.
Molecular switch
A molecular switch is a molecule that can be reversibly shifted between
two or more stable states. The molecules may be shifted between the
states in response to changes in pH, light (photoswitch), temperature, an
electric current, microenvironment, or the presence of a ligand.
193
Molecular shuttle
A molecular shuttle is a molecule capable of shuttling molecules or ions
from one location to another. A common molecular shuttle consists of a
rotaxane where the macrocycle can move between two sites or stations
along the dumbbell backbone
Nanocar
Nanocars are single molecule vehicles that resemble macroscopic

automobiles and are important for understanding how to control molecular
diffusion on surfaces. The first nanocars were synthesized by James M.
Tour in 2005. They had an H shaped chassis and 4 molecular wheels
(fullerenes) attached to the four corners. In 2011, Ben Feringa and co-
workers synthesized the first motorized nanocar which had molecular
motors attached to the chassis as rotating wheels. The authors were able
to demonstrate directional motion of the nanocar on a copper surface by
providing energy from a scanning tunneling microscope tip. Later, in 2017,
the world's first ever Nanocar Race took place in Toulouse.
Molecular balance
A molecular balance is a molecule that can interconvert between two and
more conformational or configurational states in response to the dynamic
of multiple intra- and intermolecular driving forces, such as hydrogen
bonding, solvophobic/hydrophobic effects, π interactions, and steric and
dispersion interactions. Molecular balances can be small molecules or
macromolecules such as proteins. Cooperatively folded proteins, for
example, have been used as molecular balances to measure interaction
energies and conformational propensities.
Molecular tweezers
Molecular tweezers are host molecules capable of holding items between
their two arms. The open cavity of the molecular tweezers binds items
using non-covalent bonding including hydrogen bonding, metal
coordination, hydrophobic forces, van der Waals forces, π interactions, or
electrostatic effects. Examples of molecular tweezers have been reported
that are constructed from DNA and are considered DNA machines.
Molecular sensor
A molecular sensor is a molecule that interacts with an analyte to produce
a detectable change. Molecular sensors combine molecular recognition
with some form of reporter, so the presence of the item can be observed.
Molecular logic gate
194
A molecular logic gate is a molecule that performs a logical operation on
one or more logic inputs and produces a single logic output. Unlike a
molecular sensor, the molecular logic gate will only output when a
particular combination of inputs are present.
Molecular assembler
A molecular assembler is a molecular machine able to guide chemical
reactions by positioning reactive molecules with precision.
Molecular hinge
A molecular hinge is a molecule that can be selectively switched from one
configuration to another in a reversible fashion. Such configurations must
have distinguishable geometries; for instance, azobenzene groups in a
linear molecule may undergo cis-trans isomerizations when irradiated
with ultraviolet light, triggering a reversible transition to a bent or V-shaped
conformation. Molecular hinges typically rotate in a crank-like motion
around a rigid axis, such as a double bond or aromatic
ring. However, macrocyclic molecular hinges with more clamp-like
mechanisms have also been synthesized.
2. Biological
The most complex macromolecular machines are found within cells, often
in the form of multi-protein complexes. Important examples of biological
machines include motor proteins such as myosin, which is responsible
for muscle contraction, kinesin, which moves cargo inside cells away from
the nucleus along microtubules, and dynein, which moves cargo inside
cells towards the nucleus and produces the axonemal beating of motile
cilia and flagella. "In effect, the [motile cilium] is a nanomachine
composed of perhaps over 600 proteins in molecular complexes, many of
which also function independently as nanomachines. Flexible
linkers allow the mobile protein domains connected by them to recruit
their binding partners and induce long-range allostery via protein domain
dynamics. Other biological machines are responsible for energy
production, for example ATP synthase which harnesses energy
from proton gradients across membranes to drive a turbine-like motion
used to synthesise ATP, the energy currency of a cell. Still other
machines are responsible for gene expression, including DNA
polymerases for replicating DNA, RNA polymerases for
producing mRNA, the spliceosome for removing introns, and
the ribosome for synthesising proteins. These machines and
195
their nanoscale dynamics are far more complex than any molecular
machines that have yet been artificially constructed.
These biological machines might have applications in nanomedicine. For

example, they could be used to identify and destroy cancer
cells. Molecular nanotechnology is a speculative subfield of
nanotechnology regarding the possibility of engineering molecular
assemblers, biological machines which could re-order matter at a
molecular or atomic scale. Nanomedicine would make use of
these nanorobots, introduced into the body, to repair or detect damages
and infections. Molecular nanotechnology is highly theoretical, seeking to
anticipate what inventions nanotechnology might yield and to propose an
agenda for future inquiry. The proposed elements of molecular
nanotechnology, such as molecular assemblers and nanorobots are far
beyond current capabilities.
15.4 NANO BIOMETRICS
Nano biometrics is a Part of Nano biomechanics which will be useful for

the estimation of the small strengths that follow up on the cells and might
be identified with illnesses and their cure.
It Utilizes biological mechanisms to create materials
➢ Mimicking biological self-assembly processes
➢ Using single biological units as a building block along with
inorganic materials
It Mimics biology at the molecular level
➢ Synthesizing structures that mimic biological structures
Utilizing biological mechanisms
❖ Atom-precise manipulation yields composite materials and nano-
scale structures with desirable properties
❖ Parallel self-assembly processes achieve precision with high
speed and reproducibility
Biological self-assembly
Bottom-up fabrication process
Continuing miniaturization of devices in nanotechnology
196
Nature already assembles its smallest components into ordered
structures.
LET US SUM UP
❖ Nanoelectronics refer to the use of nanotechnology on electronic

components, especially transistors.
❖ SET is three-dimensional switching devices which can transfer
electrons from source to drain one by one. That is the purpose of
the SET is to individually control the tunnelling of electrons into
and out of the quantum dot.
❖ A molecular machine, nanite, or nanomachine is a molecular
component that produces quasi-mechanical movements (output)
in response to specific stimuli (input). In cellular
biology, macromolecular machines frequently perform tasks
essential for life, such as DNA replication and ATP synthesis.
❖ Nano biometrics is a Part of Nano biomechanics which will be
useful for the estimation of the small strengths that follow up on
the cells and might be identified with illnesses and their cure.
1. Define nanoelectronics?
2. What is single electron transistor?
3. Define nanobiometrics.
1. Nanoelectronics refer to the use of nanotechnology on electronic

2. SET is three-dimensional switching devices which can transfer
electrons from source to drain one by one
3. Nano biometrics is a Part of Nano biomechanics which will be
197
1. Nanoelectronics refer to the use of nanotechnology on electronic

2. SET is three-dimensional switching devices which can transfer
electrons from source to drain one by one
3. Nano biometrics is a Part of Nano biomechanics which will be
UNIT END EXERCISES
1. Give an account of nanoelectronics devices

2. Explain the construction and working of SET
3. Discuss in detail about artificial molecular machine
4. Write a short note on nanobiometrics.
SUGGESTED READINGS

Education, 2009
Web Resources
2. http://www.digimat.in/nptel/courses/video/117108047/L35.html
courses/electronics/NanoelectronicsDevicesMaterials-IIT-
Bangalore/lecture-09.html
198
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1 BLOCK I THEORY OF DIELECTRICS
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MASTER OF SCIENCE IN PHYSICS

CONDENSED MATTER PHYSICS – II

Course Coordinator & Content Editor

Total No of Pages: 210

March 2023 ( First Edition)

ISBN No: 978-93-5706-518-4

©Tamil Nadu Open University

COURSE TITLE : CONDENSED MATTER PHYSICS – II

COURSE CODE : MPHS 43

CO 1: Learn the basics of theories of dielectrics

BLOCK I: THEORY OF DIELECTRICS

BLOCK II: THEORY OF FERROELECTRICS AND PIEZO ELECTRICS

BLOCK III: MAGNETIC PROPERTIES OF MATERIALS

BLOCK IV: SUPERCONDUCTIVITY

BLOCK V: PHYSICS OF NANOSOLIDS

COURSE LEARNING OUTCOMES

1.1 Unit 1: Polarization 2

1.2 Unit 2: Types of Polarization 16

1.3 Unit 3: Dielectric Relaxation 28

2.2 Unit 5: Phase Transitions 56

2.3 Unit 6: Antiferroelectricity and Piezoelectricity 67

3 BLOCK III: MAGNETIC PROPERTIES 80

3.1 Unit 7: Classification of Magnetic Materials 81

3.2 Unit 8: Diamagnetism and Para magnetism 91

Unit 9: Ferromagnetism, Anti-ferromagnetism and Ferrimagnetism 102

4.1 Unit 10: Introduction to Superconductivity 119

4.2 Unit 11: BCS Theory 132

4.3 Unit 12: Applications of Superconductivity 143

5 BLOCK V: PHYSICS OF NANOSOLIDS 157

5.1 Unit 13: Physics of Nanosolids 158

5.2 Unit 14: Carbon Nanotechnology 177

5.3 Unit 15: Nanoelectronics 187

Appendix – Plagiarism Certificate 199

Unit 2: Types of Polarization

Unit 3: Dielectric Relaxation

The term dielectric is used in broad sense, as relating to various electrical

Dielectric materials include some solids such as glass, porcelain, etc.,

After learning this unit, learners will be able to

1.1 DIPOLE MOMENT

If we have two equal and opposite charges, +q and -q as shown in

Where rn is the position vector of the charge qn.

When a dielectric is placed in an external electric field, it becomes

The mechanism of polarization differs for non-polar and polar dielectric

If we choose the coordinates such that polarization vector P lies at the

Fig 1.2 Electric field of a dipole

To simplify this, let us make the following substitution

𝑦 = 𝑟 sin 𝜃 and 𝑧 = 𝑟 cos 𝜃

The radius vector r lying in the yz plane can be written as

= 𝑗̂𝑟 sin 𝜃 + 𝑘̂𝑟 cos 𝜃

1.4 LOCAL ELECTRIC FIELD AT AN ATOM

When a dielectric material is placed in an external electrical field, it

Lorentz method to find internal field (Derivation)

Macroscopically, we can take E = E0 + E1, i.e., the electrical field externally

If we consider a dielectric that is highly symmetric, the electrical field due

Now, the equation is rewritten as

𝑑𝐴 = 2𝜋𝑟 sin 𝜃 𝑟𝑑𝜃 = 2𝜋𝑟 2 sin 𝜃 𝑑𝜃

The force acting in the direction of the applied electric field,

From eq. 9 we have,

The Lorentz force Fx can be determined by integrating eq. 10 over the