COURSEWARE

COURSEWARE
FOR EEE307
PREPARED BY:
Dr. FARSEEM MANNAN

MOHAMMEDY
DEPT OF EEE, BUET
1st Edition: February 2014; 2nd Edition: June 2015

Dedicated to
Prof Ali Asgar

who taught me Drude Model
Prof M Rezwan Khan

who taught me about 3/2kT
Prof David Thompson

who taught me all about semiconductors and their practicalities
Prof M Jamal Deen

who taught me about top-notch research
4/12/2015
Properties of Materials
Instructor:
Farseem M. Mohammedy PhD
Associate Professor, ECE 424,
Dept of EEE, B.U.E.T., Dhaka-1000.
https://www.facebook.com/farseem
The instructor, 2013.
Course book
• A course-ware is under preparation, will be
handed out in steps
• Recommended text
– Priciples of Electronic Materials and
Devics by Safa O. Kasap, Professor of
Electrical Engineering, University of
Saskatchewan, Canada.
• My personal favorite
– Lectures on Electrical Properties
of Materials by Solymar and Walsh,
8th ed
• Reference
– Electronic Properties of Materials,
by Rolf Hummel. 4th edition
Dr. Farseem Mohammedy 2
1
4/12/2015
Solid state series in Bengali
কাশক -- র
Internet sources
• Wikipedia in general
2
4/12/2015
Course outline
Weeks Sections Topics
1 1.8 General introduction, Crystal structure
2,3 Ch. 2 Theory of Conduction
4-7 Parts of Ch. 3, Quantum Mechanics: wave equation,

tunneling, band theory of solids, Kronig-
parts from Beiser Penney model, effective mass, density of
states, carrier stat
8-11 Ch.7 Dielectrics
12-13 Ch. 8 Magnetics
14 Ch. 15 of Solymar Metamaterials and other advanced topics

and Walsh
Course evaluation
• Class tests/assignments – 30%

– Class Tests 2 nos. (15%)
– Project Presentation (15%)
• Final exam – 70% (210)
3
It
Handout#0
Solymar and Walsh
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caronlyn er th e e\ isicnce of certain rclalionships trom the final oxlcome. Will
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ls no eas,v $aI to qua.tun nechinics: no short.uts and no bro{d highltals.
wc jnsi hevc Lo slruggle th xgh 1 belicve il \'ill bc $'ofih the effoft. It \il1
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and pnlilege ofihc physicis$:r I do not thmk so lfyou \vani lo inlent nc\
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approach thc su|ject in caretully planned slels |i*1, \\'e shall rlr' to ded'rce
as much infommtion is tossible on thc basis ofthc classical !ictuc Then.$e
shalltalk abont anumbcrolphenorncDa thal are clcarlv inconlmsttiLh classicaL
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superconductors. and a nnmbcr of rclaled solid
s;remcDt $ill be purely qualitrlive but in most cases ne sha11 nf to give the
cssential quanrihtive relationships
Thcse lectures will l1ot tnake you atr e)ipeft iD qruntun mechanics nor will
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vou no more than a general idea
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this counel I hope th. answer to this question ls ler. I believe ilrat once voLr 1-1 lnl'od.
have bcen exposed (ho\{ever supeficiall, to qxantum nechanical reasontug,
it will lcave pcmanenr marks o you lt $ ill infixence voul ideas on the nlture
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Fig. : -l *to
6/22/2015
Crystals
Sections:
Kasap 1.8
1
6/22/2015
“The chocolate microstructure” contains “six

types of cocoa butter crystal structure, each with
a different melting temperature, create very
different textures in the chocolate. At this scale
too are the crystals of sugar and the grains of
cocoa solids containing the flavour molecules of
chocolate. Controlling this microstructure
controls the taste and texture of chocolate, and
this is a large part of the craft of the chocolatier”.
Dr. Farseem Mohammedy – Mark Miodownik 3
Forms of Carbon
2
6/22/2015
Crystalline solids
• A Crystalline Solid is a solid object in which atoms bond with

each other in a regular pattern to form a periodic collection, or
array, of atoms.
• Most important property of a crystal is periodicity, leading to

long-range order (location of each atom is well-known by virtue
of periodicity)
• Examples of periodic array/crystalline solids: nearly all metals,

many ceramics, semiconductors, various polymers.
Crystalline solids
• All Crystals  a lattice + a basis
• Lattice  an infinite periodic array of geometric
points in space (without atoms)
• Basis  an identical group of atoms
• By putting the basis at each lattice point, we
obtain the actual crystal.
• Thus the crystal becomes essentially a periodic
repeatation of a small volume, called the unit cell.
• The length of the cubic unit cell is called lattice
constant.
• The repeatation of the unit cell in 3D will generate
the whole crystal.
3
6/22/2015
Packing of solids
• Crystals can be
– Face centered Cubic, FCC
– Body Centered cubic, BCC
– Hexagonal closed pack, HCP
FCC
• Each atom in the corner

• One atom in the center of each face
• One atom at the center
• In one FCC unit cell, there is one
atom in the center, 1/8th atom in 8
corners and ½ atom in each of 4-
planes
• Total of 4 atoms in FCC unit cell
• Cu is an example: a = 0.362 nm
• Closed packed structure with packing
density of 74%
4
6/22/2015
BCC
• Each atom in the corner

• One atom at the center
• In one BCC unit cell, there is one
atom in the center, 1/8th atom in 8
corners
• Total of 2 atoms in BCC unit cell
• Fe is an example
• Closed packed structure with packing
density of 68%
HCP
The Hexagonal Close Packed (HCP)

Crystal Structure.
(a) The Hexagonal Close Packed
(HCP) Structure. A collection of
many Zn atoms. Color difference
distinguishes layers (stacks).
(b) The stacking sequence of
closely packed layers is ABAB
(c) A unit cell with reduced spheres
(d) The smallest unit cell with
reduced spheres.
• See the book
5
6/22/2015
Covalently bonded cubic solids

• Covalently bonded solids have diamond structure due to the
directional nature of the covalent bonds.
• Example: Si and Ge
• Si-Si bonding dictates a rigid local geometry resulting in
tetrahedral configuration - diamond cubic crystal structure.
• Similar to FCC, the unit cell has a total of 8 atoms
– If we place 2 Si-atoms at each site appropriately, we can generate the
diamond cell
• In Zinc-Blende structure (e.g. ZnS, GaAs), since there are
binary compounds involved, now for each Ga-atom, there is
also As-atom.
• Thus it looks like a diamond cubic, but Ga and As-atoms
alternating positions.
• Also similar to FCC.
Diamond and Zinc-Blende
The diamond unit cell is cubic. The The Zinc blende (ZnS) cubic crystal
cell has eight atoms. Grey Sn (α-Sn) structure. Many important compound
and the Elemental semiconductors crystal
Ge and Si have this crystal Structures have the zinc blende
structure. structure. Examples: AlAs, GaAs, Gap,
GaSb, InAs, InP,
InSb, ZnS, ZnTe.
6
6/22/2015
Directions and planes

• Crystal properties – such as elastic modulus, electrical
resistivity, magnetic susceptibility – are different in different
directions and planes.
• In order to explain crystal properties, we need to specify a
direction in a crystal, or a particular plane of atoms.
• As a conventions, we represent the geometry of the unit cell as
a parallelopiped with sides a,b,c and angles , ,  – known as
crystal parameters.
• To apply 3D geoemtry, we insert an x-y-z coordinate; with the
origin at the left inner corner of the parallelopiped.
• Any point P within the crystal can be expressed through the
lattice parameters a, b,c.
• For example, P-vector can have components – 1/2a, b, 1/2c
7
6/22/2015

P  12 a, b, 12 c
P  12 , 1, 12
P  1, 2, 1

• Some directions are equivalent, since the setting of the
coordinate system x-y-z is arbitrary.
• Directions [100] and [010] are equivalent
• All equivalent directions are called a family of directions.
   
100  100, 010, 001, 1 00 , 0 1 0 , 00 1
8
6/22/2015
Miller indices
• Miller indices are the reciprocal of the [a,b,c] intercepts of the
plane
• Take any plane, note the x-y-z intercepts in terms of lattice
parameters a-b-c
• Invert the numbers – you get the Miller indices of the plane
• [hkl] = [a-1,b-1,c-1]
• A bar is used for a negative integer due to a negative intercept.
• planes can have the same [hkl] only if they are separated by a
multiple of lattice parameters.
• There also family of planes.
• Study Example 1.14
Think: why [010] is not equivalent to [020]?

9
2/23/2014
Electrical Conduction in Solids
Chapter 2
Kasap
Handout‐1
The Drude
The Drude Model (Kasap 2.1,P-114))
•
1
2/23/2014
The Drude
The Drude Model (continued)
•
1
v dx  [ v x 1  v x 2  v x 3      v xN ]
N
How to incorporate electric field in

the above equation ??
Dr. Farseem Mohammedy
….continued
….
• Under an electric field Ex , electrons accelerated in x-direction in

addition to its random motion.
• There can be collisions,
collisions but still on the avg
avg. , there is a drift velocity
along x-direction.
• Suppose its (i-th electron) last collision was at time ti ,therefore for
time (t-ti), it accelerated free of collisions.
2
2/23/2014
….continued
….
•
1
vdx  [v x1  v x 2  v x 3      v xN ]
N
qE x t  t i qE x
 ( )  m (t  ti )
me N e
….continued
….
• (t  ti )
 [ u xi averaged over N is
assumed to be zero]]
q q
Vd  E  E  
me me
3
2/23/2014
….continued
….
• Mobility is important because it is a widely used electronic parameter
in semiconductor device physics. The drift mobility measures how
fast electrons will drift under an applied electric field.
• scattered so  will be large.
A long  means electrons are not highly scattered, large
This means electrons will be highly mobile and responsive to the
applied field.
• A large  does not necessarily mean a high conductivity since 
depends also on concentration of the conduction electron.
• Self study:- Example 2.4(P-120) for an alternate explanation

- Ex: 2.2, 2.3(problem)
Temperature dependence of resistivity
• When conduction electrons are scattered predominantly [ by several
orders of magnitude ] by thermal vibrations of metal ions, the

resulting conductivity and resistivity is denoted by  T and T ,
T for thermal
‘T’ thermal.
Let’s study the temperature dependence of
 :
• An electron with an avg. velocity u can
be scattered by a scattering center
(having a cross-sectional area S)
• The scattering center can be a vibrating
atom, impurity, vacancy or any defect or
dislocation.
• If  is the mean free path betn two
successive collisions then   u 
4
2/23/2014
• If N s is the scattering center concentrations, then within the volume of S
there will be one scattering center : S (u ) N s  1
1
 
N s uSS
1
• If a is the amplitude of vibration of the metal atom, S  a 2 and  
i.e. if an electron’s path crosses a , it gets scattered.
2 a 2
• Also, a thermally vibrating atom can be thought of in ᵚ
terms of a simple harmonic motion of mass M having
an avg. KE of oscillation ,
1 1
K .E .  Ma 2 2  kT a2  T
4 2
1 1 C
Thus,   , These all leads to,  ‘C’ is a temperature
a 2
T T dependent const.
q qC
• Since,   , we have  
me m eT
1 1 m T
• And the resistivity T    2e
T qn  q nC
(A is temperature
 T  AT independent const.)
• So, resistivity of a pure metal is linearly dependent on

temperature The resistivity is only due to the scattering of
temperature.
conduction electrons by thermal vibrations of the atoms.
5
2/23/2014
Matthiessen’s Rule
• The chief mechanism for scattering in pure metals is assumed to be lattice
vibrations. For metallic alloys, the resistivities are weak function of
temperature. We should also consider the contribution to scattering from
impurity atoms.
• When
Wh an impurity
i it atom
t off a
different size than that of the host
atom is placed in the crystal
lattice, the impurity atom distorts
the region around it.
• The cross-section (S) that
scatters, is now the lattice region
that has been elastically distorted
by impurity atoms.
atoms
• Electrons in the distorted region
feels a force of,
d
F   ( Potential Energy )
dx
due to a change in P.E.
• The area due to this distortion is large, since the elastic deformation may
extend a number of atomic distances.
• Thus there are two types of mean free times:
= Scattering from thermal vibration only (  T )
= Scattering from impurity atoms (  I )
• Electrons can be scattered by both processes. So the effective  will be less
than individual  T or  I
Since 1  is the probability of scattering, then the net probability of
scattering for two independent events is :
1 1 1
 
 T I
q L  due to lattice scattering
Since,   ,
1

1

1
I  due to impurity scattering
me  L I
1
But since   , Hence ,   T  I Matthiessen’s
qn  Rule
6
2/23/2014
• So the effective resistivity is the sum of resistivities due to
lattice and impurity scattering - Matthiessen’s Rule
• There are various temperature dependencies of  :

1.   AT B (A,B are T-independent)
1   
2.   o[1o (T To )] ; o  (To  273k)
o T T To
n
T 
3
3.   o  
To 
All these formulas are based on semi-empirical analysis, and

does not have very much physical basis
• For Most of pure metals,

 varies linearly with T.
But metal alloys vary very
weakly
The resistivity of various metals as a function of temperature above 0 °C.
7
2/23/2014
• Copper metal has

subtleties that
complicate its
temperature
dependence.
Please study P.129-131
The resistivity of copper from lowest to highest temperatures (near melting temperature,
1358 K) on a log-log plot.
Nordheim coefficient
• Nordheim’s rule applies to metal alloys. The alloy components affect
the effective resistivity that results from impurity scattering:
( C is a const. )
 I  Cx(1  x)
( x is
i atomic
t i fraction
f ti off solute
l t atom)
t )
Summary:
* Matthiessen’s rule says that the total effective resistivity is a sum of
lattice vibrations and all other scattering phenomena, specially the
one originating from impurities   T  I
* Nordheims rule expresses the contribution of each component, in a
solid-solution that makes up a metal alloy towards the total
resistivity arising from impurity atoms  I  Cx(1  x)
8
2/23/2014
Resistivity of mixtures
• Nordheim’s rule applies only to single phase solid solutions. It is

valid for homogeneous mixtures, e.g. Cu-Ni alloy.
• For multiphase materials
eff       [   ,
are volume fractions of , 
phases]
resistivity mixture rule
• Similarly
Similarly, effff     for conductivity.
conductivity
• There are other complexities, and hence, empirical formulas for

effective resistivity. See pages 140-141, Kasap
Resistivity of mixtures
The effective resistivity of a material with a layered structure.

(a) Along a direction perpendicular to the layers.
(b) Along a direction parallel to the plane of the layers.
(c) Materials with a dispersed phase in a continuous matrix.
9
2/23/2014
Hall Effect
•
F  qv  B
F y   q  dx B z
Illustration of the Hall effect.

Hall Effect
•
q  dx B z  q
qE H (at, steady state)
 1 
E H    J x B z [ J x  qn  dx ]
 qn 
1 Ey
 is the Hall-coefficient ( R H ).
qn J xBz
This is a measureable quantity.
RH
1
because R H 
n
10
2/23/2014
Thermal Conduction
• Metals are good electrical and good

thermal conductors.
• The transport of heat is done by

conduction electrons in case of
metals.
• But it is done by lattice vibrations in

case of non-metals.
• Thermal conductivity measures the ease with which heat or

thermal energy is transported through the material.
Thermal Conduction
• The rate of heat flow

through a thin section  x
is proportional to the
T
temperature gradient  x
and area A.
T
 Q   A Fouriers Law : an empirical law
x
is thermal conductivity.
• The –ve sign shows that the heat flow is towards the decreasing
temperature.
• For metals, electrons participate in the process of charge and
heat transport, characterized by  and  respectively.
11
2/23/2014
Wiedemann--Franz
Wiedemann Franz--Lorenz Law
• The Wiedemann-Franz-Lorenz Law relates the two quantities:
  2k 2
 C WFL C WFL   2 . 44  10 8
WK 2
T 3q 2
(Lorenz no.)
• For a variety of metals &

alloys, this formula holds
true.
See fig. 2.21(P.150)
Heat Conduction in non‐‐metals
Heat Conduction in non
• Non-metals do not have “free conduction electron” to carry
thermal energy. Here it involves atomic vibrations of the crystal
(lattice vibrations).
• At the ‘hot’ end, there are large amplitude vibrations. The

springs couple the vibrations to neighbouring atoms. The
vibrations propagate as vibrational waves.
12
2/23/2014
Heat Conduction in non‐‐metals
Heat Conduction in non
• The efficiency of heat transfer depends on
- The efficiency of coupling betn atoms (and hence on the
nature of interatomic bonding)
- The way vibrational waves propagate through the crystal
(how they are scattered by various imperfections)
• The stronger the coupling, the higher the thermal conductivity.
Diamond has very strong covalent bond, thermal conductivity

is very high (  1000Wm 1 K 1 )
Polymers have weak secondary bonding, hence  is small
(  1Wm  1 K  1 )
 Study Table 2.5, P.152
Thermal Resistance
•
T
L
T T
Q  A 
L (L A)
V V
I  
R (L A)
L
 
A
 T
Q  

Thermal Circuit
13
2/23/2014
Electrical conductivity in non
Electrical conductivity in non‐‐metals
• Metals are good conductors because of the availability of a large number of
electrons “free” inside the metal.
• Non-metals do not have the luxury of “free” electrons. Hence, we have
insulators and semiconductors.
• Non-metals, however, have a finite, non-zero conductivity however small.

This is because of other types of carriers that can drift.
Semiconductors
• Semiconductors have a special kind of band-structure that
results in a quite distinct band-gap that separates the
conduction band from the valance band.
• At sufficiently high temperature, because of the constant

vibration of the atoms, some electrons break-away from the
atom, and become available in the conduction band.
14
2/23/2014
Semiconductors
• Electrons in the conduction band are free to move, or ‘drift’
under an applied field.
• Electrons that leave valance band and jump into conduction
band leave an empty space in the valance band.
band, band This is called
‘hole’, with a +ve charge.
• Both holes and electrons can drift, and give off a net current
flow inside the semiconductor. Electrons and holes drift in the
opposite direction, however, due to their opposite charges.
• Impurities can replace some of the lattice atoms, by intentional
d i
doping. This
Thi will
ill create
t additional
dditi l electron
l t and
d holes.
h l
Overall conductivity of a semiconductor is,
  qn  n  qp  p
Ionic Crystals
• All crystalline solids possess

vacancies and interstitials. Some
of tthe
o e interstitial
te st t a ato
atomss a
are
e
charged. These interstitial ions
can diffuse from one site to
another. This causes a drift by
diffusion under an applied E-field.
See fig. 2.28(a)
• Thus there are various charge g
e 1 , h  ,
15
2/23/2014
Ionic Crystals
•
   q in i i
 E 
   o exp  
 kT 
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Quantum Mechanics
Modern physics by
ARTHUR BEISER
Chapters:
2: Particle Properties Of Waves
3: Wave Properties Of Parcle
5: Quantum Mechanics
6: Quantum Theory Of The Hydrogen
Atom.
Handouts: 2 & 3
Contents
• Lights as a wave. • Steady-State form of Schrödinger
equation.
• Blackbody radiation.
• Planks formula. • Particle in a box.
• Photoelectric effect. • Wave function on the box and

normalization.
• Quantum theory of light.
• Finite potential well.
• De Broglie Wave.
• Quantum tunneling.
• Probability Density.
• Applying the boundary condition.
• Uncertainty Principle.
• Bohr’s atom.
• The wave equation.
• The Hydrogen atom.
• Schrödinger equation.
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Contents
• Separation of variables.
• Quantum number.
• Magnetic quantum number.
• Electron probability density.
• Angular variation of probability density.
Light as a wave:
• For many reasons light was being treated as waves. The phenomena of
interference, diffraction ,refraction and reflection all can be explained by
treating light as propagating waves.
• In 1864, James C. Maxwell made the remarkable suggestion that

accelerated charges generate electric and magnetic disturbances that can
propagate through the space. The electric and magnetic fields vary together,
being perpendicular to each other and to the direction of propagation.
Maxwell also calculated free-space velocity of such an Electro-magnetic
wave to be,
1
c  3 108 ms 1
0 0 Study : figure 3.1-3.3 kasap
In 1888, Heinrich Hertz experimentally proved the existence of EM-waves.

He determined the wavelength and speed of the waves.
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Blackbody radiation:
• The origin of radiation emitted by matter was giving scientists severe
headaches. All objects radiate energy continuously at all frequencies,
the peak frequency will depend on the temperature.
• A blackbody is an idealized body that absorbs all radiation that is

incident on it. At equilibrium, such a blackbody constantly absorbs
and emits radiation with the ambient. If the blackbody temperature is
raised above the surroundings, there is a net emission.
• A small hole in a hollow object with perfect reflectors inside can be

used as a laboratory blackbody. The blackbody radiation emitted from
the hole of the cavity can be sampled .A blackbody radiates when it
is hot , the spectrum has its peak at a higher frequency (shorter
wavelength) than that of a colder blackbody.
• At the end of 19th century Lord Rayleigh and James Jeans calculated
the emitted radiation by a cavity at absolute T. The density of
standing waves in such a cavity is given by,
8 2 d
G ( )d  3
c
• This formula is independent of cavity size. The higher the
frequency(), the shorter the wavelength(), the greater the no. of
possible standing waves. There are two-degrees of freedom
associated with the wave , and hence , from the theorem of
equipartition of energy , the total avg. energy in these two-degrees
of freedom:
1
  2( )kT  kT
2
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• Hence, the total energy per unit volume in the cavity within the
frequency range of v and v+dv is:
• The radiation rate is proportional to this energy density. This is the

Rayleigh-Jeans formula , that summarizes what classical physics can
say about blackbody radiation.
• As frequency increases (toward the ultraviolet) , the energy density

increases as (2)
• This implies as   , energy density becomes infinite. But in reality the

energy density falls off as   . This is known as the ultraviolet
catastrophe.
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Planck’s formula:
• In 1900, German scientist Max Placnk used a “lucky guesswork” to propose
the following formula to match the experimental data points of a blackbody
spectrum
8h  3d
u ( )d  3 h ; h = 6.626x10-34 J.s
c
e kT  1
• At very high frequencies h >>KT and eh/kT →∞ , thus u( )h0. Thus

the ultraviolet catastrophe has been avoided in the new quantum theory.
1 kT
• At low frequencies h <<KT, for small x, ex  1+x and thus , h

h
e kT 1
• Hence for low frequencies
8  h 3  kT  8kT 2
u ( ) d   3
  d   d ; This was the Rayleigh-Jeans
c  h  c3 formula
How to justify Planck’s formula?

• After several weeks of “the most strenuous work of my life”,
Planck found the justification: the oscillators in the cavity walls
could not have a continuous distribution of possible energies ,
but must come in discrete packets: n=nh, n = 0, 1, 2 …
• The oscillator absorbs/emits energy in discrete packets or in
‘quanta’, the average energy per oscillator in the cavity walls –
and so per standing wave – is :
h
 h
e kT 1
• This quantization was an “act of desperation” on Planck’s part,

and was in direct contrast to Classical Physics.
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Photoelectric Effect*
• When light falls on a clean metal surface, electrons are sometimes given off.
These are called photoelectrons, and their ejection by light is called the
photoelectric effect. For a given value of  or  of the incident light, there is
a spread of photoelectron energies down to essentially zero. However, the
maximum kinetic energy (Kmax) of a photoelectron is fairly sharply defined
and varies linearly with . … The Kmax energy does not depend at all on the
intensity of the incident light, its frequency. Moreover, below a minimum
‘threshold’ frequency o for the incident light, no electrons are ejected at all,
irrespective of the incident light. The threshold frequency o is the
characteristic of the metal being used as the photoemitter.
• These results are difficult to explain classically.
• According to Einstein’s photon concept, however, the basic process is the
absorption of a quantum energy of E = h by an individual electron. Most
such electrons will use part or all of this energy plowing through the metal.
However, some of the electrons situated near the surface will escape with a
maximum retained energy. Even these maximum-energy electrons must pay
an ‘energy tax’: they must surmount a potential-energy step at the surface
of the metal. The height of this step measures the tenacity with which the
metal confines its electrons and has different values of different metals.
• The photoelectric effect is strong evidence for the existence of photons. The
fact that the same value of h is obtained from experiments with different
metals strengthens this evidence.
Dr. Farseem Mohammedy *A P French and E F Taylor, An Introduction to Quantum Theory, pp18-21. 11
R A Millikan, Phys. Rev., 7, 355 (1916)
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Quantum theory of light:

• In 1905, Albert Einstein postulate that
light consist of quantum of photons. Each
photon of light with frequency  has an
energy h.
• There is a minimum energy φ for an
electron to escape from a particular metal
surface. This energy is called work
function : φ= h.
• The greater the work function, the more
energy is needed for an electron to leave
its surface.
• According to Einstein the photoelectric
effect is a given metal should obey:
• h= KEmax +Ф = KEmax + h
• KEmax =h(-)
• If the energy h (work function) is
needed to remove an electron from a
metal surface, the maximum KE will be
h(-) when light of  is directed at the
surface.
13
De Broglie Waves:
• A photon of light of frequency  has a momentum p = h/c = h/,
then =h/p, photon wavelength
• De Broglie suggested that this wavelength applies to material

particles as well as to photon.
• A particle of m and velocity v has momentum p =mv and =h/mv

This is called De Broglie wavelength.
• This conjecture was experimentally proved by diffraction of electrons

in crystal, after Bohr proposed his model for H2 atom in 1913.
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Uncertainty Principle
• It is impossible to know both the exact position and exact momentum of an object at
the same time. This was proposed by W.Heisenberg in 1927.
• The spread in position coordinate ∆x and spread in momenta values ∆p are related
through the uncertainty equation ∆x ∆p ≥h/4 => ∆x ∆p ≥ ћ/2 (ħ=h/2)
• If ∆x is small, ∆p becomes large, and vice-versa.
• This uncertainty is due not to inadequate apparatus but to the imprecise character in
nature.
• A similar relation can be shown to exist: ∆E ∆t ≥ ћ/2
• This uncertainty can be seen in any two complementary quantities.
• Planck’s constant (h) is so small that the limitations imposed by the uncertainty
principle are significant only in the relation of atom.
Study examples 3.6, 3.7-3.9, Beiser, 5th Ed.
Interference patterns
Airy disk: A 1927

electron interference
pattern photograph
Fun read:
http://www.benbest.com/science/quantum.html
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The wave Function:

• The wave function Ψ(x,y,z,t) of a body has no physical significance
itself, but |Ψ|2 evaluated at a particular space and time is
proportional to the probability of finding the body there at that time.
Linear momentum, angular momentum and energy of the body are
other quantities that can be established from Ψ. The problem is to
determine Ψ for a body when its freedom of motion is limited by the
action of external forces.

2
• Ψ must be normalizable :

| | dV  0

• Ψ must be
a) Continuous and single-valued everywhere.
b) ∂Ψ/∂x, ∂Ψ/∂y, ∂Ψ/∂z must be continuous and single valued
everywhere.
c) Normalizable:   0, if x, y, z  
Wave Function as a Field of Complex Numbers

• The wave function of a single particle, like its probability cloud,
assigns an amplitude to all possible positions of the particle.
Wave function is an assignment of a complex number to every
point in space, at each time.
• The particle does not occupy a definite position at each time; instead, it is
assigned a probability cloud that extends over all space.
• The probability cloud is an extended object, which has some
non-negative density at each point.
• The density of the probability cloud at a point represents the relative
probability of finding the particle at that point. Thus, the particle is more
likely to be found where the density of the its probability cloud is high, and
it is less likely to be found where the cloud’s density is low.
• Probability clouds are calculated from wave functions.
Interpretation by Frank Wilczek,

Nobel Prize in Physics 2004, Professor
at MIT, “A Beautiful Question”, 2015.
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Wave Function, cont’d

• To pose questions, we must perform specific experiments that
probe the wave function in different ways.
• Answering these questions requires different ways of
processing the wave function.
• There are also mutual incompatibilities due to uncertainty
principle.
• However, major synopsis are –
– You get probabilities, not definite answers. (Determinism)
– You don’t get access to the wave function itself, but only a peek at
processed versions of it. (Many Worlds)
– Answering different questions may require processing the wave
function in different ways. (Complementarity)
– To probe is to interact, and to interact is potentially to disturb.
Probability Density:
• A wave function ψ can be associated with a moving body at a

point in space x,y,z and time t.
• Ψ itself is not an observable quantity.
• lψl² is known as probability density.
• The probability of experimentally finding the body, with a wave

function ψ,is proportional to lψl².
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A note on wave function normalization

• "[Schrodinger's] approach is based on the wavefunction , which gives (via
2) the probability of finding a particle at a particular point. Since we shall
have to be content with inexact knowledge we will not insist that our electron is
to be found at a definite point but simply require that it is localized within an
interval of space of length x. this means that we shall have to choose a 
which is only non-zero within a range of x. such a wavepacket … cannot be
made of a wave with a unique value for its wavelength since such a wave
stretches on for ever. Instead it has to be made up of a band of waves of
different wavelengths, cunningly chosen to cancel each other out outside the
region of width x and to reinforce each other inside it. … the mathematicians
assure us that it can be done [through Fourier analysis].”
– JC Polkinghorne, p.44-45, The Quantum World
Entanglement
• The quantum mechanical description of two or more particles is also based

on wave functions. It brings in an important new feature: entanglement.
• The correct description for two-particle system employs a wave function that
is a field in a six-dimensional space whose coordinates are the three
coordinates that describe the position of the first particle, followed by three
coordinates that describe the position of the second particle.
• When we square this object to get the joint probability, we generally find
that the particles are no longer independent. Measuring the position of one
of them affects the probabilities for where we will find the other.
• Entanglement is neither a rare phenomenon in QM, nor an untested corner
of the theory. It arises when we compute the wave functions for a Helium
atom’s two electrons. The spectrum of helium has been both measured and
computed with great accuracy, and we find that the highly entangled wave
functions of QM give results that match reality.
• It is near magical to discover that six-dimensional space, a beautiful product
of creative imagination is embodied is something as specific and concrete as
a helium atom.
-- Frank Wilczek
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EPR Paradox
“The philosopher in the street, who has not suffered a course in

QM, is quite unimpressed by EPR correlations. He can point to
many examples of similar correlations in everyday life. The case
of Bertlmann’s socks is often cited. Dr. Bertlmann likes to wear
two socks of different colours. Which colour he will have on a
given day is quite unpredictable. But when you see (Fig.1) that
the first sock is pink you can be already sure that the second sock
will not be pink. Observation of the first, and experience of
Bertlmann, gives immediate information about the second. There
is no accounting for tastes, but apart from that there is mystery
here. And is not the EPR business just the same?”
As a hot cup of coffee equilibrates with the

surrounding air, coffee particles (white) and air
particles (brown) interact and become entangled
mixtures of brown and white states. After some
time, most of the particles in the coffee are
correlated with air particles; the coffee has
reached thermal equilibrium.
http://www.wired.com/2014/04/quantum-
theory-flow-time/#slide-5
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Schrödinger equation:
• For a particle moving freely in +x direction is given by:
x x
 i ( t  )  2i (t  )
  Ae v
 Ae 
; (  2 )
• Since, E=h=2ħ, and =h/p=2ħ/p.
E and p being the total energy and momentum, respectively, of
a free particle.
• Free particle wave equation:

i
{ ( Et  px )}

  Ae
• At speeds v<<c the total energy E of a particle is : E=p2/2m +

U(x,t)
• U(x,t) is a potential energy that represents the influence of the

‘external’ on the particle.
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p2 p2
• Now, E   U ( x, t )  E    U ( x, t )
2m 2m
  2  2
 i   U
t 2m x 2
This is the time –dependent Schrödinger equation in 1D.
• In 3-D: Where,
2 2 2
2   
x 2 y 2 z 2
Schrodinger Equation in Cartoon .
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• Any restrictions that may affect the particle’s free motion is
contained within U(x,t). Once U is known, Schrodinger’s
equation can be solved.
• Schrodinger equation cannot be derived from other basic
principles of physics.
• “We must emphasize that there is no derivation for the Schrodinger

equation. It is simply an assumption. We must derive the consequences
of this assumption and confront them with experiments. We shall see that
the triumphs of the Schrodinger equation are far too many to be accidental.
It is indeed the basic equation which describes non-relativistic microscopic
physical phenomena successfully.” – Prof A M Harun Ar Rashid,
Quantum Mechanics, 2nd ed., 2004, DU.
Steady-State form of Schrödinger equation:
• In order to extract the position-dependence of ψ, all time –

dependent reference to Ψ can be separated:
• = A exp{- i/ħ (Et-px)}
=A exp{-iEt/ħ} exp{ipx/ħ}
=Ψ
• Thus the total wave function ψ has two components:
one t-dependent, one space-dependent.
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Steady-State form of Schrödinger equation:

• Now,
; Time–independent Schrodinger
 equation in 1D.
• 2Ψ+ (2m/ħ2 ) (E-U)Ψ=0 , in 3-D.

• Each of the wave-functions, that are solutions to the steady-
state equation, corresponds to a specific value of E. Thus
energy quantization appears in wave mechanics as a natural
element. Energy quantization is revealed as a universal
characteristics of all stable systems in the physical world.
Particle in a box:
• The simplest quantum mechanical problem is
that of a particle trapped in a box of infinitely
hard walls(so collisions are elastic).The
particle moves only in x direction , i.e.
boundaries are at x=0 and x=L.
• Since the particle can not have infinite
energy to stay outside the box, the particle
remains completely confined within the box.
Ψ=0 for x ≤ 0 and x ≥ L . Within the box ,
Schrödinger equation becomes:
,( U=0 inside)
2mE 2mE
• Solution to this equation is :   Asin x  Bcos x
 
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Particle in a box:
• Lets now evaluate A, B .
• At x=0, Ψ=0 . At x=0, Ψ=A.0 + B.1 = 0 » B=0.
• At x=L ,
• This means the particle can only have certain values. These
eigenvalues, constituting energy levels of the system are:
Wave functions in the box and normalization:

• Wave functions within the box are:
• Normalization of Ψn :
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Wave functions in the box and normalization:

• Thus:
• Ψn may be +ve or –ve Ψn 2always positive.
• At a particular place in a box, the probability

of the particle being present may be very
different for different quantum numbers. For
example, a particle at n=1 is most likely found
in the middle of the box, while for n=2, the
particle is never there! Classical physics says
that the particle should be anywhere in the
box with equal probability.
Standing Wave
• Electron probabilities in a box has resemblance in the standing wave
patterns of sound Ancient way to visualize the
effects of vibrations on
mechanical surfaces. Chladni
patterns were discovered by
Ernst Chladni.
Sound waves on a guitar
Electron orbitals
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Finite potential well

• Boxes with infinitely hard walls are an
idealization. In reality, potential
energies are never infinite and box
walls are usually softer
• Let’s consider a box that is U high, L
wide and contains a particle whose
energy E<U. We shall see that, in such
a case, wave function will penetrate
the walls.
• Within the finite well, Schrödinger
equation gives the solution :
2mE 2mE
 II
 A sin

x  B cos

x

• For infinite well, we found the cosine component did not exist
(B=0).However in the finite well:
 II =A @ x=0 and  II =B @x=L.
• For either solution, both  and d/dx must be continuous at x=0,x=L. The
wave function inside and outside each side of the well must not only have
the same value, but also they must have the same slopes. So they match up
perfectly. When these boundary conditions are considered, the result is that
exact matching only occurs for certain values of En.
• In regions Ï and ÏÏÏ, Schrödinger equation is:
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Finite Pot. Well

• Solutions are:
ax ax ax ax
 Ce  De and   Ee  Fe
1 3
• As x→ - ∞ , e-ax→ 0 ; x→ +∞ , eax → 0, then D,E=0
ax ax
• Thus  Ce and   Fe
1 3
• These exponentials decrease inside the barriers at the sides of

the well.
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Quantum tunneling:
• Lets consider a particle of energy E hitting a thin barrier of height U having E<U.
• We will find that the particle has a finite probability of passing through the barrier.
Thus the particle can tunnel through the barrier and emerge at the other side of the
barrier. This is in direct contrast to classical mechanics, which does not allow any
such barrier penetration.
• There are plenty of examples in nature showing quantum tunneling in the sub-
atomic realm. For example an α-particle (K.E.~few MeV) escapes from the potential
well of a nuclei (~ 25MeV high). The probability of escape is so small that the α-
particle has to hit the wall 1038 times or more before it emerges. There are resonant
tunneling diodes (RTD) that depend on tunneling of electrons.
Quantum tunneling:
• A beam of energy E<U is incident from left. On both sides of
the barrier U=0. Thus Schrödinger equation becomes :
;
 A e k1  B e k 1  F e k 1  G e k1
i x i x i x i x
  I
  III
2mE P 2
• Where , k 1       is the wave function outside the
barrier.
Here,  I   Ae k is the incoming wave and  I   Be k is the
i x i x
• 1 1
reflected waves.
• Also,  I  I   I  I III
II
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Quantum tunneling:
•  III 
 Fe k1
i x
is the transmitted wave that is travelling in +x
direction in region III . In this region , there's no reflected or –
x directed wave.
• So,  III    III  Fe k
i x1
• If S is the no of particles /m2s , then S  |  | v I  , I+ is the

2
group velocity of the of the incoming wave, which is also the

velocity of the particles.
• Now the transmission probability T for a particle to pass
through the barrier is the ratio:
2
 III   III  FF* III 
T 2

 I I AA* I 
Quantum tunneling:
• T is the fraction of incident particles that succeed in tunneling.
Classically , T=0.
• Within region II, Schrödinger equation becomes:
2
d II

2m
( E  U ) 0
2 2
dx  II
2m(U  E)
  Ce k 2  Dek 2
 x x
II
; k
2

• Since the exponents are real, ΨII does not oscillate and
therefore is not a moving particle. The probability density,
• |ΨII|2  0. so there is a finite probability that we will find a
particle within the barrier.
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Applying the boundary condition:

• Boundary condition @ x=0 : ΨI = ΨII , (d ΨI/dx)=(d ΨII/dx)
@ x=L : ΨII = ΨIII , (d ΨII/dx)=(d ΨIII/dx)
• If we substitute the value of ΨI, ΨII , ΨIII then we get:
A+B=C+D
iK1A - iK1B=-K2C+K2D
C ek2  Dek2  F eik2
L L L
 k 2 C e k2  k2 D ek2  i k1 F e k2
 L L i L
• Solving for (A/F):

• Since U>E, K2/K1 > K1/K2 and K2/K1 - K1/K2 ≈ K2/K1.
• Also assuming the barrier to be thick enough to weaken ΨII ,
then K2L>>1 and exp(K2L)>> exp-(K2L),then
• Then,
• Finally the transmission probability is
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2
2 m (U  E )
• And,
(k2)
2
  
U
1
2 mE E
k1 2

16
• With approximation: T  k2L
2  1
e 2
k 2)
4(
k1
• See ex. 5.5
Potential Box (Kasap 3.6)

• What happens if a particle is trapped in a 3-D box?
• Consider a box of size a, b, c along the x-y-z axes. The potential is zero
inside and is infinite outside – constituting a 3-D potential energy well.
• Need to solve the Schrodinger equation in 3-D: 2 2m
   2 E  U   0

• Solve this by separation of variables: let us say the wave function is (x,y,z)
= A sin(kxx) sin(kyy) sin(kzz)
• Now apply the boundary condition: (x,y,z) = 0 at x=a, y=b, z=c.
• At x=a, (x,y,z) = 0 gives kxx = n1. Thus kyy = n2 kzz = n3 [n1 n2 n3 are
quantum numbers associated with x(x), y(y), z(z)]
• The eigen functions of the electron in a 3-D infinite potential well is
 n1x   n 2y   n3z 
 n n n x , y , z   A sin   sin   sin  
 a   b   c 
1 2 3
• Each possible eigenfunction can be labeled a state for the electron. Thus,
111 and 121 are two possible states.
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3-D Box
• To find the constant A of the wave function, we need to use the
normalization condition that (x,y,z)2 integrated over the volume
of the box must be unity. This gives A = (2/a)3/2.
• The total energy is obtained as:
2 2 2
2 h 2  n1 n2 n 
En1n2 n3 
2m
 2 2 2
kx  k y  kz  
 2  2  32 
8m  a b c 
• If a=b=c as in a square box, E = h2(n12+n22+n32)/8ma2. Thus,
energy is quantized, and it depends on three quantum numbers.
• In 3-D, we have threee quantum numbers, each one arising from
boundary conditions along one of the coordinates. The energy of the
electron is also quantized.
• The lowest enrgy of the electron is E111, not zero. The next level of
energy is either of E211, E121, E112.
• Having multiple allowed states at one energy level is said to have
degeneracy. Since there are more than one state in the 2nd energy
level - 211, 121, 112, it has three-fold degeneracy.
The wave function of a particle in an infinite 2D well for nx = 4 and ny = 4 [- wiki]
See :
http://www.nyu.edu/classes/tuckerman/adv.c
hem/lectures/lecture_7/node2.html
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6/7/2016
Bohr’s atom:
• An electron of charge –q with mass m is moving in a circle
around a proton of charge +q. the proton is sufficiently massive
to be treated as fixed. The radius of circle is r and the velocity
is v.
• The electrostatic attraction between electron and proton must
exactly match the electrons mass times its centrifugal
acceleration in the circular orbit:
• The energy of the electron is made up of its kinetic and

electrostatic potential energies:
Bohr’s atom:
• The Bohr condition for the quantization of angular momentum
(mvr) is
mvr = nħ, n=1,2,3……..
m 2v 2r 2 n 2 2
 
mv 2 r q2
2 2
• Then, r  n  2
m q
4
qm
• Thus the energy quantization becomes: E   . 1n 2 2
2 n
• Which is just the Bohr formula for the energy levels of
hydrogen atom, leading to the Balmer series.
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6/7/2016
The Hydrogen atom:

• The first problem Schrödinger tackled with his wave equation is
the problem of hydrogen atom. At the end of the rigorous
math, the discovery of how naturally quantization occurs in
wave mechanics was evident.
• The Schrödinger equation is :
2 2m
 2
( E  U )  0

• The potential energy is :
2
U 
q
4  0 r
• Since U is a function of r , we cannot directly substitute U( r) in

Schrödinger equation. The best options is to rewrite the
equation in spherical coordinates because of the special
symmetry of the physical situation.
The Hydrogen atom:

• The polar coordinates are r, θ, Ф of P:
• r= radius vector to P=
• θ= zenith angle =
• Ф= azimuth angle =
• In spherical polar coordinates, Schrödinger equation becomes:
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The Hydrogen atom:

• Substituting U ( r ) and multiplying by r2sin2θ throughout.
• This is the partial differentiation of the wave function Ψ of an

electron in a hydrogen atom.
• When this equation is solved, we’ll see that three quantum
numbers are required to describe the e- in H2 atom.(against
one quantum no. in Bohr’s theory)
• In Bohr’s model, electron’s motion is in 1-D. But a particle in a
3-D box needs three quantum no. In a H2 atom ,the electrons
motion is restricted by the inverse square electric field of the
nucleus.
Separation of variables:
• The advantage of writing Schrodinger equation in spherical
coordinates is that now it may be separated into three
independent equations, each involving one variable only.
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6/7/2016
• Substituting Rθφ for Ψ and then divide by Rθφ will give ,
• This equation can be correct only if both sides of it are equal to

the same constant , since they are function of different
variables. Thus,
2
1 d  2
 2
 me
 d 
• Lets substitute me 2 for the RHS of the above Schrödinger
equation and divide the entire equation by sin2 θ, yields
• Again we have an equation with different variables appealing in

each side. RHS is only a function of θ and LHS being a function
of r only.
• Then
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6/7/2016
• Equation for φ:
• Equation for θ:
• Equation for R:
• Each of these 3 equations are ordinary differential equation for

a single function of a single variable.
Quantum number:
• There three degrees of freedom, hence three quantum numbers
• ---The eqn for Ø can be solved Ø(θ)=A exp(i mL Ф)= A exp{imL(Ф+2x)}.
mL is known as magnetic quantum number: [mL = 0,±1,±2,±3……….]
• ---The eqn for Ѳ(ѳ) has a solution provided that the constant ‘ L ’ is an
integer equal to or greater than lmLl. The requirement can be imposed on
m L:
mL=0,±1,±2,±3……±L
• The constant ‘ L ’ is known as orbital quantum number.
• ---The equation for R(r) can also be solver provided E fulfills some condition:
• This is the same for Bohr’s formula.
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Quantum number:
• Another condition that must be obeyed is that n, known as principle
quantum number, must be equal to or greater than L+1.
L=0,1,2….(n-1)
• Principle quantum no: n=1,2,3… [ The set of quantum
• Orbital quantum no: L=0,1,2,…..(n-1) number]
• Magnetic quantum no: mL= 0,±1,±2……….±L
• Thus ,   mnl l 
ml ml
• It is worth noting that quantum number naturally arise in quantum-

mechanical theories of particles trapped in space.
• Normalized wave functions of hydrogen atom for n=1,2,3 are tabulated in

table 6.1 , Beiser(5th ed), p.205
• Self study : see 6.4,6.5
MAGNETIC QUANTUM NUMBER:

• Orbital quantum no. l =|L| is the magnitude of electron’s
angular momentum L. ‘L’ is a vector quantity that has both
direction and magnitude.
• The electron revolves round a nucleus and creates a minute

current loop and has a magnetic field (as if it’s a magnetic
dipole). Hence, an atomic electron possesses angular
momentum interacts with an external magnetic field ‘B’. The
number ml specifies the direction of ‘L’ by determining its
component in the field direction.
• This phenomenon is called space quantization.
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6/7/2016

• If the magnetic field is z-directed, then [Lz=mLħ]; mL=0, ±1,
±2… ±L
• Thus the no. of possible orientations of the angular-momentum
vector ‘L’ in a magnetic field is 2L+1.
• @L=0, Lz=0; @L=1, Lz=ħ,0,-ħ; @L=2,Lz=2ħ,ħ,0,-ħ,-2ħ…..etc
• ‘L’ can never point in any specific direction, but instead is

somewhere on a cone in space, such that its projection Lz is
mLħ. Otherwise, the uncertainty principle would be violated. In
reality, only Lz has definite values and [L]>[Lz]. Thus the
electron is not limited to a single plane. Thus there is a built in
uncertainty in the electrons z-coordinate. Since ‘L’ is not fixed,
and since Lzalways has a specific value mℓħ, so Lx and Ly
average values are zero.
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6/7/2016
Electron probability density:

• In Bohr’s model electron is visualized as revolving around the
nucleus in a circular path. Thus the electron can be found at a
distance of r = n2qo from the nucleus.
• The quantum theory of the H2 atom modifies the Bohr model:
a) No definite value of r,θ,Φ can be given but only relative

probability for finding the electron at various locations.
b)We cannot even think of the electron as moving around
the nucleus in any conventional sense since probability density
|Ψ|2 is independent of time and varies from place to place.

• The probability density | Ψ|2 =|R|2 | θ |2 | Φ |2 :
• The azimuthal probability density is: | Φ |2 = A2
• Thus the electron’s probability density is symmetrical about the

z-axis ,i.e. the electron has the same chance of being found at
any one angle Φ.
• The radial part R(r) varies with r and the variation is different
for each combination of n and l. Study fig. 6.8, Beiser
• dV=(dr) (r dθ) (r sinθ dΦ)= r2 sinθ dr dθ dΦ is the volume
element.
• Then,
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• A plot of P(r)dr vs r shows that the 1st electron is found at a0.
• a0= (4 ħ2/mq2 ) = 0.53Å
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Angular variation of probability density:

• The function θ varies with zenith angle θ for all L and mL
|θ|2=1/2 for an s-state. Thus electron probability density |Ψ|2
is spherically symmetric for s-state since |Ф|2 is also a constant.
It has the same value at a given r in all directions.
• Electron is other states (p,d,f,g,h) do have angular preferences.
The pronounced patterns are sometimes very important in
determining chemical bonds.
• Study Fig. 6.12 of Beiser

sec 3.7.4, Kasap, Electron spin: Sz=msħ, ms=±(1/2)
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Cartoons!
36
2/23/2014
Theory of Solids
•Excerpts from Advanced
Semiconductor Fundamentals By
Robert Pierret [Handout-3]
•Excerpts from D.Pulfrey’s

Understanding Modern
Transistors and Diodes,
[Handout-4]
Prolegomena
• Once the quantum mechanical foundation has
been established, it will be straightforward
now to trace the development of energy band
ode for
model o tthe
e so
solids.
ds
• Extrapolating from the discrete energy states
available to electrons in isolated atoms, the
interaction between atoms leads to the
formation of energy bands – ranges of
allowed electron energies, when the atoms
g into close proximity
are brought p y in formingga
crystal.
• Energy bands arise naturally when one
considers the allowed energy states of an
electron moving in a periodic potential-the
type of potential present in crystalline lattices.
1
2/23/2014
Prolegomena
• The highest energy band containing electrons at temperatures

above absolute zero is identified as the conduction band;
• The next-lower-lying band, separated from the conduction band
by an energy gap on the order of an electron-volt in
semiconductors, and mostly filled with electrons at
temperatures of interest, is identified as the valence band.
• The carriers involved in charge transport or current flow are
associated with filled states in the conduction band and empty
states (holes)
(h l ) in
i the
h valence
l band,
b d respectively.
i l
Sneaky electrons
• " … when asking anything about electrons in atoms,
molecules or solids: If you want to know what an
electron does, forget about it and pretend there is a
wave there. Calculate where the wave goes and there
you will find electrons.”
-- Sir Nevill Mott, Scientific American (Sept 1967)
Sir Nevill Mott

Cavendish Professor at University
of Cambridge; Nobel laureate
1977
• “When I started to think about it, I felt that the

main problem was to explain how the electrons
could sneak by all the ions in a metal …. By
straight Fourier analysis, I found to my delight Felix Bloch
that the wave differed from the plane wave of The first Director
of CERN
free electron only by a periodic modulation.”
Dr. Farseem Mohammedy --Felix Bloch, Physics Today (1976) 4
2
2/23/2014
The game plan
• Electrons moving inside a semiconductor crystal may be likened
to particles in a 3-D box with a very complicated interior.
• We will assume that the lattice structure to be perfect and the
atoms to beb fixed
f d in position.
• We will neglect any atomic vibration and lattice defects,
whatsoever.
• We shall treat a 1-D analog of the actual crystal.
• The game plan starts with identifying the potential energy
function U(x)
( ) in Schrodinger
g equation
q – this p
potential energy
gy is
associated with the crystalline lattice
• Consider a one-dimensional lattice where atomic cores (nucleus
+ core electrons) are separated by a lattice constant a.
1‐D Crystal
• If the atomic core electron
interaction is assumed to be
purely coulombic, the attractive
force between the atomic core
and an electron close to it would
give rise to the potential energy
versus x-dependence shown left.
• Ultimately, accounting for the
electron interaction with all
atomic cores
cores, one obtains the
periodic crystalline potential
sketched in below left.
• It is assumed that the non-core electron-
electron interaction approximately averages
out to zero
3
2/23/2014
Electron in a periodic potential –
Electron in a periodic potential –
Bloch Theorem
• This theorem relates the value of the wavefunction within any

"unit
unit cell"
cell of a periodic potential to an equivalent point in any
other unit cell.
• Thus, it allows one to concentrate on a single repetitive unit
when seeking a solution to Schrodinger's equation.
• In 1-D, it says – If U(x) is periodic such that U(x+a) = U(x),
Then (x+a) = eika (x)
• l l (x)
Equivalently, ( ) = eikx
ik u(x)
( ) where
h the
h unit cellll wavefunction
f
u(x) has the same periodicity as the potential u(x+a) = u(x)
• Thus, it means that (x) has the form of a plane wave, eikx,
modulated by a function that reflects the periodicity of the
crystalline lattice and the associated periodic potential.
• An aside

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2/23/2014
General points about Bloch Thm
• The Bloch Theorem asserts that solution in periodic potential is
always a product of two terms:
– a periodic function (with the same period)
– a plane wave
• Note that this equation does not state that (x) is periodic, but it
does lead to |(x)|2 being periodic. The latter is comforting because
one would expect an electron to have an equal probability of being at
any of the identical sites in the linear array.
• The periodicity breaks down at the edges of the crystal, but that
g
shouldn’t have a significant effect on the electrons deepp within the
crystal if the array is very long compared to the separation between
atoms, i.e., if N, the number of primitive cells, is very large.
• The boundary conditions imposed at the end points of the periodic
potential totally determine the permitted values of the Bloch function
k in any given problem.
General points about Bloch Thm
• For 1-D case, there can exist only two distinct values of k for
each and every allowed value of E.
• If the periodic potential (or crystal) is infinite in extent, then k
must be real and it can assume a continuum of values.
• For finite crystals, periodic boundary conditions are assumed – .
to envisioning the lattice to be in the form of a closed N-atom
ring. Then –
  x     x  Na   eikNa  x 
• This requires eikNa = 1 or

2 n
k n  0,1,2,   N / 2
Na
• Thus, k has only discrete values in a finite crystal. For a real
crystal – the large value of N yields a quasi-continuum of
allowed k-values.
5
2/23/2014
Kronig
ronig‐‐Penney Model
• In order to further simplify the periodic potential problem posed
by set of atoms in a 1-D crystal, we can assume a periodic
square potential array to simulate the crystal structure.
• This
h is exactly l what
h Kronig-Penney did d d [in Kronig, R. de L.; Penney,
W. G. Proc. Roy. Soc. (London), 1930, A130, pp499].
• Robert Pierret says, correctly, "The Kronig-Penney analysis must be
considered a "classic" – required knowledge for anyone with a serious
interest in devices. The value of the admittedly crude model stems from the
fact that the associated analysis illustrates energy band concepts in a
straightforward manner, with a minimum of math, and in a quasi-closed
form "
form.
• Kronig-Penney is a simple model of a crystalline solid that leads
to an electronic band structure. The development requires no
quantum mechanics beyond that taught in most basic
introductory courses and can be taught in a single one-hour
lecture 
KP Model
• The KP model closely follows that of a finite
potential well problem in quantum mechanics.
• Consider an electron of mass m and fixed
gy E subject
energy j to the periodic
p potential
p of a 1-
D crystal. There will be , similarly, two different
scenarios –
– The electron is within the well, E<Uo
– The electron is outside the well, E>Uo
• Even though the model is one-dimensional, it is the periodicity

of the potential that is the crucial property that yields electronic
band structure
structure.
• The mathematical form of the repeating unit of the potential is
U(x) = Uo for -b < x < 0
= 0 for 0 < x < a
As shown in above, the potential has a period of c = a +b.
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2/23/2014
KP Model
• The Schrodinger equation in this case is
d 2 2mE
 2   0, 0  x  a
dx 2 
d  2mE  U o 
2
   0,  b  x  0
dx 2 2
• The coefficients in both of these equations are constants, so
the solutions are similar to that of a particle in a box:
 1  Aeix  Be ix , 0  x  a
 1  Ce x  De  x ,  b  x  0
• Where   2mE  and   2mU o  E  
KP Model
• Now the wavefunction goes through a series of boundary
conditions
– Wave functions and its derivatives must be continuous at x = 0
– Wave functions and its derivatives evaluated at cell boundaries must
obey the periodicity requirements imposed by Bloch theorem
• These reuirements translate into FOUR boundary conditions
• These boundary conditions, in turn, give a set of FOUR
simultaneous equations
• After solving these simultaneous equations, using the
determinant rule,, and after a rigorous
g simplifying
p y g procedure,
p ,
[which you don't need to follow, but if you actually DO that would be
great!] one gets –
7
2/23/2014
KP Model
• There is also another equivalent way [1] of re-phrasing the above
equation in an elegant and friendly-looking form:
• This key equation unlocks the secret of bands:

– the right-hand side is a function of ga, and g is a function of the energy
E: g  2mE 
– but the left-hand
left hand side decrees that f(ga) must be bounded by ±1. ±1 Thus,
Thus
values of E are only allowed when −1 ≤ f (ga) ≤ 1.
[1] See Handout‐5 * For another alternate derivation: see
http://ecee.colorado.edu/~bart/book/book/
chapter2/ch2_3.htm#2_3_3
KP Model
• The above equation is plotted here :
• Note that this figure is arbitrarily truncated at g = 6/a, but, in reality, g

could be extended indefinitely; thus, there are an infinite number of ranges
of allowed energy, each one of which is called an energy band.
8
2/23/2014
Extended zone plot
• The energy bands corresponding to the allowed values of ga, and the
forbidden regions (bandgaps) separating the bands, are usually displayed on
a plot of energy E versus Bloch wavevector k.
• The version shown in the later slide is known as an extended-zone plot. p
• The first zone spans the range −π/a < k < π/a; the second zone is split into
two: −2π/a < k < −π/a and π/a < k < 2π/a; etc.
• Thus each zone extends over a range of 2π/a in k.
• In the Bloch Function k for finite crystals, it is seen that the corresponding
range in n is N, the number of primitive cells. As the latter number will be
usually very large in semiconductor devices, the separation of neighbouring
k values ((=2π/Na),
2π/Na), is so small that the E
E-kk relation appears continuous
within a band.
Extended zone plot
9
2/23/2014
Extended zone plot
• An E-k plot is often interpreted as an energy-momentum
relationship. This is because, momentum can be written as ħk,
where ħ = h/2π is Dirac’s constant, and k = 2π/λ is the general
relationship between wavelength and wavevector
wavevector.
• For the specific case of a Bloch wavevector, k is called the
crystal momentum. The crystal momentum is not the actual
mechanical momentum of the electron: it is the momentum of
the electron due to the action of applied forces
• More details will be discuseed in course EEE 461:
S i
Semiconductor
d t Device
D i Theory
Th
10
2/23/2014
Electron wave in a crystal
• Wave function of an electron moving in a
crystal lattice is modulated by the
electrostatic influence of the ions it
encounters. In this illustration the three
different wave functions (solid curves
below) correspond to three different
directions through a body-centered-cubic
lattice of sodium (diagram above). In all
three cases the total energy of the
electron (kinetic energy plus potential
energy(, and hence its wavelength
(broken curves below), ar the same. The
rapid wiggles of the waves in the vicinity
of an ion imply that the electron has a
higher kinetic energy there than
elsewhere.
l h Thi iin turn
This t means th
thatt the
th
electron travels very rapidly through this
region and spends comparatively little
time in it. As a result the influence of the
ionic cores is not nearly as large as one
might expect, and in many simple solids
the conduction electrons can be
described as if they were free particles.
Origin of bandgaps
• For a physical explanation of how energy bandgaps arise in a periodic
structure, consider a beam of electrons of wavelength λ propagating
through our 1-D lattice
• Imagine that there is scattering of the beam from two neighbouring
lattice sites. The two portions of the reflected beam would reinforce
constructively if the Bragg condition for normal incidence were
satisfied, i.e., 2a = bλ where a is the spacing between lattice sites and
b = 1, 2, 3, … is an integer.
• Further Bragg reflections would lead to our beam bouncing around in
the crystal, being reflected back and forth, and taking-on the
property of a standing wave, rather than that of a propagating wave.
• The wavevectors at which this would occur are k=±2/
• Thus, energy bandgaps, within which there are no propagating
waves, open up at the Brillouin-zone boundaries because of the
strong Bragg reflection.
11
2/23/2014
Take Home Lesson
Please note that the single The lattice periodicity
reason of having a band coupled with the wave
structure in a solid is due to the nature of the electron
fact that electron behaves as a gives rise to band
wave and the lattice is periodic.
structure.
Effective mass
• An electron confined within the solid, bound by lattice structure

potential, behaves differently than a free electron in space.
• This difference is due to the lattice potential.
• While a single wavefunction doesn’t give us precise spatial
information about the electron, it does give us the electron’s
crystal momentum, via the wavevector k.
• It is more convenient to think as a wave packet, by superposing
waves of slightly different k: the wider the range of k’s used,
the more tightly constrained in space the wavepacket will be,
and the more the electron will appear to have mass at a point,
i.e., to be particle-like.
12
2/23/2014
Effective mass
• The electron can then be treated as in a classical trajectory,

which is obviously helpful when following an electron through a
device.
device
• Thus, come the group velocity in mind.
• We can re-phrase the question: what happens when an
"external" force F acts on the wavepacket?
• This could be any force other than the crystalline force
associated with the periodic potential. The crystalline force is
already
l d accounted d for
f ini the
h wavefunction
f i solution.
l i
• This force might arise, for example, from dopant ions within the
crystal or could be due to an externally impressed electric field.
Effective mass
• The work done by this force F on a wavepacket is then:
dE=Fdx=Fvgdt, so: 1 dE 1 dE dk d k 
F  
v g dt v g dk dt dt
dv g 1 d  dE  1 d 2 E d k 
• But, dt   
 dt  dk   2 dk 2 dt
1 dv g
• Substituting, F = m*a; where m*  and a 
1 d 2E dt
 2 dk 2
• m* is the effective mass of the electron while in a solid.
13
2/23/2014
Physics of Effective mass
• This implies that the motion of electrons in a crystal can be visualized and
described in a quasi-classical manner. In most instances the electron can be
thought of as a "billiard ball," and the electronic motion can be modeled
using Newtonian mechanics, provided that one accounts for the effect of
crystalline forces and quantum mechanical properties through the use of the
effective-mass factor.
• An electron moving under the combined influence of an externally applied
force and the forces associated with the lattice ion cores, responds to the
external force just as if it were a free particle, but with a mass that is
determined by the band structure of the host material.
• This means that, once we know the band structure of a semiconductor, we
can compute m*(E), and, d thereafter,
h f not concern ourselves
l about
b the
h
internal details of how the potential varies according to the electron-ion core
interactions.
• Practically speaking, because of this simplification, device analyses can be
performed easily with minimal direct use of the quantum mechanical
formalism.
Physics of Effective mass
• The effective-mass relationship also underscores the practical
importance of the E-k diagrams. Having established the
crystal band structure or E-k relationship, one can determine
the effective mass exhibited by the carriers in a given material.
• Mathematically, the effective mass is inversely proportional to
the curvature of an E versus k plot.
• In general, the effective mass of an electron is a function of the
electron energy E.
• However, near the top or bottom band edge the region of the
band normally populated by carriers in a semiconductor – the
E-k relationship is typically parabolic.
• Thus, carriers in a crystal with energies near the top or bottom
of an energy band typically exhibit a constant (energy-
independent) effective mass.
• Self-study: how to measure effective mass, p.80 from Handout-4
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2/23/2014
Supplementary [1]
Dr. Farseem Mohammedy [1] See Handout‐5 30
15
2/23/2014
Supplementary: selfie
How to Measure the Effective Mass*
Cyclotron Resonance Technique B
‐‐
Centripetal force = Lorentzian force
mn v 2
 qvB Microwave
r
•fcr is the Cyclotron resonance frequency.
qBr
v •It is independent of v and r.
•It is independent of v and r
mn •Electrons strongly absorb microwaves of
v qB
f cr   that frequency.
2r 2mn •By measuring fcr, mn can be found.
* Modern Semiconductor Devices for Integrated Circuits by C. Hu, section 1.5.2.
Also see p.80 from Handout‐4
Carrier Statistics
• The energy band considerations provided fundamental information about the carriers
inside a semiconductor. Two types of carriers, electrons in the conduction band and
holes in the valence band, were identified as contributing to charge transport.
• The allowed energies and crystal momentum available to the carriers in the
respective
ti bands
b d were specified.
ifi d
• It was also established that the motion of carriers in a crystal can be visualized and
described in a quasi-classical manner using the effective mass approximation.
• Device modeling, however, requires additional information of a statistical nature.
• The desired information includes, for example, the precise number of carriers in the
respective bands and the energy distribution of carriers within the bands.
• Hence, we need a quantitative relationship that can be used to characterize the
carrier p
populations
p inside semiconductors under equilibrium
q conditions.
• Equilibrium is the condition that prevails if the semiconductor has been left
unperturbed for an extended period of time. Essentially all practical material and
device computations use the equilibrium condition as a point of reference.
• Non-equilibrium concept is used for high-level modelling and is discussed in higher
classes.
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Carrier Statistics
• Recall the solution of electron energies for a 3-D box. There we
calculated the allowed quantized energies of the electron.
• Now we need to calculate the number of allowed states as a
f
function off energy.
• In a real crystal, the sizes are enormous compared to our
previous assumptions and the incremental k-values are also
small – giving a huge number of possible states – 1020 or more.
• Let us construct a grid of points

corresponding to each solution of the
Schrodinger equation for 3-D box –
each solution has a unique point in the
k-space grid – each point has a distinct
k-value
Counting Carriers
• Recall, from the 3-D problem: kxx = nx, kyy
= ny kzz = nz
• In this lattice-like arrangement of the
solution dots,
dots a kk-space
space "unit
unit cell"
cell of volume
(/a) ( /b) ( /c) contains one allowed
solution,
• Thus
 solutions  abc
   3
 unit volume of k - space  
• For n = [nx, ny, nz] = [±1,±1,±1]

[±1 ±1 ±1] has eight
possible solutions correspond to the same
allowed state; since there is no physical
difference between wavefunction solutions
which differ only in sign, the above formula
must be divided by 8
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Counting carriers
• But there is spin too – an electron can have either an 'up' spin
or a 'down' spin
• So the previous formula should account for that too – multiply
it by
b 2.
2
 solutions  abc
   3  8; and then 2.
 unit volume of k - space  
• We therefore have:
 allowed energy states  abc
   3
 unit volume of k - space  4
• Now, we have to determine the no. of states within a small
increment of k and k+dk.
Counting carriers
• This can be done by adding up the
states lying between two k-space
spheres-
• This
h can be b done
d analytically,
l ll byb
multiplying the previous result by 4k2dk
– i.e. the k-space volume between the
two spheres
• This will give:
 abc 
Energy between k aandd k  dk   4k 2 dk  3 
e gy states betwee
 4 
• This result in incremental dk, can be  2k 2 2mE
E  k2  2
converted to incremental dE, using – 2m 
 2k 1 m dE
dE  dk  dk 
m  2 E
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Counting carriers
• A direct substitution will result in:
 
Energy states between E and E  dE   abc m 2mE
dE

  
2 3

• Finally, the density of states is obtained by dividing this result

by the volume V = abc:
m 2mE
g E  
 2 3
Specific materials
• To obtain the conduction and valence band densities of states near the band
edges in real materials, the mass m of the particle in the previous derivation
is replaced by the appropriate carrier effective mass.
• Also, if Ec is taken to be the minimum electron energy in the conduction
band and Ev the maximum hole energy in the valence band band, the 'E' should
be replaced by E - Ec in treating conduction band states and by Ev - E in
treating valence band states.
• Introducing the subscripts c and v to identify the conduction and valence
band densities of states, respectively, we can then write –
me* 2me* E  Ec 
g c E  
 2 3
m*p 2m*p Ev  E 
g v E  
 2 3 Think:
1. Why do we need
a separate
• me* and mp* are density-of-states effective masses effective mass
here?
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Carrier concentration
• To complete the calculation of the carrier concentrations, we
need to know the distribution function f (E).
• Under the non-equilibrium operating conditions of a
semiconductor
d device
d this
h is not an easy task.k
• However, the distribution function under equilibrium conditions
is well-known
• The electron and hole concentrations (per unit volume) can be
written as
n   g c E  f E dE
p   g v E 1  f E dE
Distribution function
Dr. Farseem Mohammedy http://www.gitam.edu/eresource/Engg_Phys/semester_2/ 40
mod phys/dist func.htm
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• Energy band diagram is the workhorse of semiconductor

models. Without knowing what it is, or not knowing how to
draw or derive such relationships, NO device modeling can be
achieved.
Density of States of some Electronic structures
Density of States of some Electronic structures
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Dielectric Material and

Insulation
Kasap Ch 7
Dielectric Polarization and Relative Permittivity

• Let’s consider a parallel plate capacitor with charges Q0
on the plates and vacuum inside.
• The capacitance in free
space is: =
• The electric field directed
from high to low potential
is defined by the potential
dV
gradient: E  
dx
• If now a slab of non-conducting dielectric is inserted
betn. the plates, if the same V is maintained, then the
2
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Dielectric Polarization and Relative Permittivity

charges stored are changed from Q0 to Q > Q0.
• The capacitance would be C > C0.
• The relative permittivity or dielectric constant ( r ) is defined
to reflect this increase in capacitance due to the presence of

Q C
the dielectric medium.  r  
Q0 C0
• The observed increase in storage charge is due to the
polarization of dielectric material by the applied E-field.
Dipole moment & Electronic polarization

• The electric dipole moment is created by the separation
of equal but opposite charges: P  Q a ( a is the vector
from –ve to +ve).
• When an electrically neutral atom

is placed under an external E-field,
the electron cloud, which is
otherwise a concentric circle with
the same center as the nucleus,
gets displaced relative to the nuclear center.
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•
Since electrons are lighter
than protons, they get
easily displaced. Thus it
creates a dipole moment.
• This separation of –ve and
+ve charges result in an
induced dipole moment and the atom gets polarized.
• The dipole moment is proportional to the E-field.
Pinduced   E (  is polarizability)
• Since the polarization of a neutral atom involves displacement
of electrons,  is called electronic polarization (  e).

• If the atom has Z electrons orbiting the nucleus, then under
E-field, they get shifted by a distance x.
• The force on the electrons, due to E, is QE=(Zq)E.
• But due to the Coulombic attraction, there is a restoring force

Fr    x . In equilibrium, ( qZ ) E   x
• The magn. of the induced moment,

Pinduced   E  Qa  Qx  ( qZ ) x
( qZ )( qZE ) q 2 Z 2
 Pinduced   E
 
• This is valid under static dc-conditions.
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• If the E-field is withdrawn, then the restoring force F will pull
r
the Z electrons toward the nucleus:

Fr    x  mass  acceleration
d 2x
   x  Zme  2
dt
 x (t )  x0 cos( 0 t )
• After the removal of E-field, the electron cloud executes
simple harmonic motion about the nucleus with frequency  0:


0 
Zme
• This is the electronic polarization resonance frequency.

• The harmonic motion dies out of course.
• Finally the electronic polarizability becomes:
q2Z 2 q2Z 2 Zq 2
e   
  02 Zme  02 me
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Polarization Vector
• When a material, e.g. the dielectric in the capacitor, is placed
in an E-field, the atoms and molecules of the material become
polarized. In such a case, as shown in the following figure, a
net +ve charge develops on Right
Hand Side surface and -ve on the
LHS surface.
• These are called surface

polarization charges, that are
bound and are a direct result of the
polarization of the molecules.
Polarization Vector
• The total dipole moment per unit volume is called
Polarization (P) and represents polarization of a medium.
1
P  P1  P2  P3  .........  PN  (P1 , P2 , P3 ........ are dipole
volume  
moments in each N molecules)
 N P (Pav is the avg. dipole moment in each molecule
av
N is no. of molecules per unit volume.)
• The polarized medium can be thought of as having two
separate charges +Qp and –Qp displaced by d. Then the total
dipole moment from –Qp to +Qp is: Ptotal  Q p d

Ptotal Q p .d Q p
• Now the magnitude of P is P    p
vol a.d a
• p is surface polarization charge density
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Polarization Vector
For directional information of P, study Fig 7.6
• The charge/unit area appearing on the surface of a polarized
medium is equal to the component of polarization vector
normal to this surface.
• The polarization induced in a dielectric medium depends on

the field under which it is placed. Thus: P  e 0 E ,where
susceptibility e is a proportional constant. (e relates the

‘effect’ to its ‘cause’).
1
• But Pinduced eE P  NPinduced  NeE  e0E   e   N e
0
• This relates the electric susceptibility to the polarization.

Polarization Vector
• There are ‘free’ charges ( Q and Q0 ) and ‘polarization’
charges (Qp) in a metal.
• The E-field, before a dielectric is inserted, is:
V Qo Qo o Qo
E    (o   Free surface charge
d C od  o A  o A
density)
• After the insertion of dielectric, Qo changes to Q, but E=V/d
remain same.
• Also, there are bound polarization charges on the dielectric
surface. Thus, the flow of current, during the insertion, is due
to free charges Q- Qo needed on the capacitor plates to
neutralize the polarization charges Qp appearing on the
dielectric surfaces.
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Polarization Vector
• Thus Q  Q O  Q P
 Q  Q O  Q P
Q Q O Q P
  
A A A
   o   p   oE   p
Since  P  P  e  oE ,   oE  e  oE  (1  e)  oE
•Since, by definition, relative permittivity is,

Q 
r     0 
r 0 r E
Qo  o
Then
r  1   e
Or in terms of electronic polarization:r  1  N  e is related to e
(Microscopic 
0 macroscopic  )
r
Clausius-Mossotti Equation:
• The actual field experienced by a molecule in a
dielectric is called Local field (Eloc).
It depends on-
•Free charges on plate
•Arrangement of all polarized molecules around.
How To Evaluate Eloc :

• Remove the molecule in question and calculate the
field at the point coming from all sources.
• Eloc depends on the arrangement of polarized
molecules around the point of interest and hence
depends on crystal structure.
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How To Evaluate Eloc :

• In the simplest case
for a cubic crystal or
liquid:
1
E loc  E  P,
3 o
Lorentz local field.
• The induced polarization

in the molecule now
depends on Eloc, rather
than E,
Pinduced   e Eloc
Other relations:
P  e0E  (r 1)0E (e 1  r ) = =N
and
1 1
(r 1)0 E  Ne Eloc  Ne (E  P)  Ne E{1 (r 1)0}
30 30
Ne N 2 N N
 (r 1)0  Ne  r  e  Ne  e r  e (2  r )
3 3 3 3 3
−1
= Clausius-Mossotti equation
+2 3
• This relation allows the calculation of macroscopic

property  r from microscopic property  e .
Self study: sec 7.2 (Kasap)

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Polarization Mechanism
In addition to electronic polarization, there are other

polarization mechanisms.
Ionic polarization:
• Ionic crystal ( NaCl , KCl etc )have distinctly identifiable
ions ( Na+ , Cl- etc). Thus oppositely charged ions have
a dipole moment.
• In the absence of an external field, the net polarization

is zero : Pnet =P+ - P- =0 .
Ionic polarization:
• In the presence of a E-field , Pnet≠0 ; since charged ions
get displaced in opposite directions .Thus induced avg.
dipole moment per ion pair depends on E : Pavg=αi Eloc ,
where αi is ionic polarizability . Generally , αi > αe . As a
result , ionic crystals have larger dielectric constants .
• Polarization P =Ni . Pavg = Ni αi Eloc ( Ni is the no. of ionic

pairs per unit volume ) .
The Clausius-Mossotti equation: −1

=
+2 3
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Ionic polarization:
• Each ion has a core of electron. These are also
displaced under an E-field.
• This electric polarization adds to the ionic polarization,

but is much smaller in magnitude.
Dipolar Polarization
•Some molecules have
permanent dipole moments.
For examples, HCl or H20.
•In liquid/gas phase, w/o any
E-field, these molecules are
randomly oriented due to
thermal agitation.
•Under an E-field, the
randomized molecules align
themselves with the E-field.
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• Under an E-field, Cl- and H+ charges experience force
in opposite directions. The Cl--H+ bond holds them together.
• The net result is a torque (τ) about its center of mass.
• If all such molecules rotate and align with the field, the
polarization would be: P=N.Po (N=no. of molecules per
unit volume).
• Thermal agitation causes the molecules to collide with the
container wall and randomize the dipole moment.
• Nonetheless, there is a net polarization that leads to a
dielectric constant.
• This is called dipolar/orientational polarization.
• 
A dipole at an angle θ to the E-field, experiences a torque( )
  ( F sin  ) a
= [po=a.Q]
@ θ=0,  = 0 and @ θ=1800,  is maxm
= =2
•The avg. dipole moment Pav along E is directly proportional to

the magn.of Po and also to the avg. dipole energy to avg. thermal
energy ratio.
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• If the Boltzmann distribution for the dipole energies among the
molecules are considered (probability of a dipole having energy
 E 
E is  exp a
), then
 k T 
1 PO 2 E
Pavg   Pinduced   d E
3 KT
2
1 po
Hence, d  Dipolar/Orientational polarizability.
3 KT
 d is strongly temp-dependent. As T ,  d ,r 
• Dipolar polarizability is shown in polar liquids (H2O, HCl &

various electrolytes) and polar gases.
Additional Dipolar polarization [Kasap 7.11]

• Consider a medium with molecules with permanent dipole
moment p0.
• Under an E-field, the dipole try to align themselves along the
E-field, but the thermal vibration acts against it, by collisions
and randomizing the net polarization.
• Let’s consider an arbitrary
dipole with p dipole moment
at θ with E.
• The torque experienced by the
dipole is   ( FSin ).a
 Ep0 Sin ( p0  aQ)
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Dipolar polarization
• Potential energy of this dipole is

E   d   poESin d   poECos   poE
0
• The fraction of molecules that is oriented at θ has a

Boltzmann distribution and is proportional to
E

f e kT
 e p oE cos  / kT
4
 ( p Cos  ) fd 
o
• In 3-D, this becomes p av  0

4
(  d   4 ) solid
 fd 
0 angles in 3D
• The result of this integration is a special function called

Langevin function (L(x)): pav=poL(x) , (x=E/kT)
Dipolar polarization
• At high-fields L(x) tends to

unity: Pav=Po.
-- This mean nearly all dipoles are
aligned with E. Thus increasing the
field doesn’t yield anything.
• At low-fields, Pav is linear
with the field. In this range

1 Po2E
L(x) ≈ ⅓ x. Then Pav 
3 kT
•Then the dipolar/orientational polarizability is then:
1 Po2
d 
3 kT
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Interfacial polarization:
• Internal polarization occurs whenever there is an

accumulation of change at an interface between two
materials.
• The +ve charges accumulating at the interface & the

remaining -ve charges in the bulk constitute a dipole
moment giving rise to interfacial polarization.
Total polarization:
• The sum of all polarization effects:
Pavg   e Eloc   i Eloc   d Eloc
• Each effect adds linearly to the net dipole moment per

molecule.
• Interfacial effects cannot be added to the net dipole
moment.
• The Clausius-Mossotti equation however apply only to

electronic & ionic polarization:
r 1 1
 ( N e e  N i i )
r 2 3 o
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Dielectric constant and dielectric loss

• Static dielectric constant is for dc-conditions. When the
applied field is sinusoidal, then dielectric constant is different.
• Let’s consider that after a longtime of
exposure to E0, the field is reduced
from E0 to E abruptly ( E  E ).
• This results in the decrease of dipole
moment from  d (0) E0 to  d (0) E ;
(@   0,  d   d (0))
• The dipole is said to “relax” from a

higher value to a lower one, by random
Dr. Farseem Mohammedy collision. 29

• This randomization is done in time  . The excess
dipole moment is ( P   d (0) E ) .
• The rate at which the induced dipole moment is
changing is given by:
dP P   d (0) E
 (-ve sign for decrease)
dt 
jt
• For an ac-field: E  E0 sin t  E0e
dP  P d (0) jt
So,   E0e  P  d ()E0e jt
dt  
 d (0)
Here,  d ( )  1  j ;  d ( ) is the Orientational
polarizability under “ac”.
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• At low frequency, ≪ 1, ≈ 0 , p in-phase with E.
• Rate of relaxation (1/) is much faster than the frequency of
the field.
• At high frequency, ≫ 1 , 1/ is much slower than
frequency of the field. p then can no longer follow changes
in E.
• Since  d ( ) is complex, then  r is also complex:
 r   r  j r

• The real part  r  decreases from its
maximum r  (0) (@ d (0) ) to 1.0 at
high frequencies (d  0 @ ).
• This represents the relative
permittivity in capacitances.
• The imaginary part  r  is zero
at low and high frequency, but
peaks at   1 .
• This part represents the energy
lost in dielectric medium as the
dipoles are oriented against
random collision.
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• The capacitance C is then: C 

r A
d
 ZC  X C 
1

d
jC j r A 0
• Admittance:Y 
j r A 0 jA 0 

 A  A
( r  j r )   0 r  j  0 r

d d d d
o rA o rA
 Y  jC  Gp(C  , Gp  )
d d
• Thus, the admittance of the dielectric medium is a parallel
combination of a lossless C with a relative permittivity r
and a resistance of Rp 
1 .
Gp

• Real power is dissipated in R p
V2
I/P power= IV  YV 2  jCV 2 
• The real power delivered to theR p
dielectric is proportional to  r  and
peaks when   1

• The rate of energy storage by the field is determined by .
• The rate of energy transfer to the molecular collisions is
determined by 1/.
• @   1 , the processes are occurring at the same rate and

hence, energy is being transferred to heat most efficiently.
This is called relaxation peak and this process is called
dielectric resonance.
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• At this frequency the dipole relaxations are at right rate for
maximum power dissipation.
• For engineering applications, of dielectrics, r is minimized
(since this determines the energy loss) for a given r.
• Their ratio is called Loss tangent:
tan  
 r
 r
This loss peaks at  = 1/ and is in GHz range (μ –wave frequencies).
Power_ Loss V 2 1 V2 1 V2
• Power
volume
  
Rp dA d
  2 0 r
dA d

A 0 r 

 Power  E 2 0 r tan  V 
• . ( E 
d
& tan   r )
 r
• This is the dielectric loss per unit time. This represents the
power dissipated per unit volume in the polarization
mechanism: energy lost per unit time to random molecular
collision as heat.
• Dielectric loss depends on: ω, E, tanδ.
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• In general, a dielectric medium will exhibit electron and ionic
polarization also.
• For I, it would depend on frequency.
• At I, in the IR range, lattice vibration will dissipate the
energy stored in induced dipole moments.
• Thus the energy loss will be greatest when the frequency of
the polarizing field is the same as lattice vibrations ( = I)
that randomizes the polarization.
Study: page 608-609 (Kasap) Important: Example 7.5 & 7.6

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Debye equation:
• Assume a dipolar dielectric having  d and  e .
• Below optical frequencies,  e is independent of  .
• At high frequency,  d will be too sluggish to respond.

N N N N  d (0 )
• Then,  r  1
0
e 
0
 d ( )   r 
0
 d ( )   r  
 0 1  j
N  d ( 0)
• Now
0
determines the contribution of orientational
Nd (0)
polarization to the static dielectric constant.r.dc: = r.dc 0
0
 
• Thus,  r   r  j r   r  r.d .c. r
1  j
• By equating real and imaginary parts:
r.d.c r  (r.d.c r )()
Debye Equation:  r   r   ,r 
1 ()2 1 ()2
Debye equation:
•  rshows a peak at   1 representing Debye loss peak.

• This peak is much broader for solids. Because relaxation in
solids is usually represented by a distribution of relaxation
times.
• Also, in solids the dipoles can also couple.
• A plot of imaginary part  r  vs. real part r as a function of
frequency is called Cole-Cole plot.
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Debye equation:
• Debye equations can represent a

parallel combination of C  and R S
in series with C S .
0r A 0 (r.d.c r) A 
C  , Cs  , Rs 
d d Cs
• These are the circuit elements of a

Debye dielectric.
Self Study: Sec. 7.5 (Gauss’s Law) Kasap
Dielectric Strength: Insulation Breakdown
• Dielectrics are used as insulating material between conductors

at different voltages.
• The voltage across a dielectric cannot be increased
indefinitely.
• When a voltage is reached that causes a substantial current

flow between the electrodes, that is called Dielectric
breakdown.
• For non-solids (gas, liquid), generally dielectric breakdown is

not irreversible.
21
5/12/2015
Dielectric Strength
• If the voltage is removed, the dielectric can sustain voltages
again.
• For solids, this leads to irreversible damage, however.
• The dielectric strength (E br ) is the maximum field that can be

applied to an insulating material w/o causing breakdown.
• Dielectric strength of solids depend on -- molecular structure,
microstructural defects, sample geometry, nature of
electrodes, temperature, ambient conditions, duration &
frequency of the applied field.
• This strength is different under ac and dc conditions.
Study: Table 7.5 (P.621) Kasap
Study: Table 7.5 (P.621) Kasap
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Dielectric breakdown
Gases:
• There are always some free electrons in a gas due to cosmic
radiation.
• Under sufficiently large field, these electrons can be
accelerated to produce avalanche mechanism giving rise to
discharge current. This leads to gas discharge.
• This breakdown also depends on gas pressure.
• Shorter mean free path inhibits the free electrons from
accelerating.
• Thus E br increases with gas pressure.
• An air gap of 1cm at RTP is 31.7 kV/cm(@ 60Hz).
• For SF6, this is 79.3 kV/cm and is higher when pressurized.
That’s why, SF6 is used in HV circuit breakers.
Liquids:
• For impure liquids with small conductive particles in
suspension coalesce end-to-end to form a conducting bridge
between electrodes.
• This gives rise to discharges.
• Sometimes this partial discharge can be initiated in gas
bubbles entrapped in the liquid.
• Final discharges can be a series of discharges.
• Moisture absorption and absorption of gases generally
deteriorate strength.
Solids:
• There are various mechanisms of dielectric breakdown in
solids: intrinsic breakdown, thermal breakdown,
electromechanical breakdown, discharges.
Self-study: Sec 7.6.4
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Study: Kasap, Table 7.5
Piezoelectricity, Ferroelectricity & Pyroelectricity

Piezoelectricity:
• Certain crystals (SiO2, BaTiO3) become polarized under
mechanical stress.
• Charges appear on the crystal surface.
• The appearance of such surface charges lead to a voltage

difference between the two surfaces.
• The same crystal also exhibits mechanical strain/disorder

under an E-field.
• The two effects are complementary and is called

piezoelectricity.
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Piezoelectricity:
• Crystals having no center of symmetry can exhibit
piezoelectricity. These are called noncentrosymmetric crystals.
• Under stress they develop a net polarization (P).
• The direction of the induced polarization depends on the

direction of the applied stress.
• Generally, an applied stress in one direction can give rise to

induced polarization in other crystal directions.
• Suppose Tj is the applied mechanical stress along some j-
direction and Pi is the induced polarization along some i-
direction, then the two are linearly related by: Pi  dijTj
(dij are piezoelectric coefficients)
Piezoelectricity:
• The converse piezoelectric effect is that between an induced
strain Sj along j and applied electric field Ei along i: S j  dij Ei
• Piezoelectric crystals are essentially electromechanical
transducers: they convert electric signal (E-field) to
mechanical signal (strain) and vice versa.
• The transducer is simply a piezoelectric crystal (quartz) that is
appropriately cut and electroded to generate mechanical
vibrations.
• An important engineering factor in the use of piezoelectric
transducers is the electromechanical coupling between
electrical and mechanical stresses.
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Piezoelectricity:
• The electromechanical coupling factor:
2
Quartz oscillators and filters:

• Consider a suitably cut thin plate of a quartz crystal that has
thin gold electrodes on opposite sides.
• Mechanical vibrations are set-up by applying E-field (ac
source).
• Mechanical standing waves can be set-up if the wavelength
 of the waves and the length  along the travelling
directions satisfy the following condition:
1  (n is an integer)
n    
2 
• Because of the coupling of energy between electrical and
mechanical vibrations through piezoelectric effect, mechanical
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vibrations appear like a series RLC ckt. that has a minimum
impedance at the mechanical resonant frequency:
1
fs 
2 LC
• In the RLC-ckt., R  losses or mechanical damping;
L  mass of the transducer; C  stiffness
• Due to the parallel plates of electrodes, there is an additional
C 0 in parallel with the RLC circuit.

• There is a second higher
resonant frequency ( f a ) that
is due to oscillations between
L and C Co .
Antiresonant frequency
1 1 1 1
fa     
2 LC  C C C0 
• Frequencies f s and f a are
called series and parallel
resonant frequencies.
Between f s and f a , the
reactance is inductive, it is
capacitive outside.
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• The quartz oscillator is used in either of two modes.
• At f s , it behaves resistive (w/o reactive).
• Outside f s , the crystal will have reactance, and no sustained

oscillations.
• In a different mode, the circuit is designed to use the

inductance of the crystal just above f s .
Ferroelectric and Pyroelectric Crystals :

• Some crystals are permanently polarized even in the absence of
an applied field. These are ferroelectric crystals and contain a
finite P.
• Barium Titanate (BaTiO3) is a ferroelectric crystal. Above 130

C, this crystal has a cubic cell. There is no net polarization.
• Below 130 C, the structure is tetragonal. The crystal is

therefore polarized by the separation of the centers of mass of
–ve & +ve charges.
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• The critical temperature above which ferroelectric property is
lost is known as Curie temperature (TC).
• Below TC, the whole crystal becomes spontaneously polarized.
• Above TC, there is no net P.
• If we apply a temporary field E and let the crystal cool below
TC, this will induce a spontaneous polarization P to develop
along the field direction. This process is called poling.
• The polar axis (C) along which the spontaneous polarization
develops is called ferroelectric axis.
• Because of their large dielectric constants, ferroelectric
ceramics are used as high-k dielectrics in capacitors.
• All ferroelectric crystals are piezoelectric, but NOT vice versa

• A temperature
change of δT
induces a change
of polarization ∆P in
ferroelectric crystals .
This is called
pyroelectricity.
• The magnitude of this effect is quantized by pyroelectric

dP
coefficient ( ):  
dT
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Study: Kasap, Table 7.9 (p.650) for a list of materials & p values

• Pyroelectric crystals are used as infrared detectors.
• The incident IR radiation can raise the temperature of the
crystal. This can generate a voltage that can be detected.
• The induced polarization δP in a small time interval δt, due to

change in temperature δT, generates an induced
polarization charge density δP on the crystal surface .
• The flow of charges δP over time δt creates an induced

polarization current density (Jp):
dP dT
Jp  P , pyroelectric density
dt dt
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• Pyroelectric current responsivity (RI) can be defined as
pyroelectric current generated per unit input radiation power:
JP
RI  
I
• Pyroelectric voltage responsitivity (RV) is
RV 
Ionic polarization and Dielectric resonance, Kasap 7.12

• Under an alternating ac-field (E=Eoejωt), let’s calculate ionic
polarizability i in an ionic solid, two oppositely charged ions
experience a force Q.E in opposite directions.
• This stretches the bond betn the ions from ro (equilibrium
separation) to ro+x. (Fig 7.57)
• The polarization force is F=QE along the x-direction.
• This applied force is resisted by restoring force (Fr) and is
proportional to the amount of bond stretching: Fr = -βx (β is
spring const.).
• Fr is opposite to F. The net force acting on solid ions: QE-βx
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Ionic polarization and Dielectric resonance

• The ions are oscillated by the applying force.
• Some of this energy is lost to thermal vibrations by the lattice
atoms. This loss is modeled as frictional force (Floss) that
acts against the applied force.
dx
• The frictional force is: Floss   
dt
(  is a const. That
depends on the exact mechanism for energy loss from the
field.)
dx
• Thus the total force is: Ftotal  F  Fr  Floss  QE   x   dt
d 2x
Newton’s 2nd law implies: Ftotal  M r 2 (Mr is the reduced
dt M M 
mass= M  M ,
 
M± are the ± ve ions respectively)

• 2
Now d x   dx   2 x  Q E e j t
I I 0
dt 2 dt MP
(soln: the displacement of the ions under ac-field is =

(xo is complex))
• Here,  I  Mr , I
   M and  I is called the resonant

r
or natural angular frequency.
• The model described by the above eqn is called Lorentz
dipole oscillator model.
• The relative displacement of the ions from the equilibrium
(r0) separation gives rise to a net or induced polarization,
Dr. Farseem Mohammedy = . 64
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• Ionic polarizability  i is given by:
.
= = =
•Thus there is a phase difference bet E and induced P .

n
i
• Also  is complex:      j .
i i i i
2
• For dc-conditions (  0 ),  (0)  MQ i 2
• We can rewrite  ( ): i
r I
1
   2 I  
 i ( )   i (0) 1     j . . 
   I  I I 


• I is normalized frequency

•  i  peaks near the
resonant frequency,

I  1
• The sharpness and
magn. of  i  depends

on the loss-factor (  ) .
I
• The peak is sharper and

higher for a smaller  I .
•  i remains close to a constant, except around  I , where

it changes from +ve to –ve values.
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Phase of i :
• The phase of i and hence the phase of polarization w.r.t.
field, are zero at low  ( ≪ ).
• As  increases, the polarization lags behind the field and the
phase of i becomes more –ve.
• At = , the polarization lags behind field by 90ͦ.
• However, the rate of change of polarization is in phase with

the field oscillations, which leads to a maxm. energy transfer.
• For ≫ , the ions cannot respond to the rapidly changing

field, then the coupling betn. the field and ions become
negligible
Phase of i :
• The peak in i around   I is called dielectric resonance
peak.
• It can also be called ionic polarization relaxation peak and is
due to the strong coupling of the applied field with the natural
vibrations of the ionic bond at    I .
• The Clausius-Mossotti eqn. gives the relative permittivity:

Ni = concn. of +ve & -ve ions.
∈
• ∈
=
∈
+ + i = electronic polarizability of
+ve & -ve ions.
• This is the dielectric const. of an ionic solid.

• This type of polarization operates upto optical frequencies
≫
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Dispersion relation:
• At very high frequencies, ≫ , i  0 . r is then r_opt .
• So,  r ( )  1  r _ opt ( )  1 N i i N iQ 2
  
 r ( )  2  r _ opt ( )  2 3 0 3 0 M r ( I2   2  j I  )
• The above relation is the dielectric dispersion relation betn.

relative permittivity due to ionic polarization and the
frequency of the electric field.
• As    I , there are rapid changes in r () .

• The resonant frequencies ( I ) for ionic polarization
relaxations are typically in the infrared frequency range.
Dispersion relation:
• The applied oscillating field is usually an actually propagating
EM wave .
• 12
For KCl,  I  2 (4.5  10 ) rad / sec
Study: Example 7.17 (p.666)
Self-study: Electrical Displacement and Depolarizing Field

(sec 7.9)
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Refractive Index
• The refractive index is defined as the ratio of the velocity of

light in a vacuum to that in the material :
= = ∈ = ∈
• Conventionally, we talk of ‘dielectric constant’ or permittivity
for lower frequencies in the EM spectrum and of refractive
index for light. They are related through the above equation –
a measure of polarizability of a material in an alternating E-
field.
• An important application of dielectrics to optics has been that
of multilayer reflecting thin films.
Refractive Index
• Consider a layered structure with alternate layers of transparent
material having refractive indices of n1 and n2. At each
interface, there will be some light reflected, and some a b
transmitted.
• At any interface, the reflection coefficient is:
• At interface a: =
n2 n1 n2 n1 n2
• At interface b: = =− (since,  = )
• Now suppose all the layers are /4 thick (actual thickness being
n1(/4) and n2(/4)). Then the wave reflected back from ‘b’ will
be -radian out-of-phase from ‘a’ due to the path difference
(/4 + /4) and another due to phase difference. So a total of
2-radian difference has occurred. As a result, they add up in
phase.
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5/12/2015
Refractive Index
• A large number of such layers can make a good mirror.

Provided good dielectrics, overall reflection of 99.5% is
possible. Whereas, the best metallic mirror can be only 97%-
98% reflecting.
• This great reduction in losses with dielectric mirrors are
exploited in optoelectronic devices (in laser cavities).
• A related application of this multi-layer reflection can be
exploited with /4 thick layers, where successive reflection
cancel each other and we have a reflection-less coating.
-- Solymer and Walsh, 4th ed., p.268
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i
Magnetics
Sections:
Kasap Ch. 8
Handouts: #6 & #7
Now to other things!

And I'll begin to treat by what decree
Of Nature it came to pass that iron can be
By that stone drawn which Greeks the magnet call
After the country's name (its origin Being in country of Magnesian
folk).
This stone men marvel at; and sure it oft Maketh a chain of rings,
depending, lo,
From off itself! Nay, thou mayest see at times
Five or yet more in order dangling down
And swaying in the delicate winds, whilst one
Depends from other, cleaving to under-side,
And ilk one feels the stone's own power and bonds-
So over-masteringly its power flows down.
- ON THE NATURE OF THINGS by Titus Lucretius Carus, 50 BC
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Mysterious Attraction
Mysterious Attraction
• There are many curious paradoxes relating

the workings of magnet.
• Lodestone was known for its magnetic

property and eluded people since antiquity
“The discovery of magnetism began with a type of rock. Magnetite is

a mineral with chemical formula Fe3O4 … it gets its name from
Magnesia, a region of central Greece … This mysterious [magnetic
attraction] was known by the Greeks (it is mentioned by Thales of
Miletus in 6th century BCE) and also to the Chinese (there is a
reference to magnetism in literature of the 4th century BCE).” –
Stephen Blundell
Fatal Attraction
• Modern thinking about magnets started with Gilbert.
• William Gilbert wrote about magnets, apart from many other

matters of science, in the courts of Queen Elizabeth I in 1600.
• He originated scientific understanding of magnetic properties

and the term ‘electricity’.
2
2/23/2014
Prolegomena
• In the World, greater than 20,000 TWh of electricity are
generated in 2012, electrical power in this quantity would be
hopelessly impractical without large quantities of expertly
controlled ferromagnetic material
• The majority of engineering devices use farromagnetic and
ferrimagnetic materials.
• But there is also the immensely interesting property of
superconductivity which is related to the magnetic properties
of solids
• High-temperature superconductivity was doscovered in 1986
Magnetization of solids
• Consider a current loop where there is a circulating
current I.
• The area enclosed by the loop is A and the unit
vector un comes out off the
h plane
l and
d its direction
d is
such that looking along it, the current ciculates
clockwise.
• Then the magnetic dipole moment is defined as:
μ m  IAu n
Unit vector normal to the
Magnetic moment Current surface
Area circled by current
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2/23/2014
Magnetic dipole moment
• The magnetic moment, when placed in a magnetic field,
experiences a torque – this torque tries to align the dipole axis
with the magnetic field
• Also
l since the
h dipole
d l is a current loop,
l it gives rise to a
magnetic field B.
• The B at a distance r from the magnetic moment is: B  m/r3.
Atomic moment
• Extending the idea of magentic moment, an
electron orbiting around a nucleus also behaves
like a current loop, and has associated orbital
magnetic moment orb.
• I = charge flowing per unit time
= -q/period = -q/2.
• Moment = current[I] x area[r2] = -qr2/2
• Orbital angular momentum L = (mv).r = (mr).r
• Then
q
 orb   L
2me
• Thus orb  orbital angular momentum and the
proportionality constant is electron charge-to-mass
ration, i.e. gyromagnetic ratio.
4
2/23/2014
• The electron also has an intrinsic angular momentum – spin.

And this relates to spin magnetic moment
q
spini   S
me
• Overall magnetic moment for an electron is orb + spin.
• The total megnetic moment for the whole atom consists of
orbital motions and spins of all the electrons – but electrons
from only unfilled sub-shells contribute to the overall magnetic
moment.
• Because L ans S are quantized, and in a closed shell, these
values get netly canceled.
Bohr Magneton
• Let us consider an atom of closed inner shells (l=0) and a single

electron in an s-orbital.
• This means that orbital magnetic
g moment = 0,, thus atom =  spin
• Now in the presence of an external Bz along z-direction, the magnetic
moment cannot simply rotate and align itself to z-direction.
• Since Sz must be space quantized, i.e. Sz must have values ±1/2 ħ.
• The torque experienced by the spinning electron causes the spin
moment to precess about the z-axis; such that Sz = -1/2 ħ
• The averageg magnetic
g moment thus becomes,,
e
 z   S z   ms   
e e
 B
me me 2me
• B is called the Bohr magneton and has the value 9.2710-24 A m2 or
J T-1.
5
2/23/2014
Magnetization Vector
• Consider an ideal solenoid – enclosing free space. If current
flow through the wound wire, then a magnetic field Bo is
observed.
• Now if the free space is filled with some material
material, the magnetic
field changes from Bo to B.
• The medium gets magnetized.
• Each atom of the filling medium responds to Bo and acquires a
net magnetic moment um along the applied field. The
precession of each atomic magnetic moment about Bo gives
rise to m.
• The magnetic vector M describes the extent of magnetization
of the medium.
• M is defined as magnetic dipole moment per unit volume: M =
nat . av
• nat = no of atoms per unit volume, av = avg magnetic moment per atom
• We can assume that each atom acquires av along Bo. Each of
these magnetic moments can be viewed as elementary current
loop at atomic scale. These current loops are due to electronic
currents within the atom and arise from both orbital and spin
motions of electrons.
• Magnetization = surface current
• Study Figure 8.7, page 690, Kasap.
6
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Magnetic Field Intensity H
• The magnetic field in a solenoid filled with a medium is given
by B = o (I' + Im) = o I' + o Im = Bo + oM
• Here, I' is the conduction current per unit length of the solenoid, Im is the surface
current
• The field inside the material is the sum of the applied field Bo
and a contribution from the magnetization M of the material.
• The magnetization arises from the application of Bo due to the
current of free carriers (conduction current) in the wires. It is
useful to define a vector field that represents the effect of the
external.
external
• So [B - oM] represents the magnetizing field caused by
external effects: 1 1
H BM  B0
o o
• This is also known as the magnetic field intensity, H = NI
Permeability
• Permeability  relates the effect B to the cause H at the some
point inside a material.   B
H
• It represents to what extent a medium is permeable by
magnetic fields.
• μ indicates how permeable the material is to the magnetic field.
A material which concentrates a large amount of flux density in
its interior has a high permeability
• Relative permeability r of a medium is the fractional increase

in magnetic field with respect to the field in free space when a
material medium is introduced B B
r  
Bo  o H
• And of course,  = 0 . r
7
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Susceptibility
• The properties of a material are defined not only by the magnetization, or
the magnetic induction, but by the way in which these quantities vary with
the applied magnetic field.
• The magnetization produced in a material depends on the magnetic field,
and of course to the magnetic field intensity:
M  mH
• The proportionality constant m is the magnetic susceptibilty
• The susceptibility indicates how responsive a material is to an applied
magnetic field – the degree of magnetization of a material in response to an
applied magnetic field.
• m is a small number and rarely exceeds 10-5
• Note: the above relations is only true for isotropic [properties are same in all
directions] material.
• B = o.[H + M] = oH + oM = oH + o m H = o[1+m]H
• Therefore, r =1+m
• The inductunce of a solenoid with a magnetic medium inside increases by a
factor of r.
8
2/23/2014
Quantum Magnetism
• If one assumes nothing more than Classical Physics and then go on
modeling a solid material as a system of electric chanrges, then one
can show that the system can have NO magnetization – Bohr - van
Leeuwen Theorem
• In other words, there can be no natural/permanent magnets: the
lodestone should not exist
• Yet lodestonses exist in nature and magnets do stick to your
refrigerator and that shows that quantum world is no less real.
• In 1920s and 1930s, physicists applied the newly developed quantum
theories to magnetism and found that magnetic properties of many
real materials can be explained by quantum theories
• Many materials are known to be weakly diamagnetic, and when
placed under a magnetic field, they become weakly magentic in the
opposite direction – water is an example
• This phenomena is the background of Andre Geim's famous
experiemnt of levitating frog
Geim's frog
• Read Andre Geim's Nobel lecture 2010 :

http://www nobelprize org/nobel prizes/physics/laureates/2010/g
http://www.nobelprize.org/nobel_prizes/physics/laureates/2010/g
eim-lecture.html
• Read Handout # 6 for quantum explanations of magnetic

properties
9
2/23/2014
Magnetic Materials*
"A sensitive compass having a Bi needle would be ideal for the young man
going west or east, for it always aligns itself at right angles to the magnetic
field". - William H. Hayt Jr., Engineering Electromagnetics, 1958
• The magnetic properties of electrons combine to produce the

magnetic properties of atoms
• When the atoms aggregate in a solid, the individual magnetic
properties of solids combine to produce a resultant magnetic
moment.
• The electrons that are responsible
p for chemical bonds are also
responsible for magnetic properties
• The fixed ions have filled shells, hence they do not contribute to
magnetism
• However the conduction electrons' spin do align and give rise to
magnetic properties [1] A good references is Magnetic Materials by Nicola
Dr. Farseem Mohammedy Spaldin, 2nd Ed, Cambridge University Press, 2011 19
Magnetic Materials
• Remember that we have four main classes of magnetic materials: the para-,
antiferro-, ferro-, and ferrimagnets.
10
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Paramagnets
• The individual atoms or ions have magnetic moments, but

th
these moments t are didisordered,
d d so that
th t there
th is
i no nett
magnetization.
• The susceptibility is positive, because the external field causes
the moments to partially align with it; and it is small, because
the thermal energy which tends to disorder the moments is
large compared with the magnetic energy that tends to align
them along the field direction
direction.
• Many metals are paramagnetic – due to the alignment of the
majority of spins of conduction electrons with the field
Magnetic Materials
• Antiferromagnets. Here the magnetic moments on the individual
atoms or ions align in an antiparallel fashion so as, overall, to cancel
each other out. As in the case of the paramagnets, there is no net
zero-field magnetization and a small positive susceptibility; note that
the
h microscopic
i i structure is
i very different,
diff however.
h
• Ferromagnets. In the ferromagnets the moments align parallel to
each other, yielding a large net magnetization. The susceptibility can
be very large and is often hysteretic because the magnetization
process proceeds via domain-wall motion.
• Ferrimagnets. The ferrimagnets are microscopically similar to the
antiferromagnets, in that they consist of two sublattices within which
th moments
the t are aligned
li d parallel,
ll l with
ith the
th two
t sublattices
bl tti aligned
li d
antiparallel to each other. However, the magnitudes of the magnetic
moments in the two sublattices are different, so that there is a net
magnetization. As a result they behave macroscopically like the
ferromagnets, with large positive susceptibility and hysteresis.
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2/23/2014
Diamagnets
• Diamagnetism is such a weak
phenomenon that only those atoms
which have no net magnetic moment
as a result of their shells being filled
are classified as diamagnetic.
• Having closed sub-shells and shells
means that each constituent atom has
no permanent magnetic moment in
the absence of an applied field.
A diamagnetic material
• We stated that the susceptibility of a placed in a non‐uniform
diamagnetic mate
material
ial is negative,
negati e that magnetic field experiences
is, the magnetization decreases as the a force towards smaller
magnetic field is increased. fields. This repels the
diamagnetic material away
Daimagnets try to expel the applied from a permanent magnet.
magnetic field
12
2/23/2014
Origin of ferromagnetism
exchange interaction
• Self study:
– Section 8.3, Kasap
Section 8 3 Kasap
– Handout#6, Blundell
Curie temperture
• When all the atomic magnetic moments are aligned as mush as
possible, at that instant the magnetization in a ferromagnet
does not increase any fruther
• This
h is saturation magnetization Msat.
• For an iron crystal, Msat corresponds to each Fe atom with an
effective spin magnetic moment of 2.2 Bohr magneton aligning
in the same direction to give oMsat = 2.2 Tesla
• Now if you increase the temperature of the material, lattice
vibrations become more energetic – disrupting the spin
alignment
• The ferromagetic property dissappears at some elevated
temperature called the Curie temperture, Tc.
• Above Tc, the material behaves as if its paramagnetic.
13
2/23/2014
Curie temperture
• Msat decreases from its

maximum
i value
l att absolute
b l t
zero to zero value at Tc
• The thermal energy at Tc is kTc
and it is an order of magnitude
approximation to the exchange
interaction Eex.
• For Iron,
F I Tc = 1043K,
1043K Eex = 0.09eV
0 09 V
• For Cobalt, Tc = 1400K, Eex = 0.1eV
Magnetic Domains
• A magnetic domain is a region of the
crystal in which all the spin magnetic
moments are aligned to produce a
magnetic moment in some direction
• The magnetization of each domain is
normally along one of the preferred
directions in which the atomic spin
alignments are easiest (Eex is
strongest)
• F Iron,
For I th magnetization
the ti ti iis easiest
i t
along the six directions of 100 family.
• Along the boundaries of micro-regions
having different net magnetization,
there are Domain walls.
14
2/23/2014
Magnetic domains
• Magnetic domains in a single grain (outlined
with a black line) of non-oriented electrical steel.
The photo shows an area 0.1 mm wide. The
sample was polished and photographed under
Kerr-effect microscope. The polishing was not
perfect - there is an angled scratch through the
whole width of image (top half of the photo).
The area outside of the grain has different
crystallographic orientation, so the domain
structure is much more complex. The arrows
show the direction of magnetisation in each
domain - all white domains are magnetised "up",
all dark domains are magnetised "down".
Magnetic Domains
• In an unmagnetized crystal of iron in the absence of an applied magnetic

field, domains A and B are the same size and have opposite
magnetizations.
• When an external field is applied the domain wall migrates into domain B
which enlarges A and B. The result is that the specimen now acquires net
magnetization M along H.
• Self-study, section 8.5.3 Domain Walls, Kasap Think:

1. What causes the migration
of the domain walls?
15
2/23/2014
Magnetization Curves
• Let us consider a single-crystal unmagnetized iron – there are
lots of domain, and the magnetization in each domain is ine
one of six easy directions.
• Now apply l a magnetic field
f ld along
l one off the
h easy directions
d
• As the field increases, domains in the direction of the applied
field will increase at the expense of other domains, untill the
whole material contains only one single domain
• Since the domain walls move easily, the magnetic field required
to reach Msat is small.
• The scenario is slightly different when the magnetic filed is
applied along [111] direction.
B‐H curves
• The magnetization curve of a typical
ferromagnetic material exhibits
hysteresis.
• Starting with a completely demagnetized material, we move up the curve
along 2, 3, 4, 5 as the magnetic field is increased. Reducing then the
magnetic field, we get back to point 6, which is identical with point 4, but
further decrease takes place along a different curve. At 7 there is no
applied magnetic field, but B is finite. Its value, B = Br, is the so called
remanent flux density. Reducing further, the magnetic field B takes the
values along 8, 9, 10.
• R
Returning from 10, we find that 11 is identical with 9 and then proceed
i f 10 fi d h 11 i id i l i h 9 d h d
further along 12 and 13 to reach finally 4.
• The loop 4, 7, 8, 9, 12, 13, 4 is referred to as the hysteresis loop. It clearly
indicates that the magnetization of iron is an irreversible phenomenon.
• Note that the value of H at 13 is called the coercivity, denoted by Hc. It
represents the magnetic field needed for the flux density to vanish.
16
2/23/2014
B‐H Curves
• The paths 4, 5 and 9,10 suggest that rotation from easy into
difficult directions is reversible, thus the causes of irreversibility
should be sought in domain movement.
• Because off theh presence off allll sorts off defects
d f in a reall
material, the domain walls move in little jerks, causing the
magnetization to increase in a discontinuous manner (region 2,
3 magnified in Fig).
• The walls get stuck once in a while and then suddenly surge
forward, setting up in the process some eddy currents and
sound d waves, which
hi h consume energy. SuddenS dd jerks
j k ini wallll
motions lead to small jumps in the magnetization of the
material – This is called Birkhausen Effect.
• If energy is consumed, the process cannot be reversible, and
that is the reason for the existence of the hysteresis loop.
17
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Demagnetization
• It is easy to demagnetize – due to
domain wall motions being reversible
and as soon as the field is removed,
there is some domain wall motion
'bouncing backwards' .
• The simplest method to demagnetize is
to subject the material with ample
magnitude of magnetic intensity to
reach full saturation levels
• Th apply
Then l repeated
t d cycles
l off
hysteresis loop, each time with
decreasing magnitude, untill the B-H
loops are so small that they end up at
the origin when H = 0.
The B vs. H hysterisis loop depends on the

magnitude of the applied field in addition to the
Material and sample and size.
18
2/23/2014
• How can we classify

magnetic materials?
• There is a simple division
into soft and hard
magnetic materials.
• Why soft and hard?
• Well, the hard materials
are those which are hard
to magnetize and
demagnetize.
• So materials which are
easy to magnetize an
demagnetize should be
called easy materials. In
fact, they are called soft
materials, and there is
nothing we can do about
that.
• We have to remember,
though, that these are
only very tenuously related
to mechanical properties,
which may also be hard
and soft.
Applications of Ma
Applications of Magnetism
• From Giant Magneto-Resistance (GMR) to spintronics, magnetism has
diverse applications in everyday life
• Read Handout#6
19
2/23/2014
Applications of Magnetism
• Magnetic separators, magnetic holding devices, such as magnetic latches.
• Magnetic torque drives
• Magnetic bearing devices
• Magnetos
• G
Generators
t and
d alternators
lt t
• Eddy current brakes (used widely for watt-hour meter damping).
• Motors
• Meters
• Loudspeakers
• Relays
• Actuators, linear, and rotational
• M
Magnetic
ti focused
f d cathode-ray
th d t b
tubes
• Traveling Wave Tubes
• Magnetrons, BWO, Klystrons
• Ion Pumps
• Cyclotrons
• More applications at http://www.cndailymag.com/use.htm
20
2/23/2014
Giant
iant M
Magneto
agneto‐‐Resistance
• Read the Nobel 2007 lecture by Albert Fert on GMR
The first printable magnetic sensor relying on the giant magnetoresistance
effect (GMR) is demonstrated. It is prepared in the form of magneto‐sensitive
inks adherent to any kind of arbitrarily shaped surface. The fabricated sensor
exhibits a room‐temperature GMR of up to 8% showing great potential for
contactless switching in hybrid electronic circuits (discrete semiconductor and
printable elements) applied to the surface by regular painting.
The challenges of creating low temperatures
• Michael Faraday was the first to liquefy chlorine gas in 1823.
• He employed a technique to liquefy gas by producing high
pressures in a sealed tube
• In 1852, James Joule and Lord Kelvin developed a method of
cooling gases by rapid expansion
• Sir James Dewar on 10 May 1898 produced 20 cm3 [= 5
teaspoonfuls] of liquid hydrogen.
• Howeever, it was Heike Kamerlingh Onnes who in 1908
liquefied
q helium at 4.2K
• And superconductivity began!
Read handout#7 for details on the hunt for
cryogenics
21
2/23/2014
• "Faraday's problem
as to whether all
gases can be
liquefied has now
been solved step by
stepp in the sense of
van der Waals' words
'matter will always
show attraction' and
thus a fundamental
problem has been
removed"
- H. K. Onnes
Nobel Committee on Low Temperatures
• "As early as 100 years ago research into the behaviour of gases at various pressures and temperatures gave a great impetus to
physics. Since this time the study of the connection between the pressure, the volume and the temperature of gases has
played a very important part in physics, and particularly in thermodynamics - one of the most important disciplines of modern
physics.
In the years 1873 and 1880 Van der Waals presented his famous laws governing gases which, owing to their great importance
for thermodynamics, were rewarded by the Royal Academy of Sciences in 1910 with the Nobel Prize for Physics.
The thermodynamic laws of Van der Waals were laid down on atheoretical basis under the assumption that certain properties
could be attributed to molecules and molecular forces. In the case of gases the properties of which are changed by pressure
p
and temperature, , or in one wayy or another do not agree
g with Van der Waals' hypothesis,
yp , deviations from these laws occur.
A systematic experimental study of these deviations and the changes they undergo due to temperature and the molecular
structure of the gas must therefore contribute greatly to our knowledge of the properties of the molecules and of the
phenomena associated with them.
It was for this research that Kamerlingh Onnes set up his famous laboratory at the beginning of the 1880's, and in it he
designed and improved, with unusual success, the physical apparatus needed for his experiments.
It is impossible to report briefly here on the many important results of this work. They embrace the thermodynamic properties
at low temperatures of a series of monatomic and diatomic gases and their mixtures, and have contributed to the development
of modern thermodynamics and to an elucidation of those associated phenomena which are so difficult to explain. They have
also made very important contributions to our knowledge of the structure of matter and of phenomena related to it.
Whilst important on its own account, this research has gained greater significance because it has led to the attainment of the
lowest temperatures so far reached. These lie in the vicinity of so-called absolute zero, the lowest temperature in
thermodynamics.
The attainment of low temperatures in general was not possible until we learnt to condense the so so-called
called permanent gases,
gases
which, since Faraday's pioneer work in this field in the middle of the 1820's, has been one of the most important tasks of
thermodynamics.
After Olszewski, Linde, and Hampson had prepared liquid oxygen and air in a variety of ways, and after Dewar, having
overcome great experimental difficulties, had succeeded in condensing hydrogen, all temperatures down to -259°C, i.e. all
temperatures down to 14° from absolute zero, could be attained.
At these low temperatures all known gases can easily be condensed, except for helium, which was discovered in the
atmosphere in the year 1895.
Thus, by condensing this it would be possible to reach still lower temperatures. After both Olszewski and Dewar, Travers, and
Jacquerod had tried in vain to prepare liquid helium, using a variety of met hods it was generally assumed that it was
impossible.
22
2/23/2014
"The question was solved in 1908, however, by Kamerlingh Onnes, who then prepared liquid helium for the first time.
I should have to cover too much ground if I were to report here on the experimental equipment with which
Kamerlingh Onnes was at last successful in liquefying helium, and on the enormous experimental difficulties which
had to be overcome. I would only mention here that the liquefaction of helium represented a continuation of the long
series of investigations into the properties of gases and liquids at low temperatures which Kamerlingh Onnes has
carried out in so praiseworthy a manner. These investigations finally led to the determination of the so-called
isotherms of helium and the knowledge gained here was the first step towards the liquefaction of helium. Kamerlingh
q
Onnes has constructed cold baths with liquid helium which permit
p research to be done into the properties
p p of
substances at temperatures which lie between 4,3° and 1,15° from absolute zero.
The attainment of these low temperatures is of the greatest importance to physics research, for at these
temperatures both the properties of the substances and also the course followed by physical phenomena, are
generally quite different from those at our normal and higher temperatures, and a knowledge of these changes is of
fundamental importance in answering many of the questions of modern physics.
Let me mention one of these particularly here.
Various principles borrowed from gas thermodynamics have been transferred to the so-called theory of electrons,
which is the guiding principle in physics in explaining all electrical, magnetic, optical, and many heat phenomena.
The laws which have been arrived at in this way also seem to be confirmed by measurements at our normal and
higher temperatures. That the situation is at very low temperatures not the same, however, has, amongst other
things, been shown by Kamerlingh Onnes' experiments on resistance to electrical conduction at helium temperatures
and by the determinations which Nernst and his students have carried out in relation to specific heat at liquid
temperatures.
It has become more and more clear that a change in the whole theory of electrons is necessary. Theoretical work in
this direction has already been begun by a number of research workers
workers, particularly by Planck and Einstein
Einstein.
In the meantime new supports had to be created for these investigations. These could only be obtained by a
continued experimental study of the properties of substances at low temperatures, particularly at helium
temperatures, which are the most suitable for throwing light upon phenomena in the world of electrons. Kamerlingh
Onnes' merit lies in the fact that he has created these possibilities and at the same time opened up a field of the
greatest consequence and significance to physical science.
Owing to the great importance which Kamerlingh Onnes' work has been seen to have for research in physics, the
Royal Academy of Sciences has found ample grounds for bestowing upon him the Nobel Prize for Physics for the year
1913.
http://www.nobelprize.org/nobel_prizes/physics/laureates/1913/press.html
Superconductivity
• In 1911, Onnes discovered that when a sample of mercury is
cooled below 4.2K, its resistivity just vanishes
• This is a state when there is no resistance to current flow – a
state of superconductivity
• The critical temperature below which a material exhibits
superconductivity is Tc and it is different for different materials
• The resistivity of some normal conductors (Cu, Ag, Au) show a
non-zero value at absolute zero – the residual resistivity arises
from scattering and defects
• The earlyy researches in superconductivity
p y showcased quite
q a
few alloys showing zero-resistivity at extremely low
temperatures
• But later in the 1980's, researchers unveiled superconductivity
at elevated temperatures – at present the highest Tc is 133K for
HgBa2Ca2Cu3O8 alloy.
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2/23/2014
Some superconductors
• The critical temperature and critical magnetic field (at T = 4.2 K) of the
more important hard superconductors
Meissner effect
• A superconductor cooled below its critical temperature expels

all magnetic field lines from the bulk by setting up a surface
current.
• A perfect conductor (σ = ∞) shows no Meissner effect.
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2/23/2014
Magnetic levitation
Left: A magnet over a superconductor becomes levitated. The superconductor is a perfect
Diamagnet which means that there can be no magnetic field inside the superconductor.
Right: Photograph of a magnet levitating above a superconductor immersed in liquid nitrogen
(77 K). This is the Meissner effect.
Types of supercondusctors
• Two types – type I and Type II, based on their diamagnetic
properties
25
2/23/2014
Type I Superconductor
• In type I superconductors, as the applied magnetic field B
increases, so does the opposing magnetizing field till the field
reaches a critical value Bc, whereupon superconductivity
disappears
The critical field vs. temperature in Type I superconductors.
Type II Superconductor
• In type II superconductors, the transition does not occur
sharply from Meissner state to normal state
• There is an itermediate state in which the magnetic field is able
to pierce through certain local regions of the sample
• As the magnetic field increases, initially the sample behaves as
a perfect diamagnet – it exhibits Meissner effect and expels all
magnetic flux
• As the field keeps on increasing beyond a critical value, Bc1, the
magnetic flux lines are no longer totally expelled.
• As the field increases even further,, more flux lines pierce
p
through the sample till Bc2, when all fields penetrate the sample
and superconductivity ceases to exist.
• Type II's have two critical fields – lower and upper critical
fields, Bc1 and Bc2
26
2/23/2014
Characteristics of Type I and Type II superconductors. B = µoH is the
applied field and M is the overall magnetization of the sample. Field inside the
sample,
Binside = µoH + µoM, which is zero only for B < Bc (Type I) and B < Bc1 (Type II).
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2/23/2014
Critical current density
• It is seen that if a critical current density Jc passes through a
superconductor, it will generate its own magnetic field and at
sufficiently high values, the magnetic field at the surface of the
sample will exceed the critical field and extinguish
superconductivity
• This relation between Bc and Jc is only true for type I
superconductors; and is complicated in case of type II's
• The limits of superconductivity are defined by – critical
temperature Tc, critical magnetic field Bc, and critical current
d
density
it Jc
• Thus, these are important engineering parameters to consider
while designing superconducting coils in Maglev, or LHC tunnels
or elsewhere.
28
2/23/2014
BCS Theory
Cooper Pair
29
24-Nov-15
unit cell of a microwave metamaterial Split-ring resonator array Metamaterial superlens

consisting of a split-ring resonator and
metal wires
Metamaterials
Negative refraction
Solymar & Walsh

Ch. 15
Handout: #8
Read the wiki article on Metamaterial
Artificial Material
• The idea of artificial material is not new – it has been known for
about three scores of years that inclusion of bits of metal in a
dielectric will lead to some modest change in the dielectric constant.
• Gabriel Lippman in 1894 started to think about artificial materials –
developed a film in the form of a dielectric variation caused by
standing waves
• In 1898 Sir Jagdish Chandra Bose proposed twisted jute as an
artificial material that could rotate the polarization of EM waves – an
artificial chiral material
1
24-Nov-15
Natural materials vs artificial materials

• Most materials that we discussed were natural – they appeared
as they are in nature, or tweaked artificially here and there
• An artificial material is different in every respect from those
natural
Photonic bandgaps and metamaterials

• We all know what natural materials are made up by lots and
lots of small elements like atoms and molecules.
• Some of these materials are amorphous, meaning that all those
elements are heaped upon each other in a random manner
• Others are crystalline, which means that they arrange
themselves into some regular periodical pattern.
• Recently, however, there have been some new developments -
we can now think of artificial materials in which atoms and
molecules are replaced by macroscopic, man-made, elements.
• They could be roughly divided into two classes - in one case
the distance between the inclusions is comparable with the
wavelength, in the other case it is small relative to the
wavelength.
• The first one is known as the subject of photonic band gaps
and the second one as metamaterials.
2
24-Nov-15
a/λ
• Our main interest is in the interplay of waves and
materials restricted to classical physics. The key
parameter is a/λ, where a is the distance between
elements in the material and λ is the free-space
wavelength.
• We may now look at two cases: the wavelength is
comparable with a or much larger than a.
• In the first case the Bragg effect comes into play.
• An EM wave may be incident perpendicularly at a lattice. The
wave propagating then from row 1 to row 2 will cover a path a.
The part of the wave that is reflected by row 2 will have covered
an additional distance a when arriving back at row 1.
• When a happens to be equal to one-half of a wavelength then
the waves reflected by all the rows will have the same phase and
will reinforce each other.
• If there are many rows, and there are indeed many of them in a
crystal, then most of the incident power may be reflected.
• This effect is at the basis of X-ray and electron
diffraction in crystals.
a/λ
• When the wavelength >> lattice period, then no such
dramatic effect occurs, but it is nonetheless
significant.
• There may not be major reflection or diffraction but the
electromagnetic wave is still considerably affected when it
enters a material.
• We may then ignore the details and pretend that there is
no discrete structure: the material is homogeneous and
continuous.
• The aim is then to find some effective parameters
like electric permittivity and magnetic permeability.
• This is known as the effective-medium
approximation.
• Summarizing, there is the Bragg effect, when the
distance between the elements is comparable with
the wavelength, and there is effective-medium
response when that distance is much less than the
wavelength.
3
24-Nov-15
What is Metamaterials
• We shall give here two definitions –
– 1. Metamaterials are engineered composites that exhibit superior
properties not found in nature and not observed in the constituent
materials.
– 2. A metamaterial is an artificial material in which the electromagnetic
properties, as represented by the permittivity and permeability, can be
controlled. It is made up of periodic arrays of metallic resonant
elements. Both the size of the element and the unit cell are small relative
to the wavelength.
Originates from a Greek word ta: "after/beyond"
Example: metaphysics ("beyond nature"):
– a branch of philosophy concerned with giving a general and fundamental
account of the way the world is.
Metamaterials are artificially engineered materials possessing properties

(e.g., mechanical, optical, electrical) that are not encountered in
naturally occurring materials
What is Metamaterials
• Wiki says
• Metamaterials are artificial media structured on a size scale smaller than the
wavelength of external stimuli. Materials of interest exhibit properties not found in
nature, such as negative index of refraction. They are cellular assemblies of multiple
elements fashioned from materials including metals and plastics, arranged in periodic
patterns. Metamaterials gain their properties not from their constituents, but from
their exactingly-designed structures. Their precise shape, geometry, size, orientation
and arrangement can affect light or sound in a manner that is unachievable with
conventional materials.
• Potential applications of metamaterials are diverse and include
remote aerospace applications, sensor detection and infrastructure monitoring, smartsolar
power management, public safety, radomes, high-frequency battlefield communication and
lenses for high-gain antennas, improving ultrasonic sensors, and even shielding structures from
earthquakes.
• Metamaterial research is interdisciplinary and involves fields including electrical engineering,
electromagnetics, solid state physics, microwave and antennae engineering, optoelectronics,
classic optics, material sciences, semiconductor engineering, nanoscience.
• Metamaterials have become a new subdiscipline
within physics and electromagnetism (especially optics and photonics).
• They show promise for optical and microwave applications such as new types of beam
steerers, modulators, band-pass filters, lenses, microwave couplers, and antenna systems.
Furthermore, the lower density of materials means that components, devices, and systems can
be lightweight and small, while at the same time enhancing system and component
performance.
4
24-Nov-15
• The physics of "small-scale" lies at the heart of the

metamaterial advantage. The physics at small scale is different
than bulk physics and, from a performance standpoint, often
significantly better. Quantum confinement, exchange-biased
ferromagnetism, and effective media responses are all
examples of how the physics at small-scale can result in
enhanced electromagnetic properties.
- Gennady Shvets, The University of Texas at Austin
5
24-Nov-15
Photonic bandgaps
• As we know, electrons in a semiconductor have allowed and

forbidden energies.
• Why do electrons behave that way? It is essentially due to the
wave-like nature of the electron. When they see a periodic
potential in a periodic medium, they respond.
• Photons can do the same thing if they find themselves in a
periodic medium. Put photons into a periodic medium and they
will have allowed and forbidden energies which, in this context,
means that the propagation of the electromagnetic waves in
that medium is allowed or forbidden.
• The modern term for it is photonic bandgaps.
Photonic bandgaps
• What are the applications of photonic bandgap materials?
• They can be used whenever there is a need for electromagnetic
waves propagating in any direction to be reflected.
• They are singularly suitable for constructing resonant cavities –
replace a few elements of a photonic bandgap material by one capable of
lasing, pump the laser at a wavelength for which the bandgap material is
transparent and the whole laser device is ready.
• This is actually the way to produce very small lasers where very
small means that its dimensions are submicrometre.
• Another application is for guiding light. If we have a cylindrical
photonic bandgap material and we clear the area around the axis, then an
optical wave can propagate there without being able to spread outwards in
the radial direction. This is because a wave propagating in any but the axial
direction will be reflected. These photonic bandgap waveguides promise
lower losses for guiding waves to a long distance.
6
24-Nov-15
Resonant elements in Metamaterials

• Most metamaterial elements are resonant and then the problem
arises how to make them small.
• It is not trivial to satisfy the requirement for the elements to be
resonant and at the same time to be small relative to the
wavelength.
• We shall concentrate on one resonator, a member of the family
of split-ring resonators (SRRs),
• It consists of two concentric split rings with gaps on opposite
sides.
Split ring resonator

• Each ring has a self-inductance, there is a mutual inductance
between them, there is a capacitance between the rings and
there are gap capacitances at the splits.
• The exact analysis is difficult, but there is an excellent
approximation and that leads to simplified resonant frequency
formula – the capacitance of the half-ring is Chalf-ring= .ro.Cpu,
where Cpu is the inter-ring capacitance per unit length and the
resonant frequency is
 r0 LC pu
w0 
2
7
24-Nov-15
What is a dielectric permittivity?
  External field polarizes dielectric

E0 Ein  field inside dielectric is smaller
- + that outside  ratio is called
dielectric permittivity 
- +
- + E0

   Ein
Ein  E0  4P 
P
•In most materials  > 1 (e.g.,  = 12 for Si,  = 2.25 for glass)
•Permittivity depends on frequency: long lookup tables!
•Not without exceptions:  < 0 in metals (visible, IR,…)
What is a magnetic permeability?
 
B0 Bin •External B-field magnetizes
material
•More complex mechanisms:
electron and nuclear spins
   •Field inside can be smaller, or
B  H  4M larger, or much larger
B 
 0 M
Bin
•In most materials  > 0

•There are exceptions (ferrites), but only at microwave
frequencies
8
24-Nov-15
How waves propagate (or not)?
Propagation of electromagnetic waves in medium is

determined by  and  of the medium (J. C. Maxwell):
nw w
k  
c c
In most natural materials

 > 0,  > 0 waves propagate
Sometimes either  < 0, or

 < 0  no propagation
n  ( )(  )  0
DNG, SNG, ENZ and MNZ Metamaterials

• We know the expression for the refractive index in terms of the
relative permittivity and permeability, n = √εrμr .
• When both μr and εr are positive then there is no problem,
everything is familiar
• Some may ask what μr is doing in that equation. That objection
can be easily overcome by asserting that the relative
permeability may indeed be different from unity for
metamaterials.
• What happens when only ε is negative? That happens in
plasmas
9
24-Nov-15
Engheta, N., Alu, A. ; Silveirinha, M.G. ; Salandrino, A. ; Jingjing Li, “DNG, SNG, ENZ and MNZ Metamaterials and Their
Potential Applications,” IEEE Trans Antennas and Propagation Magazine, V ol 49, Issue 1, Feb 2007, p 23-36.
Engheta, N., Alu, A. ; Silveirinha, M.G. ; Salandrino, A. ; Jingjing Li, “DNG, SNG, ENZ and MNZ Metamaterials and Their
Potential Applications,” IEEE Trans Antennas and Propagation Magazine, V ol 49, Issue 1, Feb 2007, p 23-36.
10
24-Nov-15
Negative index *
• But Veselago, in a paper written in Russian in 1967 and
published in English in 1968, asked a more daring question:
What happens when both μr and εr are negative?
• He discusses the possible responses as quoted below:
• "The situation can be interpreted in various ways. First, we may admit that
the properties of a substance are actually not affected by a simultaneous
change of the signs of ε and μ. Second, it might be that for ε and μ to be
simultaneously negative contradicts some fundamental law of nature, and
therefore no substance with ε < 0 and μ < 0 can exist. Finally, it could be
admitted that substances with negative ε and μ have some properties
different from those of substances with positive ε and μ."
* For further details, read Solymar and Shamonina’s Waves in

Metamaterials, section 2.11. Also quoted in Handout-8.
Negative index
• Assuming a plane wave propagating in a medium with material
constants ε and μ in the form exp(−j k・r), we can rewrite Maxwell's
first two equations as: k×H = ωεE and k×E = −ωμH.
• It may be seen from the above equations that it makes a difference
whether the material constants are both positive or both negative. In
the former case the vectors E, H and k constitute a right-handed set,
whereas for negative ε and μ we have a left-handed set.
• The wave vector k tells us the direction of the phase velocity, the
Poynting vector tells us the direction of the group velocity. If the two
are in opposite directions we have a backward-wave material with all
that implies.
• Thus, negative refraction at the boundary of two materials, one
having positive material constants and the other negative ones,
follows immediately.
• The most striking example of what we can do with a negative-index
material (NIM) is Veselago’s flat lens. For n = −1 the angle of
refraction is equal to the negative angle of incidence hence all the
rays emanating from a line source will be refocused inside the
material and brought to another focus outside the material
11
24-Nov-15
Basic properties of Negative Index Waves

H
E
In vacuum “right-hand rule” relates
E, H, and k.
Note: normally  > 0 and  > 0 k
•Consequence: phase velocity (along k) and group velocity (along the

Poynting ExH vector) are in the same direction
•In NIMs, group and phase velocity are in opposite directions
Positive Index Medium Negative Index Medium
Positive/Negative Index Interface
Positive Index Negative Index

Medium Medium
What happens for the oblique incidence?
12
24-Nov-15
Unusual refractive properties of NIMs
Light enters n > 0 Light enters n < 0 material

material  deflection  focusing (“Veselago
Lens”)
Surface waves make Veselago’s lens a super-lens! (Pendry, 2000)
Straw in a negative index water
empty glass regular water, “negative” water,

n = 1.3 n = -1.3
13
24-Nov-15
How to Make a Negative-

Negative-Index Material
In microwave range: use “perfectly” conducting components to

simulate  < 0 and  < 0 , Smith et.al., (2000)
Metal poles:  = 1 – wp2/ w2 < 0

Split-ring resonators, Pendry’99:
“geometric” resonance at wM
1/ 2
c  2  Fw M2
w p      1 0
D  log(D/r)  w 2  w M2
Challenges:
(a) moving to optical frequencies (infrared, visible, UV)
(b) simplifying the structure ( < 0 and  < 0 from same element)
Another Example a microwave NIM
Basic Elements of a NIM:
(a) Split ring resonator: just a well designed inductor resonating at

w << c/L  gives  < 0
(b) Metal wires (continuous or cut): r << L to ensure that

 < 0 for w << c/L
14
24-Nov-15
The Perfect Lens

• Does it exist?
• It is an old subject, going back at least for half a century (Toraldo di Francia,
1953), how one can beat the classical limit of resolution.
• There are essentially two approaches: one uses the far field and relies on
changing the field distribution in the aperture of the lens, the second one is
based on near fields.
• The first attempt at high-resolution near-field imaging was made by Ash and
Nicholls (1972)
• The idea was to make use of the field leaking out of a microwave cavity through a
small hole. If an object with a structure somewhat larger than the hole is scanned in
front of the hole then the resonant frequency of the cavity depends on the relative
position of the object.
• By monitoring the resonant frequency it turned out to be possible to obtain
information about the structure with a resolution of λ/60, close to that of the size of
the hole. Their work initiated the whole new field of scanning near-field optical
microscopy.
• An entirely new idea of near-field imaging came with a proposal by Pendry
(2000). He calculated that the flat lens of Veselago (which required a
refractive index of minus unity) will be able to image an object with infinite
resolution, provided εr = −1 and μr = −1.
The Perfect Lens

• Infinite resolution means perfect imaging. Perfect imaging means
that every single detail of the object is reproduced in the image
(including both propagating and evanescent components). In terms of a
spatial frequency, it means that the spatial frequency spectrum of the image
(including both propagating and evanescent components) will be identical with the
spatial frequency spectrum of the object.
• In terms of a transfer function it means that the transfer function is
flat. Entirely flat. It is the same for every spatial frequency
component.
• Is that possible? Not really. A limit will be set, if by nothing else, then by the
period of the negative-index material. If we can make metamaterial elements of the
size of 100 nm and if the distance between them is also 100 nm then there would be
a chance of making a lens with a resolution approaching 100 nm.
• Another chance is obtained with a material in which only the
dielectric constant is negative. That will not yield a flat transfer function but it
would be flat enough for many purposes, and it would have the great advantage that
natural materials (e.g. silver) with that property exist. The period in that material will
be of the order of one tenth of a nanometer, thus, at least on that account, the
resolution could be extremely high.
15
24-Nov-15
Super lens
• This small copper coil created
the electromagnetic field by
running an alternating electric
current through it. In the
background is the
metamaterial "superlens" that
focused the electromagnetic
field onto another identically
sized copper coil on the other
side, which greatly increased
the wireless transfer's power.
• Courtesy of Guy Lipworth and
Joshua Ensworth, graduate
student researchers at Duke
University
Read more
at: http://phys.org/news/2014-01-
superlens-range-wireless-
power.html#jCp
“Poor Man’s Super-

Super-Lens”:  < 0,  > 0
Inserting a slab of matched

material with negative  (and,
one day, ) can prevent image
degradation
Super-lensing is a highly
resonant phenomenon:
frequency-dependent
permittivities must match
Recent UV results: Fang et.al, Science ’05, Melville and Blaikie, Opt. Expr. ’05
It has been demonstrated super-lensing in IR and (a) proved its resonant

nature, (b) demonstrated a new application: sub-surface imaging
16
24-Nov-15
Superlens in mid-
mid-IR: sub-
sub-surface imaging
pattern on bottom
NSOM image from top
with Taubner and Hillenbrandt

(MPQ/Munich)
SiO2/SiC/SiO2 superlens with a metallic pattern (0.5 m slits in Ag film

separated by 3 m on the bottom side) was imaged from the top using
NSOM
Sub-surface imaging of sub-l features at 800 nm depth accomplished at
10.85 m (CO2 laser) using a superlens  opens the way to applications
of super-lensing to sub-surface imaging of integrated circuits
Summary
Optical meta-materials have been shown to have remarkable
applications:
• Can be used to engineer exotic meta-media: Negative Index
Materials  plasmonic approach to making a sub-l NIM
• NIMs and negative  materials can be used to overcome
diffraction limit and construct a super-lens
• A super-lens enables ultra-deep sub-surface imaging using
NSOM probe
Very new field  lots of work to do (theory and experiments)
17
6/22/2015
End Philosophy Handout: #9
"... with a very restricted set of

atomic ingredients you can create
materials with wildly different
material properties. ... It is hard to
overestimate the philosophical as
well as the technological importance
of this dictum of materials science:
that knowing the basic chemical
composition is not enough to
understand materiality."
- Mark Miodownik
• OBJECTIVES: Students will gain a fundamental understanding of the following

topics: i) electrical conduction (transport) in solids based on quantum mechanics and
modern band theory, ii) dielectric properties of solids, iii) magnetic properties, iv)
superconductivity and v)artificial materials
• COURSE OUTCOMES: Students who have successfully completed this course will
have gained an understanding of:
– the structure of ideal crystalline solids and their defects
– the basics of electrical and thermal conduction in solids
– the behavior of electron as a particle and as a wave
– the basic free electron theory of metals
– basic semiconductor materials properties
– the basic energy band theory of solids
– free charge carrier distribution in intrinsic and extrinsic semiconductors
– Dielectric properties
– Magnetic and superconductor properties of solids
– Artificial Materials
• The students will be able to use mathematical and conceptual approaches to
applying this knowledge in solving a wide range of problems originating in part in
semiconductor research and development and industrial technology.
1
6/22/2015
• The potential of research in the field of materials and their

fascinating properties are immensely rich.
• Lev Landau (1908-1968) was fond of quipping that "all the nice
girls are already married, and all the nice problems are already
solved."
But Gamow (?) said that there will never be

any lack of nice girls and all nice girls will be
replaced by even nicer girls, and so in
physics, interesting problems will never end
popping up the horizon.
• Materials is such a field where there are always a huge supply

of neverending "nice girls" – beautiful problems are always
there
• It takes the ingenuinuty of the engineers, and the physicists in
solving such properties and life easier and smart
• The single take-home lesson from this course is –
That solids have interesting emerging properties; such as, chocolates

are tiny crystals, and just the arrangement of atoms makes diamonds
so hard and pencil lead (graphite) so soft.
That almost every property of the solid can be explained through the
electronic configuration in that solid
That the wavy electrons and the periodic/aperiodic solid lattice gives
rise to all the beauties of the solids
That even one can change the beauty of the solids artificially
• The study of Materials and its electronic property is of such a matter

of joy that it becomes the device engineer's or the device physicist's
everlasting passion
• Read the Nobel 2010 Lecture of Andre Geim to have a glimpse into
this passion
2
Handout#9
RANDOM WALK TO GRAPHENE
Nobel Lecture, December 8, 2010

by
ANDRE K. GEIM
School of Physics and Astronomy, The University of Manchester, Oxford
Road, Manchester M13 9PL, United Kingdom.
If one wants to understand the beautiful physics of graphene, they will

be spoiled for choice with so many reviews and popular science articles
now available. I hope that the reader will excuse me if on this occasion I
recommend my own writings [1–3]. Instead of repeating myself here, I have
chosen to describe my twisty scientific road that eventually led to the Nobel
Prize. Most parts of this story are not described anywhere else, and its time-
line covers the period from my PhD in 1987 to the moment when our 2004
paper, recognised by the Nobel Committee, was accepted for publication.
The story naturally gets denser in events and explanations towards the end.
Also, it provides a detailed review of pre-2004 literature and, with the benefit
of hindsight, attempts to analyse why graphene has attracted so much inter-
est. I have tried my best to make this article not only informative but also easy
to read, even for non-physicists.
ZOMBIE MANAGEMENT
My PhD thesis was called “Investigation of mechanisms of transport relaxa-
tion in metals by a helicon resonance method”. All I can say is that the stuff
was as interesting at that time as it sounds to the reader today. I published five
journal papers and finished the thesis in five years, the official duration for
a PhD at my institution, the Institute of Solid State Physics. Web of Science so-
berly reveals that the papers were cited twice, by co-authors only. The subject
was dead a decade before I even started my PhD. However, every cloud has
its silver lining, and what I uniquely learned from that experience was that I
should never torture research students by offering them “zombie” projects.
After my PhD, I worked as a staff scientist at the Institute of Micro-
electronics Technology, Chernogolovka, which belongs to the Russian
Academy of Sciences. The Soviet system allowed and even encouraged junior
staff to choose their own line of research. After a year of poking in different
directions, I separated research-wise from my former PhD supervisor, Victor
Petrashov, and started developing my own niche. It was an experimental
system that was both new and doable, which was nearly an oxymoron, taking
into account the scarce resources available at the time at Soviet research
70
AndreGeim_lect_s70_95.indd 2 2011-08-29 08:48:46

institutes. I fabricated a sandwich consisting of a thin metal film and a super-
conductor separated by a thin insulator. The superconductor served only to
condense an external magnetic field into an array of vortices, and this highly
inhomogeneous magnetic field was projected onto the film under investiga-
tion. Electron transport in such a microscopically inhomogeneous field
(varying on a submicron scale) was new research territory, and I published
the first experimental report on the subject [4], which was closely followed
by an independent paper from Simon Bending [5]. It was an interesting
and reasonably important niche, and I continued studying the subject for
the next few years, including a spell at the University of Bath in 1991 as a
postdoctoral researcher working with Simon.
This experience taught me an important lesson: that introducing a new
experimental system is generally more rewarding than trying to find new
phenomena within crowded areas. The chances of success are much higher
where the field is new. Of course, the fantastic results one originally hopes
for are unlikely to materialise, but, in the process of studying any new system,
something original inevitably shows up.
ONE MAN’S JUNK, ANOTHER MAN’S GOLD

In 1990, thanks to Vitaly Aristov, director of my Institute in Chernogolovka
at the time, I received a six month visiting fellowship from the British
Royal Society. Laurence Eaves and Peter Main from Nottingham University
kindly agreed to accept me as a visitor. Six months is a very short period for
experimental work, and circumstances dictated that I could only study de-
vices readily available in the host laboratory. Available were submicron GaAs
wires left over from previous experiments, all done and dusted a few years
earlier. Under the circumstances, my experience of working in a poverty-
stricken Soviet academy was helpful. The samples that my hosts considered
practically exhausted looked like a gold vein to me, and I started working
100 hours per week to exploit it. This short visit led to two Phys. Rev. Letters
of decent quality [6,7], and I often use this experience to tease my younger
colleagues. When things do not go as planned and people start complaining,
I provoke them by proclaiming ‘there is no such thing as bad samples; there
are only bad postdocs/students’. Search carefully and you will always find
something new. Of course, it is better to avoid such experiences and explore
new territories, but even if one is fortunate enough to find an experimental
system as new and exciting as graphene, meticulousness and perseverance
allow one to progress much further.
The pace of research at Nottingham was so relentless and, at the same time
so inspiring, that a return to Russia was not an option. Swimming through
Soviet treacle seemed no less than wasting the rest of my life. So at the age
of thirty-three and with an h-index of 1 (latest papers not yet published), I
entered the Western job market for postdocs. During the next four years I
moved between different universities, from Nottingham to Copenhagen to
Bath and back to Nottingham. Each move allowed me to get acquainted with
71

yet another topic or two, significantly broadening my research horizons. The
physics I studied in those years could be broadly described as mesoscopic and
involved such systems and phenomena as two-dimensional electron gases
(2DEGs), quantum point contacts, resonant tunnelling and the quantum
Hall effect (QHE), to name but a few. In addition, I became familiar with
GaAlAs heterostructures grown by molecular beam epitaxy (MBE) and
improved my expertise in microfabrication and electron-beam lithography,
technologies I had started learning in Russia. All these elements came
together to form the foundation for the successful work on graphene a
decade later.
DUTCH COMFORT
By 1994 I had published enough quality papers and attended enough con-
ferences to hope for a permanent academic position. When I was offered
an associate professorship at the University of Nijmegen, I instantly seized
upon the chance of having some security in my new post-Soviet life. The first
task in Nijmegen was of course to establish myself. To this end, there was no
start-up and no microfabrication to continue any of my previous lines of re-
search. As resources, I was offered access to magnets, cryostats and electronic
equipment available at Nijmegen’s High Field Magnet Laboratory, led by Jan
Kees Maan. He was also my formal boss and in charge of all the money. Even
when I was awarded grants as the principal investigator (the Dutch funding
agency FOM was generous during my stay in Nijmegen), I could not spend
the money as I wished. All funds were distributed through so-called ‘working
groups’ led by full professors. In addition, PhD students in the Netherlands
could formally be supervised only by full professors. Although this probably
sounds strange to many, this was the Dutch academic system of the 1990s. It
was tough for me then. For a couple of years, I really struggled to adjust to
the system, which was such a contrast to my joyful and productive years at
Nottingham. In addition, the situation was a bit surreal because outside the
university walls I received a warm-hearted welcome from everyone around,
including Jan Kees and other academics.
Still, the research opportunities in Nijmegen were much better than in
Russia and, eventually, I managed to survive scientifically, thanks to help
from abroad. Nottingham colleagues (in particular Mohamed Henini)
provided me with 2DEGs that were sent to Chernogolovka, where Sergey
Dubonos, a close colleague and friend from the 1980s, microfabricated
requested devices. The research topic I eventually found and later focused
on can be referred to as mesoscopic superconductivity. Sergey and I used
micron-sized Hall bars made from a 2DEG as local probes of the magnetic
field around small superconducting samples. This allowed measurements
of their magnetisation with accuracy sufficient to detect not only the entry
and exit of individual vortices but also much more subtle changes. This was
a new experimental niche, made possible by the development of an original
technique of ballistic Hall micromagnetometry [8]. During the next few
72

years, we exploited this niche area and published several papers in Nature
and Phys. Rev. Letters which reported a paramagnetic Meissner effect, vortices
carrying fractional flux, vortex configurations in confined geometries and so
on. My wife Irina Grigorieva, an expert in vortex physics [9], could not find
a job in the Netherlands and therefore had plenty of time to help me with
conquering the subject and writing papers. Also, Sergey not only made the
devices but also visited Nijmegen to help with measurements. We established
a very productive modus operandi where he collected data and I analysed
them within an hour on my computer next door to decide what should be
done next.
A SPELL OF LEVITY
The first results on mesoscopic superconductivity started emerging in 1996,
which made me feel safer within the Dutch system and also more inquisi-
tive. I started looking around for new areas to explore. The major facility
at Nijmegen’s High Field Lab was powerful electromagnets. They were a
major headache, too. These magnets could provide fields up to 20 T, which
was somewhat higher than 16 to 18 T available with the superconducting
magnets that many of our competitors had. On the other hand, the elec-
tromagnets were so expensive to run that we could use them only for a few
hours at night, when electricity was cheaper. My work on mesoscopic super-
conductivity required only tiny fields (< 0.01T), and I did not use the electro-
magnets. This made me feel guilty as well as responsible for coming up with
experiments that would justify the facility’s existence. The only competitive
edge I could see in the electromagnets was their room temperature (T)
bore. This was often considered as an extra disadvantage because research
in condensed matter physics typically requires low, liquid-helium T. The con-
tradiction prompted me, as well as other researchers working in the lab, to
ponder on high-field phenomena at room T. Unfortunately, there were few
to choose from.
Eventually, I stumbled across the mystery of so-called magnetic water. It
is claimed that putting a small magnet around a hot water pipe prevents
formation of scale inside the pipe. Or install such a magnet on a water tap,
and your kettle will never suffer from chalky deposits. These magnets are
available in a great variety in many shops and on the internet. There are also
hundreds of articles written on this phenomenon, but the physics behind it
remains unclear, and many researchers are sceptical about the very existence
of the effect [10]. Over the last fifteen years I have made several attempts
to investigate “magnetic water” but they were inconclusive, and I still have
nothing to add to the argument. However, the availability of ultra-high fields
in a room T environment invited lateral thinking about water. Basically, if
magnetic water existed, I thought, then the effect should be clearer in 20 T
rather than in typical fields of <0.1 T created by standard magnets.
With this idea in mind and, allegedly, on a Friday night, I poured water
inside the lab’s electromagnet when it was at its maximum power. Pouring
73

water in one's equipment is certainly not a standard scientific approach, and
I cannot recall why I behaved so ‘unprofessionally’. Apparently, no one had
tried such a silly thing before, although similar facilities existed in several
places around the world for decades. To my surprise, water did not end up
on the floor but got stuck in the vertical bore of the magnet. Humberto
Carmona, a visiting student from Nottingham, and I played for an hour with
the water by breaking the blockage with a wooden stick and changing the
field strength. As a result, we saw balls of levitating water (Figure 1). This was
awesome. It took little time to realise that the physics behind was good old
diamagnetism. It took much longer to adjust my intuition to the fact that the
feeble magnetic response of water (~10–5), billions of times weaker than that
of iron, was sufficient to compensate the earth’s gravity. Many colleagues,
including those who worked with high magnetic fields all their lives, were
flabbergasted, and some of them even argued that this was a hoax.
I spent the next few months demonstrating magnetic levitation to colleagues
and visitors, as well as trying to make a ‘non-boffin’ illustration for this
beautiful phenomenon. Out of the many objects that we had floating inside
the magnet, it was the image of a levitating frog (Figure 1) that started the
media hype. More importantly, though, behind all the media noise, this
image found its way into many textbooks. However quirky, it has become a
beautiful symbol of ever-present diamagnetism, which is no longer perceived
to be extremely feeble. Sometimes I am stopped at conferences by people
exclaiming “I know you! Sorry, it is not about graphene. I start my lectures
with showing your frog. Students always want to learn how it could fly.” The
frog story, with some intricate physics behind the stability of diamagnetic
levitation, is described in my review in Physics Today [11].
Figure 1. Levitating moments in Nijmegen. Left – Ball of water (about 5 cm in diameter)

freely floats inside the vertical bore of an electromagnet. Right – The frog that learned to
fly. This image continues to serve as a symbol showing that magnetism of ‘nonmagnetic
things’, including humans, is not so negligible. This experiment earned Michael Berry and
me the 2000 Ig Nobel Prize. We were asked first whether we dared to accept this prize, and
I take pride in our sense of humour and self-deprecation that we did.
74

FRIDAY NIGHT EXPERIMENTS
The levitation experience was both interesting and addictive. It taught me

the important lesson that poking in directions far away from my immediate
area of expertise could lead to interesting results, even if the initial ideas
were extremely basic. This in turn influenced my research style, as I started
making similar exploratory detours that somehow acquired the name ‘Friday
night experiments’. The term is of course inaccurate. No serious work can
be accomplished in just one night. It usually requires many months of lateral
thinking and digging through irrelevant literature without any clear idea in
sight. Eventually, you get a feeling – rather than an idea – about what could
be interesting to explore. Next, you give it a try, and normally you fail. Then,
you may or may not try again. In any case, at some moment you must decide
(and this is the most difficult part) whether to continue further efforts or cut
losses and start thinking of another experiment. All this happens against the
backdrop of your main research and occupies only a small part of your time
and brain.
Already in Nijmegen, I started using lateral ideas as under- and post-
graduate projects, and students were always excited to buy a pig in a poke.
Kostya Novoselov, who came to Nijmegen as a PhD student in 1999, took part
in many of these projects. They never lasted for more than a few months,
in order not to jeopardise a thesis or career progression. Although the
enthusiasm inevitably vanished towards the end, when the predictable
failures materialised, some students later confided that those exploratory
detours were invaluable experiences.
Most surprisingly, failures sometimes failed to materialise. Gecko tape
is one such example. Accidentally or not, I read a paper describing the
mechanism behind the amazing climbing ability of geckos [12]. The physics
is rather straightforward. Gecko’s toes are covered with tiny hairs. Each hair
attaches to the opposite surface with a minute van der Waals force (in the
nN range), but billions of hairs work together to create a formidable attraction
sufficient to keep geckos attached to any surface, even a glass ceiling. In
particular, my attention was attracted by the spatial scale of their hairs. They
were submicron in diameter, the standard size in research on mesoscopic
physics. After toying with the idea for a year or so, Sergey Dubonos and I
came up with procedures to make a material that mimicked a gecko’s hairy
feet. He fabricated a square cm of this tape, and it exhibited notable adhesion
[13]. Unfortunately, the material did not work as well as a gecko’s feet,
deteriorating completely after a couple of attachments. Still, it was an
important proof-of-concept experiment that inspired further work in the field.
Hopefully, one day someone will develop a way to replicate the hierarchical
structure of gecko’s setae and its self-cleaning mechanism. Then gecko tape
can go on sale.
75

BETTER TO BE WRONG THAN BORING
While preparing for my lecture in Stockholm, I compiled a list of my Friday

night experiments. Only then did I realise a stunning fact. There were two
dozen or so experiments over a period of approximately fifteen years and, as
expected, most of them failed miserably. But there were three hits: levitation,
gecko tape and graphene. This implies an extraordinary success rate: more
than 10%. Moreover, there were probably near-misses, too. For example, I
once read a paper [14] about giant diamagnetism in FeGeSeAs alloys, which
was interpreted as a sign of high-T superconductivity. I asked Lamarches for
samples and got them. Kostya and I employed ballistic Hall magnetometry
to check for giant diamagnetism but found nothing, even at 1 K. This
happened in 2003, well before the discovery of iron pnictide superconductiv-
ity, and I still wonder whether there were any small inclusions of a supercon-
ducting material which we missed with our approach. Another miss was an
attempt to detect “heartbeats” of individual living cells. The idea was to use
2DEG Hall crosses as ultrasensitive electrometers to detect electrical signals
due to physiological activity of individual cells. Even though no heartbeats
were detected while a cell was alive, our sensor recorded huge voltage spikes
at its “last gasp” when the cell was treated with excess alcohol [15]. Now I
attribute this near-miss to the unwise use of yeast, a very dormant micro-
organism. Four years later, similar experiments were done using embryonic
heart cells and – what a surprise – graphene sensors, and they were successful
in detecting such bioelectrical activity [16].
Frankly, I do not believe that the above success rate can be explained by
my lateral ideas being particularly good. More likely, this tells us that poking
in new directions, even randomly, is more rewarding than is generally
perceived. We are probably digging too deep within established areas,
leaving plenty of unexplored stuff under the surface, just one poke away.
When one dares to try, rewards are not guaranteed, but at least it is an
adventure.
THE MANCUNIAN WAY

By 2000, with mesoscopic superconductivity, diamagnetic levitation and
four Nature papers under my belt, I was well placed to apply for a full
professorship. Colleagues were rather surprised when I chose the University
of Manchester, declining a number of seemingly more prestigious offers.
The reason was simple. Mike Moore, chairman of the search committee,
knew my wife Irina when she was a very successful postdoc in Bristol rather
than my co-author and a part-time teaching lab technician in Nijmegen.
He suggested that Irina could apply for the lectureship that was there
to support the professorship. After six years in the Netherlands, the idea
that a husband and wife could officially work together had not even
crossed my mind. This was the decisive factor. We appreciated not only
the possibility of sorting out our dual career problems but also felt
76

touched that our future colleagues cared. We have never regretted the
move.
So in early 2001, I took charge of several dilapidated rooms storing ancient
equipment of no value, and a start-up grant of £100K. There were no central
facilities that I could exploit, except for a helium liquefier. No problem. I
followed the same routine as in Nijmegen, combining help from other
places, especially Sergey Dubonos. The lab started shaping up surprisingly
quickly. Within half a year, I received my first grant of £500K, which allowed
us to acquire essential equipment. Despite being consumed with our one
year old daughter, Irina also got her starting grant a few months later. We
invited Kostya to join us as a research fellow (he continued to be officially
registered in Nijmegen as a PhD student until 2004 when he defended his
thesis there). And our group started generating results that led to more
grants that in turn led to more results.
By 2003 we published several good-quality papers including Nature, Nature
Materials and Phys. Rev. Letters, and we continued beefing up the labora-
tory with new equipment. Moreover, thanks to a grant of £1.4M (research
infrastructure funding scheme masterminded by the then science minister
David Sainsbury), Ernie Hill from the Department of Computer Sciences
and I managed to set up the Manchester Centre for Mesoscience and
Nanotechnology. Instead of pouring the windfall money into bricks-and-
mortar, we utilised the existing clean room areas (~250 m2) in Computer
Sciences. Those rooms contained obsolete equipment, and it was thrown
away and replaced with state-of-the-art microfabrication facilities, including
a new electron-beam lithography system. The fact that Ernie and I are most
proud of is that many groups around the world have more expensive facilities
but our Centre has continuously, since 2003, been producing new structures
and devices. We do not have a posh horse here that is for show, but rather a
draft horse that has been working really hard.
Whenever I describe this experience to my colleagues abroad, they find
it difficult to believe that it is possible to establish a fully functional labora-
tory and a microfabrication facility in less than three years and without an
astronomical start-up grant. If not for my own experience, I would not
believe it either. Things progressed unbelievably quickly. The University was
supportive, but my greatest thanks are reserved specifically for the responsive
mode of the UK Engineering and Physical Sciences Research Council
(EPSRC). The funding system is democratic and non-xenophobic. Your
position in an academic hierarchy or an old-boys network counts for little.
Also, ‘visionary ideas’ and grand promises to ‘address social and economic
needs’ play little role when it comes to the peer review. In truth, the
responsive mode distributes its money on the basis of a recent track record,
whatever that means in different subjects, and the funding normally goes
to researchers who work both efficiently and hard. Of course, no system is
perfect, and one can always hope for a better one. However, paraphrasing
Winston Churchill, the UK has the worst research funding system, except for
all the others that I am aware of.
77

THREE LITTLE CLOUDS
As our laboratory and Nanotech Centre were shaping up, I got some spare
time for thinking of new research detours. Gecko tape and the failed attempts
with yeast and quasi-pnictides took place during that time. Also, Serge
Morozov, a senior fellow from Chernogolovka, who later became a regular visi-
tor and invaluable collaborator, wasted his first two visits on studying magnetic
water. In the autumn of 2002, our first Manchester PhD student, Da Jiang,
arrived, and I needed to invent a PhD project for him. It was clear that
for the first few months he needed to spend his time learning English and
getting acquainted with the lab. Accordingly, as a starter, I suggested to him a
new lateral experiment. It was to make films of graphite ‘as thin as possible’ and,
if successful, I promised we would then study their ‘mesoscopic’ properties.
Recently, trying to analyse how this idea emerged, I recalled three badly
shaped thought clouds.
One cloud was a concept of ‘metallic electronics’. If an external electric
field is applied to a metal, the number of charge carriers near its surface
changes, so that one may expect that its surface properties change, too.
This is how modern semiconductor electronics works. Why not use a metal
instead of silicon? As an undergraduate student, I wanted to use electric field
effect (EFE) and X-ray analysis to induce and detect changes in the lattice
constant. It was naïve because simple estimates show that the effect would
be negligible. Indeed, no dielectric allows fields much higher than 1V/nm,
which translates into maximum changes in charge carrier concentration n
at the metal surface of about 1014 per cm2. In comparison, a typical metal
(e.g., Au) contains ~1023 electrons per cm3 and, even for a 1 nm thick film,
this yields relative changes in n and conductivity of ~1%, leaving aside much
smaller changes in the lattice constant.
Previously, many researchers aspired to detect the field effect in metals.
The first mention is as far back as 1902, shortly after the discovery of the
electron. J. J. Thomson (1906 Nobel Prize in Physics) suggested to Charles
Mott, the father of Nevill Mott (1977 Nobel Prize in Physics), to look for
the EFE in a thin metal film, but nothing was found [17]. The first attempt
to measure the EFE in a metal was recorded in scientific literature in 1906
[18]. Instead of a normal metal, one could also think of semimetals such
as bismuth, graphite or antimony which have a lot fewer carriers. Over the
last century, many researchers used Bi films (n ~1018 cm–3) but observed
only small changes in their conductivity [19,20]. Aware of this research
area and with experience in GaAlAs heterostructures, I was continuously,
albeit casually, looking for other candidates, especially ultra-thin films of
superconductors in which the field effect can be amplified in proximity to
the superconducting transition [21,22]. In Nijmegen, my enthusiasm was
once sparked by learning about nm-thick Al films grown by MBE on top of
GaAlAs heterostructures but, after estimating possible effects, I decided that
the chances of success were so poor it was not worth trying.
Carbon nanotubes were the second cloud hanging around in the late
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1990s and early 2000s. Those were the years when nanotubes were at the
peak of their glory. Living in the Netherlands, I heard talks by Cees Dekker
and Leo Kouwenhoven and read papers by Thomas Ebbesen, Paul McEuen,
Sumio Iijima, Pheadon Avouris and others. Each time, those exceptionally
nice results inevitably triggered thoughts about entering this research area.
But I was too late and needed to find a different perspective, away from the
stampede.
As for the third cloud, I read a review of Millie Dresselhaus about interca-
lated graphite compounds [23], which clearly showed that, even after many
decades, graphite was still a material little understood, especially in terms of
its electronic properties. This influential review prompted me to look further
into graphite literature. In doing so, I encountered papers by Pablo Esquinazi
and Yakov Kopelevich, who reported ferromagnetism, superconductivity and
a metal-insulator transition, all in the same good old graphite and at room T
[24,25]. Those provocative papers left me with a distinct feeling that graphite
was very much worth having a careful look at.
The three thought clouds (and maybe some more that I cannot recall)
somehow merged into Da’s project. I reckoned that if we were to succeed in
making thin films of graphite, instead of Bi, they could exhibit some electric
field effect and/or some other interesting properties resembling those of
carbon nanotubes. In the worst-case scenario, our mesoscopic samples would
be monocrystals and this could help to clarify those controversies about
graphite. Why not try to poke in this direction for a few months, I thought.
LEGEND OF SCOTCH TAPE

To make thin graphite films, I provided Da with a tablet of pyrolytic graphite,
which was several mm thick and an inch in diameter, and suggested using
a polishing machine. We had a fancy one that allowed submicron flatness.
A few months later, Da declared that he had reached the ultimate thick-
ness and showed me a tiny speck of graphite at the bottom of a Petri dish. I
looked at it in an optical microscope and, by focusing on the top and bottom
surfaces, estimated that the speck was ~10 Pm thick. Too thick, I thought
and suggested trying a finer polishing liquid. However, it turned out that Da
had polished away the whole tablet to obtain this one speck. It was actually
my fault: Da successfully finished his PhD later, but at that time he was just
a fresh foreign student with a huge language barrier. Moreover, by mistake I
gave him high-density graphite instead of highly-oriented pyrolytic graphite
(HOPG) as was intended. The former does not shed as easily as HOPG.
Oleg Shklyarevskii, a senior fellow from Kharkov, Ukraine was working
nearby and had to listen to the typical flow of my teasing remarks, this time
about polishing a mountain to get one grain of sand. Oleg was an expert in
scanning tunnelling microscopy (STM) and worked on a project that later
turned out to be another bad ‘Friday night’ idea of mine. He interjected
by bringing over a piece of cellotape with graphite flakes attached to it.
Allegedly, he just fished out the tape from a litter bin. Indeed, HOPG is
79

the standard reference sample for STM, where a fresh surface of graphite
is normally prepared by removing a top layer with sticky tape. We used this
technique for years but never looked carefully at what was thrown away along
with the tape. I looked in the microscope at the remnants of graphite (Figure
2) and found pieces much thinner than Da’s speck. Only then did I realise
how silly it was of me to suggest the polishing machine. Polishing was dead,
long live Scotch tape!
This moment was not a breakthrough yet, but things started to look
promising and required more people to get involved. Oleg did not volunteer
to take on yet another project but Kostya did. ‘Volunteer’ is probably not the
right word. Everyone in our lab has always been welcome to move around
and participate in whatever project they want. At that time, Kostya was work-
ing on a nicely-moving project on ferromagnetism [26]. He was also our
‘caretaker’ when things went wrong, especially with measuring equipment.
As for me, at that time I used to spend a few hours a day in the lab preparing
samples, doing measurements and analysing results. It was only after 2006
that I turned into a paper-writing machine combined with a data analyser. I
have always loved the latter but hated to write papers. Unfortunately, no lab
can survive without its Shakespeare.
Figure 2. In hindsight, thin crystals of graphite are easy to obtain. a – Remnants of HOPG
left attached to Scotch tape. b – Some of the crystals are optically transparent if viewed in
an optical microscope or just with a magnifying glass. c – If placed on an oxidised Si wafer,
transparent crystals give rise to various shades of blue. d – One of our very first devices
made by using ‘a shoestring and sealing wax’: in this case, tweezers, a toothpick and silver
paint.
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Kostya and I decided to check out the electrical properties of the graphite
flakes found on the cellotape and, to this end, he started transferring them
onto glass slides, initially by using just tweezers. A few days later and keeping
in mind the initial motivation, I brought in oxidised Si wafers in order to use
them as substrates and detect the EFE. This delivered an unexpected bonus.
Placing thin graphite fragments onto those wafers allowed us to observe
interference colours that indicated that some of the fragments were optically
transparent. Moreover, the colours provided us with a very intuitive way of
judging which flakes were thin (Figure 2c). We quickly found that some of
them were just a few nm thick. This was our first real breakthrough.
EUREKA MOMENT
In graphene literature and especially in popular articles, a strong emphasis
is placed on the Scotch tape technique, and it is hailed for allowing the
isolation and identification of ultra-thin graphite films and graphene. For
me, this was an important development but still not a Eureka moment. Our
goal always was to find some exciting physics rather than just observing ultra-
thin films in a microscope.
Within a couple of days after Oleg prompted the use of Scotch tape, Kostya
was already using silver paint to make electrical contacts to graphite platelets
transferred from the Scotch tape. To our surprise, they turned out to be
highly conductive and even the painted contacts exhibited a reasonably low
resistance. The electronic properties could be studied, but we felt it was too
early to put the ugly-looking devices (see Fig. 2d) in a cryostat for proper
measurements. As a next step, we applied voltage, first, through the glass
slides and, a bit later, to the Si wafer, using it as a back gate to check for the
field effect. Figure 2 shows a photograph of one of our first devices. The
central part is a graphite crystal that is ~20 nm thick, and its lateral size is
comparable to the diameter of a human hair. To transfer the crystal by tweez-
ers from the tape and then make four such closely-spaced contacts by using
just a toothpick and silver paint is the highest level of experimental skill.
These days, not many researchers have fingers green enough to make such
samples. I challenge readers to test their own skills against this benchmark!
The very first hand-made device on glass exhibited a clear EFE such that
its resistance could be changed by several per cent. It may sound small and
of marginal importance but, aware of how hard it was previously to detect
any EFE at all, I was truly shocked. If those ugly devices made by hand from
relatively big and thick platelets already showed some field effect, what
could happen, I thought, if we were to use our thinnest crystallites and apply
the full arsenal of microfabrication facilities? There was a click in my head
that we had stumbled onto something really exciting. This was my Eureka
moment.
What followed was no longer a random walk. From this point, it was
only logical to continue along the same path by improving procedures for
cleaving and finding thinner and thinner crystals and making better and
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better devices, which we did. It was both painstaking and incredibly rapid,
depending on one’s viewpoint. It took several months until we learned how
to identify monolayers by using optical and atomic force microscopy. On the
microfabrication side, we started using electron-beam lithography to define
proper Hall bar devices and started making contacts by metal evaporation
rather than silver painting. The microfabrication development was led by
Dubonos, aided by his PhD student Anatoly Firsov. Initially, they employed
facilities in Chernogolovka but, when our new postdoc Yuan Zhang got fully
acquainted with the recently-installed lithography system at our Nanotech
Centre, the process really speeded up.
The move from multilayers to monolayers and from hand-made to
lithography devices was conceptually simple but never straightforward. We
took numerous detours and wasted much effort on ideas that only led us into
dead ends. An example of grand plans that never worked out was the idea
to plasma-etch graphite mesas in the form of Hall bars which, after cleavage,
would provide readily shaped devices, or so I thought. Later, we had to
return to the unprocessed graphite. The teething problems we experienced
at that time can also be illustrated by the fact that initially we believed that
Si wafers should have a very precise thickness of oxide (within several nm)
to allow hunting for monolayers. These days we can find graphene on practi-
cally any substrate. Crystal sizes also went up from a few microns to nearly a
millimetre, just by tinkering with procedures and using different sources of
graphite.
The most essential part of our 2004 report [27] was the electrical measure-
ments, and this required a lot of work. For several months, Kostya and Serge
Morozov were measuring full time, and I was around as well, discussing and
analysing raw data, often as soon as they appeared on the screen. The feed-
back to our microfabrication guys was almost instantaneous. As always in the
case of encountering a new system where one does not know what to expect,
we had to be particularly careful in those first experiments. We disregarded
any curve, unless it was reproducible for many devices and, to avoid any pre-
mature conclusions, we studied more than 50 ultra-thin devices. Those were
years of hard work compressed into just a few months, but we were excited
as every new device got better and better, and we could work 24x7, which
typically meant fourteen hour days and no breaks for the weekends.
Finally, by the end of 2003, we got a reliable experimental picture ready
for publication. Between that moment and the end of my timeline when the
Science paper was accepted in September 2004, there is a lengthy gap. Those
nine months were consumed by excruciating efforts to publish the results in
a high-profile journal. We continuously added data and polished the presen-
tation. Irina’s help was invaluable in this time-consuming process, which can
be fully appreciated only by those readers who ever published in such glossy
journals. First, we submitted the manuscript to Nature. It was rejected and,
when further information requested by referees was added, rejected again.
According to one referee, our report did “not constitute a sufficient scientific
advance.” Science referees were more generous (or more knowledgeable?),
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and the presentation was better polished by that time. In hindsight, I should
have saved the time and nerves by submitting to a second-tier journal, even
though we all felt that the results were ground-breaking. Readers aspiring
to get published in those glossy magazines and having their papers recently
rejected can use this story to cheer up: Their papers may also be prize
winning!
DEFIANT EXISTENCE
One of the most surprising results of our Science report was the observation
that, after being isolated, atomic planes remained continuous and conduc-
tive under ambient conditions. Even with hindsight, there are many reasons
to be surprised.
First, for many decades researchers studied ultra-thin films, and their
collective experience proves that continuous monolayers are practically im-
possible to make (see, e.g., [28,29]). Try to evaporate a metal film a few nm
in thickness, and you will find it discontinuous. The material coagulates into
tiny islands. This process, called island growth, is universal and driven by the
fact that a system tries to minimise its surface energy. Even by using epitaxial
substrates that provide an interaction working against the surface energy
contribution and cooling them down to liquid-helium T, which prevents
migration of deposited atoms, it is hard to find the right conditions to create
continuous nm thick films, let alone monolayers [28,29].
The second reason to be surprised is that theory unequivocally tells us
that an isolated graphene sheet should be thermodynamically unstable.
Calculations show that ‘graphene is the least stable [carbon] structure
until about 6000 atoms’ [30]. Until ~24,000 atoms (that is, a flat sheet with
a characteristic size of ~25 nm), various 3D configurations are energetically
more favourable than the 2D geometry [30,31]. For larger sizes, theory shows
again that a graphene sheet is unstable but now with respect to scrolling.
The latter conclusion is based on considering competing contributions from
the bending and surface energies [32,33]. These calculations are specific to
carbon, but the underlying physics is conceptually connected to the surface
energy mechanism that leads to island growth.
Third, 2D crystals cannot be grown in isolation, without an epitaxial
substrate that provides an additional atomic bonding. This follows from the
Landau-Peierls argument that shows that the density of thermal fluctuations
for a 2D crystal in the 3D space diverges with temperature [1]. Although the
divergence is only logarithmic, crystal growth normally requires high T such
that atoms become sufficiently mobile. This also implies a softer lattice with
little shear rigidity. The combination of the two conditions sets a limit on pos-
sible sizes L of 2D atomic crystals. One can estimate L as ~aexp(E/TG) where
a ~1Å is the lattice spacing, E~1eV the atomic bond energy and TG the growth
temperature. This consideration should not be applied to graphene at room
T, which would yield astronomical sizes. TG is usually comparable to the
bond energy, which renders the disorder-generating mechanism irrelevant
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at much lower T. Note that, in principle, self-assembly may allow growth of
graphene at room T but, so far, this has been achieved only for nm-sized
graphene sheets [34].
The fourth and probably the most important reason to be surprised is that
graphene remains stable under ambient conditions. Surfaces of materials
can react with air and moisture, and monolayer graphene has not one but
two surfaces, making it more reactive. Surface science research involves ultra-
high vacuum facilities and, often, liquid-helium T to keep surfaces stable
and away from reactive species. For example, gold is one of the most inert
materials in nature but, even for Au, it is hard to avoid its near-surface layer
being partially oxidised in air. What then are the chances for a monolayer
exposed to ambient conditions to remain unaffected?
Graphene flouts all the above considerations. It is instructive to analyse
how. First, any existing method of obtaining graphene starts with 3D rather
than 2D growth. Graphene sheets are initially formed either within the
bulk or on top of an epitaxial substrate, which quenches the diverging
thermal fluctuations. The interaction can be relatively weak, as in the case of
graphene grown on graphite [35], but it is always present. This allows gra-
phene to dodge the Landau-Peierls argument and, also, to avoid coagulation
into islands and 3D carbon structures. Second, if graphene is cleaved or
released from a substrate, the process is normally carried out at room T so
that energy barriers remain sufficiently high. This allows atomic planes to
persist in an isolated, non-scrolled form without any substrate [36], even
though this is energetically unfavourable. If placed on a substrate, the van
der Waals interaction may also be sufficient to prevent a graphene sheet
from scrolling. Third, graphite is even more chemically inert than gold.
Although graphene is more reactive than graphite and weakly reacts with
air and pollutants at room T, this does not destroy its crystal lattice and high
conductivity [37,38]. It requires T twice as high as room T to irreversibly
damage graphene in air. Our ambient conditions appear fortuitous enough
for the graphene lattice to survive.
REQUIEM FOR BRILLIANT IDEAS

Science literature is full of brilliant ideas that did not work. Searching the
literature for those is not a good idea at all. At a start of a new project, a
couple of decent reviews usually do the job of making sure that one does
not reinvent the wheel. The alternative can be truly detrimental. I have
met many promising researchers who later failed to live up to their promise
because they wasted their time on searching literature, instead of spending
it on searching for new phenomena. What’s more, after months of literature
search, they inevitably came to the same conclusion: Everything they planned
had been done before. Therefore, they saw no reason to try their own ideas
and, consequently, began a new literature search. One should realise that
ideas are never new. However brilliant, every idea is always based on previous
knowledge and, with so many smart people around, the odds are that some-
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one somewhere had already thought of something similar before. This
should not be used as an excuse for not trying because local circumstances
vary and, moreover, facilities change with time. New technologies offer a
reasonable chance that old failed ideas may work unpredictably well the next
time round.
In 2002–2003, the merged thought clouds that I would not even call a
brilliant idea were sufficient to instigate the project. They also provided
us with an Ariadne’s thread that helped with choosing specific directions.
Literature search was done in due course, after we roughly scouted the new
area and especially when the results were being prepared for publication. In
addition to the literature relevant to the thought clouds, our Science paper
cited the challenges of obtaining isolated 2D crystals, their thermodynamic
instability, the observation of nanoscrolls and papers on epitaxial growth.
Those references were important to show the experimental progress we
achieved. The first review of earlier literature was done in our 2007 progress
article [1]. Since then, I updated my conference presentations whenever
a historically important paper came to light. This is the first opportunity
to update the history chapter in writing by adding several new references.
Furthermore, my recent call for further historical insights [39] was answered
by a number of researchers and, for completeness, I want to acknowledge
their early ideas and contributions, too.
GRAPHENE INCARNATIONS
Looking back at graphene history, we should probably start with an obser-
vation by the British chemist Benjamin Brodie [40]. In 1859, by exposing
graphite to strong acids, he obtained what he called ‘carbonic acid’ (Figure
3a). Brodie believed that he discovered ‘graphon’, a new form of carbon with
a molecular weight of 33. Today we know that he observed a suspension of
tiny crystals of graphene oxide, that is, graphene sheets densely covered with
hydroxyl and epoxide groups [41]. Over the next century, there were quite
a few papers describing the laminated structure of graphite oxide, but the
next crucial step in graphene history was the proof that this ‘carbonic acid’
consisted of floating atomic planes. In 1948, G. Ruess and F. Vogt used
transmission electron microscopy (TEM) and, after drying a droplet of a
graphene-oxide suspension on a TEM grid, they observed creased flakes
down to a few nm in thickness [42]. These studies were continued by the
group of Ulrich Hofmann. In 1962, he and Hanns-Peter Boehm looked for
the thinnest possible fragments of reduced graphite oxide and identified
some of them as monolayers [43] (Figure 3b).
This remarkable observation received little attention until 2009–2010.
I have to mention that the 1962 identification relied on a relative TEM
contrast, an approach that would not stand today’s scrutiny because the
contrast strongly depends on focusing conditions [44]. For example, Rahul
Nair and I tried but predictably failed to distinguish between monolayers
and somewhat thicker flakes by using only their TEM contrast. Graphene
85

monolayers were unambiguously identified in TEM only forty years after the
1962 paper by counting the number of folding lines [45–47]. Nonetheless,
the Boehm-Hofmann work should, in my opinion, stand as the first observa-
tion of graphene because monolayers should have been present among
the residue, and the idea was correct. Furthermore, it was Boehm and his
colleagues who in 1986 introduced the term graphene, deriving it from the
combination of the word ‘graphite’ and the suffix that refers to polycyclic
aromatic hydrocarbons [48].
Figure 3. Prehistory of graphene. a – Graphene as probably seen by Brodie 150 years ago.
Graphite oxide at the bottom of the container dissolves in water making the yellow suspen-
sion of floating graphene flakes. b – TEM image of ultra-thin graphitic flakes from the
early 1960s (copied with permission from ref. [43]). c – Scanning electron microscopy
(SEM) image of thin graphite platelets produced by cleavage (similar to images reported
in ref. [60]). d – STM of graphene grown on Pt (copied with permission from ref. [53]).
The image is 100x100 nm2 in size. The hexagonal superstructure has a period of ~22 Å and
appears due to the interaction of graphene with the metal substrate.
In addition to the TEM observations, another important line in pre-2004

graphene research was its epitaxial growth. Ultra-thin graphitic films and,
sometimes, even monolayers were grown on metal substrates [49–53],
insulating carbides [54–57] and graphite [35] (see Fig. 3d). The first papers
I am aware of go back to 1970 when John Grant reported graphitic films on
Ru and Rh [49] and Blakely et al. on Ni [50]. Epitaxial growth on insulating
substrates was first demonstrated by van Bommel et al. in 1975 [54] whereas
86

Chuhei Oshima found other carbides allowing graphene growth (for
example, TiC) [55]. The grown films were usually analysed by surface
science techniques that average over large areas and say little about the film’s
continuity and quality. Occasionaly, STM was also used for visualisation and
local analysis.
Even more relevant were earlier attempts to obtain ultra-thin films of
graphite by cleavage, similar to what we did in 2003. In 1990, Heinrich Kurz’s
group reported ‘peeling optically thin layers with transparent tape’ (read
Scotch tape), which were then used to study carrier dynamics in graphite
[58]. In 1995, Thomas Ebbesen and Hidefumi Hiura described few-nm-thick
‘origami’ visualised by atomic force microscopy (AFM) on top of HOPG
[59]. Rod Ruoff also photographed thin graphite platelets in SEM [60] (Fig.
3c). In 2003, monolayers were reported by Yang Gan who used STM for their
cleavage on top of HOPG [61].
Finally, there were electrical studies of thin graphite films. Between 1997
and 2000, Yoshiko Ohashi succeeded in cleaving crystals down to ~20 nm in
thickness, studied their electrical properties including Shubnikov – de Haas
oscillations and, quite remarkably, observed the electric field effect with
resistivity changes of up to 8% [62,63]. Also, Ebbesen’s group succeeded in
growth of micron-sized graphitic disks with thickness down to 60 layers and
measured their electrical properties [64].
As for theory, let me make only a short note (for more references, see
[1,65]). Theoretically, graphene (‘a monolayer of graphite’) was around
since 1947 when Phil Wallace first calculated its band structure as a starting
point to understanding the electronic properties of bulk graphite [66].
Gordon Semenoff and Duncan Haldane realised that graphene could
provide a nice condensed-matter analogue of (2+1)-dimensional quantum
electrodynamics [67,68] and, since then, the material served as a toy model
to address various questions of QED (see, e.g., [69,70]). Many of the theories
became relevant to experiment well before 2004, when electronic properties
of carbon nanotubes (rolled-up graphene ribbons) were investigated. A large
amount of important theoretical work on graphene was done by Tsuneya
Ando, and Millie Dresselhaus and co-workers (see, e.g., [71–73]).
To complete the history of graphene, let me also acknowledge some
earlier ideas. Thomas Ebbesen and Hidefumi Hiura envisaged a possibility
of graphene-based nanoelectronics in 1995 (as an example, they referred
to epitaxial graphene grown on TiC) [59]. In patent literature, speculations
about “field effect transistors employing pyrolytic graphite” go back as far as
1970 [74]. Also, it was pointed out to me by Rod Ruoff and Reginald Little
that their pre-2004 papers discussed possibilities and mentioned an intention
of obtaining isolated monolayers [60,75]. Finally, the layered structure of
graphite was known since early days of X-ray crystallography, and research-
ers certainly have been aware of graphite being a deck of weakly bonded
graphene planes for an even longer time. This property has been widely used
to create a variety of intercalated graphite compounds [23] and, of course,
to make drawings. After all, we now know that isolated monolayers can be
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found in every pencil trace, if one searches carefully enough in an optical
microscope [2]. Graphene has literally been before our eyes and under our
noses for many centuries but was never recognised for what it really is.
0ȜĮȞȒĲȘ GRAPHENE
The reader may find some of the cited ideas and historical papers irrelevant,
but I tried my best to avoid any pre-2004 result, especially experimental,
being overlooked. All the mentioned studies poked in the right direction,
but there were no big surprises to spark a graphene gold rush. This is
probably because the earlier experiments had one thing in common. They
were observational. They observed ultra-thin graphitic films, and occasionaly
even monolayers without reporting any of graphene’s distinguishing proper-
ties. The very few electrical and optical measurements cited above were done
using thin films of graphite and could not assess the physics that graphene
has brought to the fore since 2004.
Our Science paper provided a clear watershed. Of course, the article
reported the isolation of graphene crystals large enough to do all sorts
of measurements, beyond the observation in an electron or scanning
probe microscope. The method of graphene isolation and identification it
described was so straightforward and accessible that even schoolchildren
could probably do it. This was important but, if we were to stop there, just
with the observations, our work would only add to the previous literature
and, I believe, disappear into oblivion. It is not the observation and isolation
of graphene but its electronic properties that took researchers by surprise.
Our measurements delivered news well beyond the Scotch tape technique,
which persuaded many researchers to join in the graphene rush.
First, the 2004 paper reported an ambipolar electric field effect, in which
resistivity changed by a factor of ~100. This is thousands of times more than
the few per cent changes observed previously for any metallic system and
amounted to a qualitative difference. To appreciate the exquisiteness of this
observation, imagine a nanometre thick Au film. No matter what you do
with such a film by physical means, it will remain a normal metal with the
same properties. In contrast, properties of graphene can be altered by simply
varying the gate voltage. We can tune graphene from a state close to a normal
metal with electrons in concentration ~1021 cm–3 to a metal with a similar
concentration of holes, all the way through a ‘semiconducting’ state with few
charge carriers.
Even more remarkably, our devices exhibited an astonishing electronic
quality. Graphene was completely unprotected from the environment, as
it was placed on a microscopically rough substrate and covered from both
sides with adsorbates and a polymer residue. Still, electrons could travel
submicron distances without scattering, flouting all the elements outside.
This level of electronic quality is completely counterintuitive. It contradicts
the common wisdom that surface science requires ultra-high vacuum and,
even then, thin films become progressively poorer in quality as their thickness
88

decreases. Even with hindsight, such electronic quality is mystifying and, in
fact, not fully understood so far.
In semiconductor physics, electronic quality is described in terms of
charge carrier mobility P. Our Science paper reported graphene with
room-T P |10,000 cm2/Vs (as of 2010, P can be 10 and 100 times higher
at room and low T, respectively [76,77]). For a general reader, 10,000 may
sound like just another number. To explain its significance, let us imagine
that in 2004 we made devices from, for example, reduced graphene oxide,
which exhibits P ~1cm2/Vs due to its irreversibly damaged crystal lattice [78].
In our second paper on graphene [79], we reported 2D dichalcogenides with
equally low P. Since then, there has been little interest in them. The reported
ballistic transport over submicron distances was essential to spark interest in
graphene and to allow the observation of many quantum effects reported
both in 2004 and later. This would have been impossible if graphene exhibited
P below several 1,000 cm2/Vs.
If not for graphene’s high quality and tunability, there would be no new
physics and, therefore, no graphene boom. In this respect, graphene his-
tory has something in common with that of solar planets. Ancient Greeks
observed them and called them wandering stars, ʌȜĮȞȒĲİȢ. After the physics
behind this wandering was discovered, people started perceiving planets
quite differently from ʌȜĮȞȒĲİȢ. Similarly, during the last six years people
discovered what graphene really is, which completely changed the earlier
perception. Our Science paper offered the first glimpse of graphene in its new
avatar as a high quality 2D electronic system and beyond.
MAGIC OF FLAT CARBON

What is this new incarnation? For me, 2004 was only the starting point for
the unveiling of many unique properties of graphene. Since then, we have
demonstrated that charge carriers in graphene are massless fermions
described by a Dirac-like equation rather than by the standard Schrödinger
equation [80]. In bilayer graphene, electrons receive yet another makeup
as massive Dirac fermions [81]. These properties were unveiled by the
observation of two new types of the integer quantum Hall effect, which
corresponded to the two types of Dirac fermions [1,65]. We also found
that graphene remained metallic in the limit of no charge carriers, even
when just a few electrons remained present in a micron-sized device [1,77].
Our experiments have revealed that graphene exhibits a universal optical
conductivity of Se2/2h, such that its visible opacity is just SD, where D is
the fine structure constant [82]. We suggested that the phenomenon of
Klein tunnelling, which was known in relativistic quantum physics for many
decades but assumed non-observable, could be probed using graphene
devices [83]. Several groups later demonstrated this experimentally. We were
lucky to be slightly quicker than others in showing that bilayer graphene was
a tuneable-gap semiconductor [84] and that graphene could be carved into
devices on a true nm scale [85]. We demonstrated sensors capable of detecting
89

individual molecules, more sensitive than any sensor before [38]. We suggested
that strain in graphene creates pseudo-magnetic fields that alter its electro-
nic properties [86] and later discussed the possibility of creating uniform
pseudo-fields and observation of the quantum Hall effect without an
external magnetic field [87]. Pseudo-magnetic fields in excess of 400 T were
reported experimentally half a year later. We made the first step into graphene
chemistry by experimentally introducing its derivatives, graphane and
stoichiometric fluorographene [88,89]. This is not even an exhaustive list of
the nice phenomena that we and our collaborators found in graphene and,
of course, many other researchers reported many other beautiful discoveries
that propelled graphene into its new status of a system that can nearly deliver
magic.
ODE TO ONE
After reading about the beautiful properties of graphene, the reader may
wonder why many atomic layers stacked on top of each other, as in graphite,
do not exhibit similar properties. Of course, any graphitic derivative has
something in common with its parent, but in the case of graphene, differ-
ences between the parent and descendants are fundamental. To appreciate
this, let us simplify the task and compare graphene with its bilayer. The
crucial distinctions are already there.
First, graphene exhibits record stiffness and mechanical strength [90]. As
for its bilayer, this strength is jeopardised by the possibility that the two layers
will slide relative to each other. This leads to a principal difference if, for
example, graphene or any thicker platelets are used in composite materials.
Second, graphene chemistry is different depending on whether one or both
surfaces of a monolayer are exposed. For example, atomic hydrogen cannot
bind to graphene from one side but makes a stoichiometric compound
(graphane) if both surfaces are exposed. This makes graphene much more
reactive than its bilayer. Third, an electric field is screened in graphite at
distances of about the interlayer separation, and the electric screening
becomes important even for a bilayer. For multilayer graphene, the electric
field can dope no more than a couple of near-surface atomic planes, leaving
the bulk unaffected. This makes it naïve to speculate about the use of gra-
phitic multilayers in active electronics. Fourth, charge carriers in a monolayer
are massless Dirac fermions whereas they are massive in a graphene bilayer.
This leads to essential differences in many electronic properties including
Shubnikov-de Haas oscillations, quantum Hall effect, Klein tunnelling and
so on. The Sorites paradox refers to a moment when a heap is no longer a
heap if the grains are removed one by one. For graphene, even its bilayer is
so different that two already make a heap.
90

TO COLLEAGUES AND FRIENDS
Our Science report was a collective effort, and I would again – on behalf of
Kostya and myself – like to thank all the other contributors. Serge Morozov
was and remains our ‘multitasking measurement machine’ working 24x7
when in Manchester. His electrical measurement skills are unmatched, and
I know that any curve he brings in is completely reliable and no questions
are ever asked whether this and that was checked and crosschecked. Da
Jiang was around from the very start, and it is unfortunate that I had to take
the project away from him because it was beyond the scope of a single new
PhD student. Sergey Dubonos and Yuan Zhang were the ones who made all
the devices without which our work would obviously have been impossible. I
utterly regret that our life trajectories have later diverged and, especially, that
Sergey has switched from microfabrication technology to goat farming. I also
acknowledge help of Anatoly Firsov in making those devices. Irina Grigorieva
helped with scanning electron microscopy but, more importantly, with
writing up the 2004 manuscript.
Figure 4. Those who made our first graphene paper possible but did not get the Prize.
91

The end of my timeline was only a start for further hard work involving
many collaborators. Our rapid progress would be impossible without Misha
Katsnelson who provided us with all the theoretical help an experimentalist
can only dream of. Since 2006, I have been enjoying collaboration with
other great theory guys including Antonio Castro Neto, Paco Guinea, Nuno
Peres, Volodya Fal’ko, Leonid Levitov, Allan MacDonald, Dima Abanin, Tim
Wehling and their co-workers. In particular, I want to acknowledge many
illuminating discussions and banter over dinners with Antonio and Paco.
As for experimentalists, the list is longer and includes Philip Kim, Ernie
Hill, Andrea Ferrari, Eva Andrei, Alexey Kuzmenko, Uschi Bangert, Sasha
Grigorenko, Uli Zeitler, Jannik Meyer, Marek Potemskii and many of their
colleagues.
Philip deserves special praise. In August 2004, before our Science paper
was published, his group submitted another important paper [91]. His
report described electronic properties of ultra-thin graphite platelets (down
to ~35 layers). Except for the thicker devices, Philip’s group followed the
same route as our now-celebrated paper. How close he was can be judged
from the fact that, after adopting the Scotch tape technique, Philip started
studying monolayers in early 2005. This allowed him to catch up quickly and,
in mid-2005, our two groups submitted independent reports that appeared
back-to-back in Nature, both describing the all-important observation of Dirac
fermions in monolayer graphene [80,92]. Later, I had the pleasure of closely
working with Philip on two joint papers, for Science and Scientific American. For
me personally, those back-to-back Nature papers signified a watershed. People
within the large semiconducting community no longer rumoured that ‘the
results were as difficult to reproduce as those by Hendrik Schön’, and friends
no longer stopped me in corridors with ‘be more careful; you know …’ I owe
Philip a great deal for this, and many people heard me saying – before and
after the Nobel Prize – that I would be honoured to share it with him.
Last but not least, let me acknowledge many bright young, and not so
young, colleagues: Peter Blake, Rahul Nair, Roman Gorbachev, Leonid
Ponomarenko, Fred Schedin, Daniel Elias, Sasha Mayorov, Rui Yang, Vasyl
Kravets, Zhenhua Ni, Wencai Ren, Rashid Jalil, Ibtsam Riaz, Soeren Neubeck,
Tariq Mohiuddin and Tim Booth. They were PhD students and postdocs
here in Manchester over the last six years and, as always, I avoid using the
feudal word ‘my’.
Finally, I acknowledge the financial support of EPSRC in its best, that is,
the responsive mode. This Nobel Prize would be absolutely impossible with-
out this mode. Let me also thank the Royal Society and the Leverhulme Trust
for reducing my teaching loads, which allowed me to focus on the project.
I have also received funding from the Office of Naval Research and the Air
Force Office of Scientific Research, which helped us to run even faster. The
Körber Foundation is gratefully acknowledged for its 2009 award. However,
I can offer no nice words for the EU Framework programmes which, except
for the European Research Council, can be praised only by Europhobes for
discrediting the whole idea of an effectively working Europe.
92

REFERENCES
1. A. K. Geim, K. S. Novoselov. Nature Mater. 6, 183 (2007).
2. A. K. Geim, P. Kim. Sci. Am. 298, 90 (2008).
3. A. K. Geim. Science 324, 1530 (2009).
4. A. K. Geim. JETP Lett. 50, 389 (1989).
5. S. J. Bending, K. von Klitzing, K. Ploog. Phys. Rev. Lett. 65, 1060 (1990).
6. A. K. Geim, P. C. Main, P. H. Beton, P. Streda, L. Eaves, C. D. Wilkinson, S. P.
Beaumont. Phys. Rev. Lett. 67, 3014 (1991).
7. A. K. Geim, P. C. Main, P. H. Beton, L. Eaves, C. D. W. Wilkinson, S. P. Beaumont.
Phys. Rev. Lett. 69, 1248 (1992).
8. A. K. Geim, S. V. Dubonos, J. G. S. Lok, I. V. Grigorieva, J. C. Maan, L. T. Hansen, P.
E. Lindelof. Appl. Phys. Lett. 71, 2379 (1997).
9. I. V. Grigorieva. Supercond. Sci. Technol. 7, 161 (1994).
10. J. S. Baker, S. J. Judd. Water Research 30, 247 (1996).
11. A. Geim. Phys. Today 51, No. 9, 36 (1998).
12. K. Autumn, Y. A. Lang, S. T. Ksieh, W. Zesch, W. P. Chan, T. W. Kenny, R. Fearing, R.
J. Full. Nature 405, 681 (2000).
13. A. K. Geim, S. V. Dubonos, I. V. Grigorieva, K. S. Novoselov, A. A. Zhukov, S. Y.
Shapoval. Nature Mater. 2, 461 (2003).
14. G. Lamarche, F. Lamarche, A. M. Lamarche, Europhys. Lett. 53, 378 (2001).
15. I. I. Barbolina, K. S. Novoselov, S. V. Morozov, S. V. Dubonos, M. Missous, A. O.
Volkov, D. A. Christian, I. V. Grigorieva, A. K. Geim. Appl. Phys. Lett. 88, 013901
(2006).
16. T. Cohen-Karni, Q. Qing, Q. Li, Y. Fang, C. M. Lieber. Nano Lett. 10, 1098 (2010).
17. Nevill Mott, A Life in Science, Taylor & Francis, 1986.
18. E. Bose, Phys. Z. 7, 373 (1906).
19. A. V. Butenko, Dm. Shvarts, V. Sandomirsky, Y. Schlesinger, R. Rosenbaum. J. Appl.
Phys. 88, 2634 (2000).
20. V. T. Petrashov, V. N. Antonov, B. Nilsson. J. Phys.– Cond. Mat. 3, 9705 (1991).
21. R. E. Glover, M. D. Sherrill. Phys. Rev. Lett. 5, 248 (1960).
22. C. H. Ahn et al. Rev. Mod. Phys. 78, 1185 (2006).
23. M. S. Dresselhaus, G. Dresselhaus. Adv. Phys. 30, 139 (1981).
24. Y. Kopelevich, P. Esquinazi, J. H. S. Torres, S. Moehlecke. J. Low Temp. Phys. 119, 691
(2000).
25. H. Kempa, P. Esquinazi, Y. Kopelevich. Phys. Rev. B 65, 241101 (2002).
26. K. S. Novoselov, A. K. Geim, S. V. Dubonos, E.W. Hill, I. V. Grigorieva. Nature 426, 812
(2003).
27. K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, Y. Zhang, S. V. Dubonos, I. V.
Grigorieva, A. A. Firsov. Science 306, 666 (2004).
28. J. A. Venables, G. D. T. Spiller, M. Hanbucken. Rep. Prog. Phys. 47, 399 (1984).
29. J. W. Evans, P. A. Thiel, M. C. Bartelt. Sur. Sci. Rep. 61, 1 (2006).
30. O. A. Shenderova, V. V. Zhirnov, D. W. Brenner, Crit. Rev. Solid State Mater. Sci. 27 227
(2002).
31. D. Tománek, W. Zhong, E. Krastev. Phys. Rev. B 48, 15461 (1993).
32. R. Seton. Carbon 34, 69 (1996).
33. S. Braga, V. R. Coluci, S. B. Legoas, R. Giro, D. S. Galvão, R. H. Baughman. Nano Lett.
4, 881 (2004).
34. C. D. Simpson, J. D. Brand, A. J. Berresheim, L. Przybilla, H. J. Rader, K Mullen. Chem.
Eur. J. 8, 1424 (2002).
35. A. Affoune, B. Prasad, H. Sato, T. Enoki, Y. Kaburagi, Y. Hishiyama, Chem. Phys. Lett.
348, 17 (2001).
36. T. J. Booth, P. Blake, R. R. Nair, D. Jiang, E. W. Hill, U. Bangert, A. Bleloch, M. Gass,
K. S. Novoselov, M. I. Katsnelson, A. K. Geim. Nano Lett. 8, 2442 (2008).
93

37. S. Ryu, L. Liu, S. Berciaud, Y. J. Yu, H. Liu, P. Kim, G. W. Flynn, L. E. Brus. Nano Lett.
10, 4944 (2010).
38. F. Schedin, A. K. Geim, S. V. Morozov, E.W. Hill, P. Blake, M. I. Katsnelson, K. S.
Novoselov. Nature Mater. 6, 652 (2007).
39. Letter to the Editor. “October 22, 2004: Discovery of Graphene” www.aps.org/publications/
apsnews/201001/letters.cfm
40. B. C. Brodie. Philos. Trans. R. Soc. London 149, 249 (1859).
41. D. R. Dreyer, S. Park, C. W. Bielawski, R. S. Ruoff. Chem. Soc. Rev. 39, 228 (2010).
42. G. Ruess, F. Vogt. Monatshefte Chem. 78, 222 (1948).
43. H. P. Boehm, A. Clauss, G. O. Fischer, U. Hofmann. Z. anorg. allgem. Chem. 316, 119
(1962).
44. J. C. Meyer, A. K. Geim, M. I. Katsnelson, K. S. Novoselov, D. Obergfell, S. Roth, C.
Girit, A. Zettl. Solid State Commun. 143, 101 (2007).
45. H. Shioyama. J. Mat. Sci. Lett. 20, 499 (2001).
46. L. M. Viculis, J. J. Mack, R. B. Kaner. Science 299, 1361 (2003).
47. S. Horiuchi, T. Gotou, M. Fujiwara, T. Asaka, T. Yokosawa, Y. Matsui. Appl. Phys. Lett.
84, 2403 (2004).
48. H. P. Boehm, R. Setton, E. Stumpp. Carbon 24, 241 (1986).
49. J. T. Grant, T. W. Haas. Surf. Sci. 21, 76 (1970).
50. J. M. Blakely, J. S. Kim, H. C. Potter. J. Appl. Phys. 41, 2693 (1970).
51. R. Rosei, M. De Crescenzi, F. Sette, C. Quaresima, A. Savois, P. Perfetti. Phys. Rev.
B 28, 1161 (1983).
52. C. F. McConville, D. P. Woodruff, S. D. Kevan, M. Weinert, J. W. Davenport. Phys. Rev.
B 34, 2199 (1986).
53. T. A. Land, T. Michely, R. J. Behm, J. C. Hemminger, G. Comsa. Surf. Sci. 264, 261
(1992).
54. A. J. van Bommel, J. E. Crombeen, A. van Tooren. Surf. Sci. 48, 463 (1975).
55. A. Nagashima, K. Nuka, K. Satoh, H. Itoh, T. Ichinokawa, C. Oshima, S. Otani. Surf.
Sci. 287, 609 (1993).
56. M. Terai, N. Hasegawa, M. Okusawa, S. Otani, C. Oshima. Appl. Surf. Sci. 130, 876
(1998).
57. I. Forbeaux, J. M. Themlin, J. M. Debever. Phys. Rev. B 58, 16396 (1998).
58. K. Seibert, G. C. Cho, W. Kütt, H. Kurz, D. H. Reitze, J. I. Dadap, H. Ahn, M. C.
Downer, A. M. Malvezzi. Phys. Rev. B 42, 2842 (1990).
59. T. W. Ebbesen, H. Hiura, Adv. Mater. 7, 582 (1995).
60. X. Lu, M. Yu, H. Huang, R. S. Ruoff. Nanotechnology 10, 269 (1999).
61. Y. Gan, W. Chu, L. Qiao, Surf. Sci. 539, 120 (2003).
62. Y. Ohashi, T. Koizumi, T. Yoshikawa, T. Hironaka, K. Shiiki. TANSO 180, 235 (1997).
63. Y. Ohashi, T. Hironaka, T. Kubo, K. Shiiki. TANSO 195, 410 (2000).
64. E. Dujardin, T. Thio, H. Lezec, T. W. Ebbesen. Appl. Phys. Lett. 79, 2474 (2001).
65. A. H. Castro Neto, F. Guinea, N. M. R. Peres, K. S. Novoselov, A. K. Geim. Rev. Mod.
Phys. 81, 109 (2009).
66. P. R. Wallace. Phys. Rev. 71, 622 (1947).
67. G. W. Semenoff. Phys. Rev. Lett. 53, 2449 (1984).
68. F. D. M. Haldane. Phys. Rev. Lett. 61, 2015 (1988).
69. J. Gonzales, F. Guinea, M. A. H. Vozmediano. Phys. Rev. B 59, 2474 (1999).
70. E. V. Gorbar, V. P. Gusynin, V. A. Miransky, I. A. Shovkovy. Phys. Rev. B 66, 045108
(2002).
71. T. Ando, T. Nakanishi, R. Saito. J. Phys. Soc. Jpn. 67, 2857 (1998).
72. Y. Zheng, T. Ando. Phys. Rev. B 65, 245420 (2002).
73. R. Saito, M. Fujita, G. Dresselhaus, M. S Dresselhaus. Appl. Phys. Lett. 60, 2204 (1992).
74. H. J. Teuschler. Method of producing isolated field effect transistors employing pyrolytic
graphite. US Patent 3,522,649.
75. R. B. Little. J. Cluster Sci. 14, 135 (2003).
94

76. C. R. Dean et al. Nature Nano 5, 722 (2010).
77. E. V. Castro, H. Ochoa, M. I. Katsnelson, R. V. Gorbachev, D. C. Elias, K. S. Novoselov,
A. K. Geim, F. Guinea. Phys. Rev. Lett. 105, 266601 (2010).
78. K. Erickson, R. Erni, Z. Lee, N. Alem, W. Gannett, A. Zettl. Adv. Mat. 22, 4467 (2010).
79. K. S. Novoselov, D. Jiang, F. Schedin, T. J. Booth, V. V. Khotkevich, S. V. Morozov, and
A. K. Geim. Proc. Natl. Acad. Sci. U.S.A. 102, 10451 (2005).
80. K. S. Novoselov, A. K. Geim, S. M. Morozov, M. I. Katsnelson, I. V. Grigorieva, S. V.
Dubonos, A. A. Firsov. Nature 438, 197 (2005).
81. K. S. Novoselov, E. McCann, S. V. Morozov, V. I. Fal’ko, M. I. Katsnelson, U. Zeitler, D.
Jiang, F. Schedin, A. K. Geim. Nature Phys. 2, 177 (2006).
82. R. R. Nair, P. Blake, A. N. Grigorenko, K. S. Novoselov, T. J. Booth, T. Stauber, N. M.
R. Peres, A. K. Geim. Science 320, 1308 (2008).
83. M. I. Katsnelson, K. S. Novoselov, A. K. Geim. Nature Phys. 2, 620 (2006).
84. E.V. Castro, K. S. Novoselov, S. V. Morozov, N. M. R. Peres, J. M. B. Lopes dos Santos,
J. Nilsson, F. Guinea, A. K. Geim, A. H. Castro Neto. Phys. Rev. Lett. 99, 216802
(2007).
85. L. A. Ponomarenko, F. Schedin, M. I. Katsnelson, R. Yang, E. W. Hill, K. S. Novoselov,
A. K. Geim. Science 320, 356 (2008).
86. S. V. Morozov, K. S. Novoselov, M. I. Katsnelson, F. Schedin, L. A. Ponomarenko, D.
Jiang, A. K. Geim. Phys. Rev. Lett. 97, 016801 (2006).
87. F. Guinea, M. I. Katsnelson, A. K. Geim. Nature Phys. 6, 30 (2010).
88. D. C. Elias et al. Science 323, 610 (2009).
89. R. R. Nair et al. Small 6, 2877 (2010).
90. C. Lee, X. Wei, J. W. Kysar, J. Hone. Science 321, 385 (2008).
91. Y. Zhang, J. P. Small, M. E. S. Amori, P. Kim. Phys. Rev. Lett. 94, 176803 (2005).
92. Y. B. Zhang, Y. W. Tan, H. L. Stormer, P. Kim. Nature 438, 201 (2005).
Portrait photo of Professor Geim by photographer Ulla Montan.
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Dr. FARSEEM MANNAN

1st Edition: February 2014; 2nd Edition: June 2015

Prof Ali Asgar

Prof M Rezwan Khan

Prof David Thompson

Prof M Jamal Deen

Solid state series in Bengali

Dr. Farseem Mohammedy 3

Dr. Farseem Mohammedy 4

Weeks Sections Topics

1 1.8 General introduction, Crystal structure

2,3 Ch. 2 Theory of Conduction

4-7 Parts of Ch. 3, Quantum Mechanics: wave equation,

12-13 Ch. 8 Magnetics

14 Ch. 15 of Solymar Metamaterials and other advanced topics

Dr. Farseem Mohammedy 5

• Class tests/assignments – 30%

Dr. Farseem Mohammedy 6

6.1 Till!o$ ma!has b.cn up igalnstNlti'rei

0- Engireeringusedtobcado\1n to c:dhlrofession T|e Roman enginee's aho

|henomcru. The fiic details reprcsenied b) .luantum mechrnics are ave.{gcd

2bout conductors. irsllalols. semiconductols,p niLrnctions. talrsistds lasers'

o;_ Fig- : -:-

Dr. Farseem Mohammedy 2

“The chocolate microstructure” contains “six

Dr. Farseem Mohammedy 4

• A Crystalline Solid is a solid object in which atoms bond with

• Most important property of a crystal is periodicity, leading to

• Examples of periodic array/crystalline solids: nearly all metals,

Dr. Farseem Mohammedy 5

Dr. Farseem Mohammedy 6

Dr. Farseem Mohammedy 7

• Each atom in the corner

Dr. Farseem Mohammedy 8

• Each atom in the corner

Dr. Farseem Mohammedy 9

The Hexagonal Close Packed (HCP)

• See the book

Dr. Farseem Mohammedy 10

Covalently bonded cubic solids

Dr. Farseem Mohammedy 11

Diamond and Zinc-Blende

Dr. Farseem Mohammedy 13

Directions and planes

Directions and planes

Dr. Farseem Mohammedy 15

Directions and planes

Dr. Farseem Mohammedy 16

Think: why [010] is not equivalent to [020]?

Dr. Farseem Mohammedy 18

How to incorporate electric field in

• Under an electric field Ex , electrons accelerated in x-direction in

• Self study:- Example 2.4(P-120) for an alternate explanation

• So, resistivity of a pure metal is linearly dependent on

• There are various temperature dependencies of  :

All these formulas are based on semi-empirical analysis, and

• For Most of pure metals,

The resistivity of various metals as a function of temperature above 0 °C.

• Copper metal has

Please study P.129-131

• Nordheim’s rule applies only to single phase solid solutions. It is