ENGINEERING

PHYSICS
[SUBJECT CODE: PHY1071]

I Year B.Tech. Course Material for Other Stream

DEPARTMENT OF PHYSICS
MANIPAL INSTITUTE OF TECHNOLOGY

[2024]
 Contents
1 LASERS AND FIBRE OPTICS ............................................................... 4
CHARACTERISTICS OF LASERS ............................................................................... 4
INTERACTION OF RADIATION WITH MATTER .................................................... 4
ESSENTIAL COMPONENTS OF A LASER .............................................................. 11
He-Ne LASER ............................................................................................................... 11
RUBY LASER .............................................................................................................. 12
SEMICONDUCTOR LASER ....................................................................................... 13
OPTICAL FIBRES ........................................................................................................ 17
ACCEPTANCE ANGLE, ACCEPTANCE CONE AND NUMERICAL APERTURE18
TYPES OF OPTICAL FIBRES .................................................................................... 20
ATTENUATION IN OPTICAL FIBRES ..................................................................... 23
QUESTIONS ................................................................................................................. 27
PROBLEMS .................................................................................................................. 28
2 QUANTUM PHYSICS ........................................................................... 31
BLACKBODY RADIATION AND PLANCK’S HYPOTHESIS ............................... 31
PHOTOELECTRIC EFFECT ....................................................................................... 34
COMPTON EFFECT .................................................................................................... 37
PHOTONS AND ELECTROMAGNETIC WAVES [DUAL NATURE OF LIGHT] . 40
DE BROGLIE HYPOTHESIS - WAVE PROPERTIES OF PARTICLES .................. 40
THE QUANTUM PARTICLE ...................................................................................... 42
DOUBLE–SLIT EXPERIMENT REVISITED............................................................. 45
UNCERTAINTY PRINCIPLE...................................................................................... 45
QUESTIONS ................................................................................................................. 46
PROBLEMS .................................................................................................................. 47
3 QUANTUM MECHANICS .................................................................... 51
AN INTERPRETATION OF QUANTUM MECHANICS .......................................... 51
THE SCHRÖDINGER EQUATION ............................................................................ 53
PARTICLE IN AN INFINITE POTENTIAL WELL (PARTICLE IN A “BOX”) ...... 53
A PARTICLE IN A POTENTIAL WELL OF FINITE HEIGHT ................................ 55
TUNNELLING THROUGH A POTENTIAL ENERGY BARRIER ........................... 57
THE SIMPLE HARMONIC OSCILLATOR................................................................ 58

1
 QUESTIONS ................................................................................................................. 59
PROBLEMS .................................................................................................................. 60
4 MOLECULES AND SOLIDS ................................................................ 62
ENERGY STATES AND SPECTRA OF MOLECULES ............................................ 62
ROTATIONAL MOTION OF MOLECULES ............................................................. 62
VIBRATIONAL MOTION OF MOLECULES ............................................................ 63
MOLECULAR SPECTRA ............................................................................................ 65
BONDING IN SOLIDS................................................................................................. 67
FREE-ELECTRON THEORY OF METALS ............................................................... 70
BAND THEORY OF SOLIDS...................................................................................... 74
ELECTRICAL CONDUCTION IN METALS, INSULATORS AND
SEMICONDUCTORS................................................................................................... 75
HALL EFFECT ............................................................................................................. 78
RESISTIVITY MEASUREMENT BY FOUR PROBE METHOD ............................. 80
PHOTOVOLTAIC EFFECT AND SOLAR CELLS .................................................... 81
SUPERCONDUCTIVITY-PROPERTIES AND APPLICATIONS............................. 88
QUESTIONS ................................................................................................................. 91
PROBLEMS .................................................................................................................. 92
5 DIELECTRICS ....................................................................................... 95
INTRODUCTION ......................................................................................................... 95
POLARIZATION IN A DIELECTRIC MATERIAL ................................................... 96
COMPONENTS OF POLARIZABILITY .................................................................... 99
FREQUENCY DEPENDENCE OF POLARIZATION ............................................. 104
TEMPERATURE DEPENDENCE OF POLARIZATION ........................................ 106
LOCAL FIELD (OR INTERNAL FIELD) IN A SOLID DIELECTRIC MATERIAL107
CLAUSIUS-MOSSOTTI EQUATION ....................................................................... 109
DIELECTRIC LOSS AND LOSS TANGENT ........................................................... 110
DIELECTRIC BREAKDOWN AND DIELECTRIC STRENGTH ........................... 111
APPLICATIONS OF DIELECTRIC MATERIALS .................................................. 111
FERROELECTRIC MATERIAL................................................................................ 112
QUESTIONS ............................................................................................................... 114
PROBLEMS ................................................................................................................ 114
6 INTRODUCTION TO NANOSCIENCE ............................................. 119

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INTRODUCTION ....................................................................................................... 119
NANOSCIENCE AND NANOTECHNOLOGY ....................................................... 121
SURFACE TO VOLUME RATIO.............................................................................. 122
QUANTUM CONFINEMENT ................................................................................... 124
QUANTUM DOTS (QDs) .......................................................................................... 126
PREPARATION TECHNIQUES................................................................................ 128
APPLICATIONSOFNANOTECHNOLOGY ............................................................. 129
MODERN ENGINEERING MATERIALS ................................................................ 132
QUESTIONS ............................................................................................................... 138

3
 1 LASERS AND FIBRE OPTICS

OBJECTIVES:

• To explain basic interactions of radiation with matter.

• To comprehend the basic principle of lasing system and their applications.
• To understand the basic working principle of optical fibre and their applications.
• To classify different types of optical fibres and explain their merits & demerits.

CHARACTERISTICS OF LASERS

Laser light is highly monochromatic, highly coherent, highly directional and can be sharply
focused. Each of these characteristics that are not normally found in ordinary light makes laser
a unique and the most powerful tool. Lasers find a wide variety of applications in the field of
scientific research, engineering and medicine.

INTERACTION OF RADIATION WITH MATTER

There are three possible ways through which interaction of radiation and matter can take place,
absorption of radiation is one means, and the emission of radiation, as suggested by Einstein in
1917, can occur in two ways namely the spontaneous emission, and the stimulated emission.

All the three are described as follows by considering an atom as a system.

Absorption: Absorption of a photon of frequency f takes place when the energy difference
E2 – E1 of the allowed energy states of the atomic system equals the energy hf of the
photon. Then the photon disappears and the atomic system moves to upper energy state E2.

Figure 1.1: Absorption

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Spontaneous Emission: Spontaneous emission is the emission of a photon when a system
transits from a higher energy state to a lower energy state without the aid of any external
agency. The average life time of the atomic system in the excited state is of the order
of 10–8 s. After the life time of the atomic system in the excited state, it comes back
to the state of lower energy on its own accord by emitting a photon of energy hf =
E2– E1 .

In an ordinary light source, the radiation of light from different atoms is not coherent.
The radiations are emitted in different directions in random manner. Such type of emission
of radiation is called spontaneous emission.

Figure 1.2: Spontaneous Emission

Stimulated Emission: When a photon (called stimulating photon) of suitable frequency
interacts with an excited atomic system, the latter comes down to ground state before its life
time. Such an emission of radiation is called stimulated emission. In stimulated emission,
both the stimulating photon and the stimulated photon are of same frequency, same
phase and are in same state of polarization. These photons are emitted in the same direction.
In other words, these two photons are coherent. This phenomenon is responsible for laser
action.

Figure 1.3: Stimulated Emission

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POPULATION INVERSION

From Boltzmann statistics, the ratio between population of atoms in two energy states E1 and
E2 at equilibrium temperature T is,

𝑵𝟐
= 𝒆−(𝑬𝟐 −𝑬𝟏 )/𝒌𝑻
𝑵𝟏
1.1
where k is Boltzmann constant, N1 is density of atoms with energy E1 & N2 is density of atoms
with energy E2 . Under normal condition, where populations are determined only by the action
of thermal agitation, population of the atoms in upper energy state is less than that in lower
energy state (i.e. N2 < N1, Figure 1.4 a).

Figure 1.4: (a) Normal thermal equilibrium distribution of atomic systems (b) An inverted
population.

For the stimulated emission rate to exceed the absorption rate it is necessary to have higher
population of upper energy state than that of lower energy state. This condition is called
population inversion (N2 > N1, Figure 1.4b). This is a non-equilibrium condition and is
facilitated by the presence of energy states called ‘metastable states’ where the average
life time of the atom is 10-3 s which is much longer than that of the ordinary excited state (
10-8s).

EINSTEIN’S COEFFICIENTS

Einstein coefficients give the probability associated with the absorption and emission
processes. Consider two energy states 𝐸1 and 𝐸2 of a system of atoms (E2 > E1 ). Let N₁ and
N2 be the density of atoms with energies 𝐸1 and E2 respectively, per unit volume of the system.
Let radiations with a continuous spectrum of frequencies be incident upon the system. Let there
be a radiation of frequency 𝑓 such that 𝑓 = (𝐸2 − 𝐸1 )/ℎ. Also let I𝑓 𝑑𝑓 be the energy
incident/unit volume of the system considering only those radiations whose frequencies lie in
the range 𝑓 and 𝑓 +𝑑𝑓 . Then, 𝐼𝑓 represents the energy density of frequency 𝑓.

Let us consider the absorption, and the two emission processes case by case.

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(1) In the case of absorption, an atom in the level 𝐸₁ can go to the level 𝐸2 , when it absorbs
a radiation of frequency 𝑓 such that 𝑓 = (𝐸2 − 𝐸1 )/ℎ (Fig. 1.1).

The number of such absorptions per unit time, per unit volume is called rate of absorption.
The rate of absorption depends upon,

(a) the number density of lower energy state, i.e., 𝑁₁, and, (b) the energy density i.e., 𝐼𝑓 .

∴ Rate of absorption ∝ 𝑵𝟏 𝑰𝒇
Rate of absorption = 𝑩₁₂ 𝑵₁ 𝑰𝒇 1.2
where, 𝐵₁₂ is the constant of proportionality called Einstein coefficient of induced absorption.

(2) In the case of spontaneous emission, an atom in the higher energy level 𝐸2 undergoes
transition to the lower energy level 𝐸1 , voluntarily by emitting a photon (Fig. 1.2).

Since it is a voluntary transition, it is independent of the energy density of any frequency in the
incident radiation. The number of such spontaneous emissions per unit time, per unit volume
is called rate of spontaneous emission which is proportional to only the number density in the
higher energy state, i.e., 𝑁2 .

∴ Rate of spontaneous emission = 𝑨𝟐𝟏 𝑵₂ 1.3

where, 𝐴21 is the constant of proportionality called the Einstein coefficient of spontaneous
emission.

(3) In case of stimulated emission, the system requires an external photon of appropriate
frequency = [(𝐸₂ − 𝐸₁)/ℎ], to stimulate the atom for the corresponding downward transition,
and thereby cause emission of stimulated photons (Fig. 1.3), the energy density 𝐼𝑓 , has a role
to play in this case.

The number of stimulated emissions per unit time per unit volume, called rate of stimulated
emission, is proportional to, a) the number density of the higher energy state, i.e., 𝑁₂ and, b)
the energy density, i.e., 𝐼𝑓 .

∴ Rate of stimulated emission ∝ 𝑵𝟐 𝑰𝒇

Rate of stimulated emission = 𝑩𝟐𝟏 𝑵𝟐 𝑰𝒇
1.4

7
where, 𝐵21 is the constant of proportionality called the Einstein coefficient of simulated
emission.

In thermal equilibrium, the total energy of the system remains unchanged in spite of the
interaction that is taking place between itself and the incident radiation. Under such a condition,
the number of photons absorbed by the system per second must be equal to the number of
photons it emits per second by both the stimulated and the spontaneous emission processes.

∴ At thermal equilibrium,

Rate of absorption = Rate of spontaneous emission + Rate of stimulated emission,

∴ From Eqs (1.1), (1.2) & (1.3), we have 𝑩₁₂ 𝑵₁ 𝑰𝒇 = 𝑨𝟐𝟏 𝐍𝟐 + 𝑩𝟐𝟏 𝑵𝟐 𝑰𝒇
1.5
Or 𝐼𝑓 (𝐵₁₂ 𝑁₁ − 𝐵21 𝑁2 ) = 𝐴21 N2

𝐴21 N2
Or, 𝐼𝑓 = (𝐵₁₂ 𝑁₁ − 𝐵21 𝑁2 )

By rearranging the above equation, we get,

𝑨𝟐𝟏 𝟏
𝑰𝒇 = [ 𝑩₁₂ 𝑵₁ ]
𝑩𝟐𝟏 −𝟏
𝑩𝟐𝟏 𝐍𝟐
1.6

But, by Boltzmann's law, we have,

𝒉𝒇 𝒉𝒇
𝑵𝟐 𝑵
= 𝒆−(𝑬𝟐 −𝑬𝟏 )/𝒌𝑻 = 𝒆−𝒌𝑻 ∴ 𝑵𝟏 = 𝒆𝒌𝑻
𝑵𝟏 𝟐
1.7
Equation (1.6) becomes,

𝑨 𝟏
𝑰𝒇 = 𝑩𝟐𝟏 [ 𝒉𝒇 ] 1.8
𝟐𝟏 𝑩₁₂
𝒆𝒌𝑻 − 𝟏
𝑩𝟐𝟏

According to Planck's law, the equation for 𝐼𝑓 , is,

𝟖𝝅𝒉𝒇𝟑 𝟏
𝑰𝒇 = [ 𝒉𝒇 ]
𝒄𝟑
𝒆𝒌𝑻 − 𝟏
1.9
Now, comparing the equations (1.8) and (1.9), term by term on the basis of positional identity,
we have,
8
𝐴21 8𝜋ℎ𝑓 3 𝐵₁₂
= and, =1 or 𝐵12 = 𝐵21
𝐵21 𝑐3 𝐵21

Hence the probability of induced absorption is equal to the probability of stimulated emission.

ℎ𝑓
𝐴21
Hence equation (1.8) can be rearranged as = 𝐼𝑓 (𝑒 𝑘𝑇 − 1) 1.10
𝐵21

Because of the above identity, the subscripts could be dropped, and 𝐴21 & 𝐵21 can be
represented simply as A and B and Eq (1.8) can be rewritten.

𝐀
∴ At thermal equilibrium the equation for energy density is, 𝑰𝒇 = 𝒉𝒇
𝑩[𝒆𝒌𝑻 − 𝟏]

1.11
INTERPRETATION OF EINSTEIN’S COEFFICIENTS:
Dependence of nature of emission on frequency:

𝐴21 8𝜋ℎ𝑓 3 𝐴21

We have, = 𝑖𝑚𝑝𝑙𝑖𝑒𝑠 ∝ 𝑓3
𝐵21 𝑐3 𝐵21

Since 𝑓 = (Δ𝐸/ℎ), the above proportionality implies that for large f values.

For higher Δ𝐸 values, the transitions in the system are such that, the probability of spontaneous
emission supersedes that for stimulated emissions by a large margin.
Case (i) 𝒉𝒇 >> 𝒌𝑻 :
ℎ𝑓
When the frequency of radiation is high, ℎ𝑓 >> 𝑘𝑇, due to which 𝑒 𝑘𝑇 ≫ 1
𝐴21
Hence in Equation (1.10), ≫ 1, i.e.. A21≫ 𝐵21
𝐵21

Hence the spontaneous emissions will be much larger in number than the stimulated emissions.

Case (ii) ≈ 𝒌𝑻 :
ℎ𝑓
For ℎ𝑓 ≈ 𝑘𝑇, 𝑒 𝑘𝑇 will be low and comparable to 1.

∴ 𝐴21 & 𝐵21 become comparable, which means, the process of stimulated emissions become
significant.

Case (iii) << 𝒌𝑻 :

ℎ𝑓
𝐴21
For ℎ𝑓 ≪ 𝑘𝑇, (𝑒 𝑘𝑇 − 1) << 1, and, ≪ 1, Or, B21 ≫ 𝐴21
𝐵21

9
Hence for lower frequencies, stimulated emissions dominate the emission process. This is what
we observe at room temperature in the atomic transitions which generate microwaves.

Non-Equilibrium conditions leading to amplification (Laser action):

We have from equation (1.4),

Rate of emission 𝐴21 𝑁2 + 𝐵21 𝑁2 𝐼𝑓 𝑁2 𝐴21 + 𝐵21 𝐼𝑓

= = [ ]
Rate of absorption 𝐵₁₂ 𝑁₁ 𝐼𝑓 𝑁1 𝐵₁₂ 𝐼𝑓

Since in the Einstein’s theory we have 𝐵12 = 𝐵21 ,

𝐑𝐚𝐭𝐞 𝐨𝐟 𝐞𝐦𝐢𝐬𝐬𝐢𝐨𝐧 𝑵𝟐 𝑨𝟐𝟏

= [𝑩 + 𝟏] 1.12
𝐑𝐚𝐭𝐞 𝐨𝐟 𝐚𝐛𝐬𝐨𝐫𝐩𝐭𝐢𝐨𝐧 𝑵𝟏 𝟐𝟏 𝑰𝒇

Now let us again get back to Eq (1.10). If for the system, the energy levels 𝐸1 & 𝐸2 , involved
in the transitions are such that Δ𝐸 << 𝑘𝑇, i.e., ℎ𝑓 << 𝑘𝑇, then as per Eq (1.10).

𝐴21
≪1
𝐵21 𝐼𝑓

𝐑𝐚𝐭𝐞 𝐨𝐟 𝐞𝐦𝐢𝐬𝐬𝐢𝐨𝐧 𝑵𝟐
∴ Eq (1.12) can be expressed as, = 1.13
𝐑𝐚𝐭𝐞 𝐨𝐟 𝐚𝐛𝐬𝐨𝐫𝐩𝐭𝐢𝐨𝐧 𝑵𝟏

Under normal conditions in all the systems, 𝑁2 will always be lesser than 𝑁₁.

Now let us consider a system which can support the energy level population status with N2>N1,
between certain pair of energy levels i.e., the system in which population inversion could be
achieved. By some suitable means of energy supply when the population is inverted between
the pair of energy levels in the system, the system will then be under non-equilibrium
conditions since the Boltzmann factor conditions are violated.

As per Eq (1.10), under non-equilibrium conditions, rate of emission exceeds the rate of
absorption. Further if the photons emitted in a particular direction are returned into the system
by reflecting them back and forth, then the rate of stimulated emission soon exceeds the
absorption rate. If right conditions are provided, all the stimulated emissions could be arranged
to be identical in respect of wavelength, phase & direction to the one starting stimulating
radiation. In other words, we can say that, the single starting stimulating radiation itself has
been multiplied or, amplified. But the amplification takes place at the cost of downward
transitions which will soon reverse the condition, 𝑁2 > 𝑁1. In order to sustain the status of

10
population inversion, energy is provided in the right manner to keep lifting atoms to higher
energy level continuously so long as amplification is required to be maintained.

This forms the basis for functioning of every laser.

ESSENTIAL COMPONENTS OF A LASER

The laser device basically consists of three elements (Fig 1.5).

• Pumping system
• Lasing medium/ active medium
• A resonant cavity or an optical cavity

Lasing medium has atomic systems (active centers), with special energy levels which are
suitable for laser action. This medium may be a gas, or a liquid, or a crystal or a
semiconductor. The atomic systems in this may have energy levels including a ground
state (E1), an excited state (E3) and a metastable state (E2).

Figure 1.5: Block diagram of laser system

He-Ne LASER

He-Ne Laser has a glass discharge tube filled with He (80%) and Ne (20%) at low
pressure. Helium gas is the “pumping” medium and Neon gas is the “lasing” medium (Figure
1.6). The simplified energy level diagram (Figure 1.7) shows four levels: Eo, E1, E2 and
E3. Electrons and ions in the electrical gas discharge occasionally collide with He-
atoms, raising them to level E3 (a metastable state). During collisions between He- and
Ne- atoms, the excitation energy of He-atom is transferred to Ne-atom (level E2),
selectively populating E2 due to resonant energy transfer. Thus, population inversion occurs
between levels E2 and E1. This population inversion is maintained because (i) the
metastability of level E3 ensures a ready supply of Ne-atoms in level E2 and (ii) level

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E1 decays rapidly to Eo. Stimulated emission from level E2 to level E1 predominates,
and red laser light is generated. The mirror M1 is fully reflective and the mirror M2 is
partially reflective to allow the laser beam to come out. The Brewster’s windows W
‘s are at polarizing angles to the mirrors, to reduce the reflection loss.

Figure 1.6 Basic elements of He-Ne gas laser

Figure 1.7: Atomic levels involved in the operation of He-Ne gas laser

RUBY LASER

In ruby laser (Figure 1.8), the lasing medium is a ruby rod which has chemical composition
of Al2O3 doped with Cr2O3. Cr3+ ions are the active centers, which has approximately
similar energy level structure as shown in Figure 1.9. The resonant cavity is a pair of
parallel mirrors to reflect the radiation back into the lasing medium. Pumping is a
process of exciting more number of atoms in the ground state to higher energy states,

12
which is required for attaining the population inversion. The atoms in the state E3 may
come down to state E1 by spontaneous emission or they may come down to metastable
state (E2) by collision. The atoms in the state E2 come down to state E1 by stimulated
emission. These radiations may be reflected due to mirror action of the end faces. When
population inversion takes place at E2, a stray photon of right energy stimulates chain
reaction, accumulates more photons, all coherent. The reflecting ends turn the coherent
beam back into active region so that the regenerative process continues and part of the
light beam comes out from the partial mirror as a laser pulse. The output is an intense
beam of coherent light.

Fig. 1.8 Construction of Ruby laser

Figure 1.9: The basic three-level scheme for laser operation

SEMICONDUCTOR LASER

The semiconductor laser was first constructed by Hall et al. in 1962. The active medium in a
semiconductor laser is a p-n junction diode and hence the semiconductor laser is also called
diode laser.

13
Principle: It is based on the principle of the emission of the recombination energy in
form of light in certain semiconducting materials such as GaAs, GaAlAs, etc. By heavily
doping the p-n junction diode and by applying a high current density, the stimulated emission
of light is produced and hence the laser operation is made possible in the semiconductor laser.
C p-n junction of a semiconductor laser is prepared using n-GaAs and p-
GaAs. The height, width and breadth of this laser are 1 mm x 1 mm x 1 mm respectively. The
upper and bottom surface of the p-n junction are used for ohmic contact, the front and back
surfaces are used as resonators. For resonators, the end faces are made perfectly parallel to each
other and highly polished. One end is made fully reflecting, whereas the other end is made
partially reflecting. The remaining two surfaces are made rough, so as to prevent the leakage
of light through these faces. The diode is forward biased, with a voltage nearly equal to the
band gap voltage of the material. The p and n-type layers are heavily doped.
heavily doping of the and n-type regions produces population inversion
in the depletion region of the diode. The diode is forward biased with a voltage equal to the V=
Eg/e energy gap voltage, and hence the recombination of the holes and electrons takes place.
In order to produce and maintain the stimulated emission continuously, a high current density
nearly in the order of 20 kA/cm2 is applied. Due to the high current density, more and more
number of electrons are injected into the n-region and more number of holes are injected into
the p-region and hence the continuous emission of light is made possible. Since, more number
of charge carriers are injected, the laser is also called injection laser. The output laser beam
emerges from the p-n junction of the partially reflecting surface as shown in Fig.1.10. The
output wavelength is given by

Figure 1.10: Semiconductor laser

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APPLICATIONS OF LASER

Laser is used in various scientific, engineering and medical applications. It is used in

investigating the basic laws of interaction of atoms and molecules with electromagnetic wave
of high intensity. Laser is widely used in engineering applications like optical communication,
micro welding and sealing etc. In medical field, laser is used in bloodless and painless surgery
especially in treating the retinal detachment. Also used as a tool in treating dental decay, tooth
extraction, cosmetic surgery.

i) Bar code scanner

Laser technology plays a crucial role in reading barcodes, primarily due to its precision and
directionality. When a laser scanner directs a narrow beam of light onto a barcode, the light
interacts with the pattern of black and white stripes. The barcode, typically in the form of a
Universal Product Code (UPC), consists of vertical stripes that represent data. Each digit is
encoded using a pattern of seven blocks, which are either black or white, to denote numbers
from 0 to 9 as shown in the Figure 1.11.

Figure 1.11: Universal Product Code (UPC)

The directionality of the laser beam ensures it can consistently scan the barcode from various
angles, enabling reliable reading even in different orientations. The laser beam’s narrow focus
allows it to distinguish fine details, making it effective in reading densely packed barcodes.
The physics of laser interaction with barcodes involves the reflection of light from the
barcode's surface. Black stripes absorb more light, reflecting less, while white spaces reflect
more light back to the scanner. This variation in reflected light intensity is captured by a
photodiode or a charge-coupled device (CCD) within the scanner. The device converts these

15
 light variations into electrical signals, which the scanner's software decodes into the barcode’s
data, enabling quick and accurate data processing. The primary advantage of laser scanners
is their ability to read barcodes quickly and accurately from a distance, making them
indispensable in retail, warehousing, and industrial applications.
ii) Laser Printer

Laser printers are a type of printer that uses a laser beam to produce an image on a
photosensitive drum, which is then transferred to paper. Schematic diagram of Laser printer is
shown in Figure 1.12. Here is a basic overview of how laser printers work:

Charging: The process begins with a photosensitive drum being given an overall positive
charge.

Writing: The laser beam is then used to selectively discharge the drum in specific areas
corresponding to the image being printed. Where the laser hits the drum, the charge is removed,
leaving behind a pattern of discharged and charged areas.

Developing: Toner, a fine powder made up of pigment and plastic particles, is then applied to
the drum. The toner particles are attracted to the charged areas of the drum, sticking to the
discharged areas and forming the image.

Transferring: The paper is given a negative charge, and as it passes by the drum, the toner is
transferred from the drum to the paper, forming the image on the paper.

Fusing: The toner on the paper is then fused into place using heat.

Figure 1.12: Laser Printer

iii) Laser Cooling

Principle of Laser cooling (Figure 1.13) is the use of dissipative light forces for reducing the
random motion and thus the temperature of small particles, typically atoms or ions. Depending
on the mechanism used, the temperature achieved can be in the milli-kelvin, micro-kelvin, or
even nano-kelvin regime. If an atom is traveling toward a laser beam and absorbs a photon

16
from the laser, it will be slowed by the fact that the photon has momentum, p =E/c = h/λ. It
would take a large number of such absorptions to cool the sodium atoms to near 0 K. The
following are the two types of laser cooling: i. Doppler Cooling and ii. Sisyphus Cooling.

Figure 1.13: Laser Cooling

OPTICAL FIBRES

Optical fibres are thin, flexible strands of transparent dielectric material such as glass or plastic.
They are basically used to guide infrared & visible light waves through curved paths.
Construction of optical fibre:

It consists of a central cylindrical core made of pure glass or plastic of refractive index n 1
surrounded by a cladding made of similar material but of lower refractive index n2 (n2 < n1).
But there is a material continuity from core to cladding. The cladding is enclosed in a
polyurethane jacket that protects the fibre from external damaging factors such as abrasion,
crushing & chemical reactions (Figure 1.14). Many such protected fibres are grouped to form
a cable. The diameter of the core varies between 10 to 200 m that of the cladding varies
between 50 to 250 m.

17
 Figure 1.14: Optical fibre – sectional view

PRINCIPLE OF OPTICAL FIBRES

Optical fibres work on the principle of total internal reflection of light. When a beam of light
traveling in an optically denser medium falls on interface separating denser medium from
relatively less dense medium, if the angle of incidence is greater than particular angle called
critical angle (C) for the pair of media, the light undergoes total internal reflection (Figure
1.15). Total internal reflection is the most superior type of reflection. Reflection is total in the
sense that almost the entire energy is returned to the first medium through reflection without
any loss of energy. Due to this the optical fibres are able to sustain light signal transmission
over very long distances despite infinite number of reflections.

Figure 1.15: Total internal reflection

ACCEPTANCE ANGLE, ACCEPTANCE CONE AND NUMERICAL APERTURE

Consider an optical fibre with refractive index of the material of the core n1 and cladding n2
placed in a surrounding medium of refractive index n0 (Figure 1.16). Let a ray AO of light enter
the core of the fibre at an angle 0. Let this ray after refraction through an angle 1 at O strikes
the interface between the core and the cladding at the critical angle such that the refracted ray
grazes the interface.

18
 Figure 1.16: Wave propagation through fibre

Applying Snell’s law of refraction at O, we have,

sin  0 n1
=
sin  1 n0

n1
 sin  0 = sin  1 1.14
n0

Similarly, applying Snell’s law at B,

sin ( 90 −  1 ) n n2
= 2 or cos 1 =
sin 90 n1 n1

n22
sin  1 = 1− 1.15
n12

Substituting Eq. (1.15) in Eq. (1.14) and simplifying,

1
sin  0 = n12 − n22 1.16
n0

0 is called the acceptance angle or half angle of the acceptance cone. The acceptance angle
is generally about 5 for a single mode fibre & 10 to 15 for multimode fibres. The term
n0 sin0 is called numerical aperture (NA), which indicates the light gathering power of the
optical fibre. It is evident that any ray that enters the fibre at an angle less than 0, strikes the
core-cladding interface at angle greater than the critical angle and undergoes total internal
reflection each time it strikes the interface. The optical fibre sustains the light signal
transmission over a long distance.

Fractional refractive index change ( ): It is the ratio of the difference in the refractive
indices (n1−n2) between the core & the cladding to the refractive index n1 of the core.

19
 ( n1 − n2 )
= 1.17
n1
Since n1 > n2,  is always positive.

Relation between NA &  :

From Eq. 1.16, assuming n0 = 1, NA = n12 − n22 = ( n1 − n2 )( n1 + n2 )

From Eq. 1.17, (n1−n2) = n1  and since n1  n2, we can approximate (n1+n2)  2 n1.

Therefore, NA = ( n1  ) ( 2n1 ) = n1 2 1.18

The light accepting capacity of a fibre can be increased by making  large. But there are
practical limitations to achieve this. Also a very large  may cause signal distortion.

Skip distance (Ls): Skip distance is the distance between two successive reflections of the ray
of light which propagates through the optical fibre. Consider a portion of the optical fibre
through which a light signal is transmitted (Figure 1.17).

Figure 1.17: Skip distance

From the Figure 1.17,

Ls = d cot  1 = d cos ec 2 1 − 1

n12 n0
Ls = d −1 ( sin  1 = sin  ) 1.19
n02 sin 2  n1

TYPES OF OPTICAL FIBRES

Based on their refractive index profile and geometry, optical fibres may be broadly classified
into
a) single mode step index optical fibres
b) multi-mode step index optical fibres
c) multi-mode graded index optical fibres

20
Number of modes of transmission through an optical fibre: Depending on the launch angle
into the fibre, there can be hundreds of ray paths or modes by which energy can propagate
down the core. The ray paths corresponding to the same propagating wave front is called a
mode. An optical fibre permits a discrete number of modes to propagate through it. Not all the
rays that enter the acceptance cone sustain propagation. Only those modes that satisfy the
coherent phase condition are successfully propagated. The rays belonging to the same
propagating wave-front must remain in step despite the phase changes that occur on reflection
and traversing different optical paths.

The number of modes supported for propagation through an optical fibre is determined by a
parameter called normalized frequency (V) given by

d
V= n0 n12 − n22 where d is the diameter of the core and  is the wavelength of the light

V2
propagated. If V >>1, then the number of successfully propagated modes is .
2

Single mode step index optical fibre: A single mode optical fibre consists of a core having a
uniform refractive index n1 that abruptly decreases at the core-cladding interface to a lower
value n2, the refractive index of the cladding. The diameter of the core is narrow (5-10m)
generally a few times the wavelength of the light propagating through it. Only rays nearly
parallel to the fibre axis will travel through. It supports a single mode propagation because of
its narrow core (Figure 1.18).

Figure 1.18: Single mode step-index fibre

Step-Index Multimode fibre: In this case also the refractive index profile is similar to step
index fibre i.e., fibre consists of a core having a uniform refractive index n1 that abruptly

21
decreases at the core-cladding interface to a lower value n2 the refractive index of the cladding.
But the diameter of the core is large (50-200 m). The comparatively large central core makes
it rugged and easily infused with light, as well as easily terminated and coupled. It also supports
a large number of modes for propagation (Figure 1.19).

Figure 1.19: Multi mode step-index fibre

Graded-Index Multimode fibre (GRIN): It consists of a core whose refractive index

decreases gradually from its axis radially outward and becomes equal to the refractive index of
the cladding at the core-cladding interface. The refractive index of the cladding remains
uniform. Dimensions of the core and cladding are similar to that of step index multimode fibres.
It supports a large number of modes for propagation because of its large core diameter (Figure
1.20).

22
 Figure 1.20: Multi mode graded index fibre

ATTENUATION IN OPTICAL FIBRES

Attenuation is the loss of power of the light signal that occurs during its propagation through
the optical fibre. The main sources of attenuation are
1. absorption
2. scattering
3. other losses
Absorption: Absorption of light during propagation occurs due to the impurities present in
the fibre material and also due to the intrinsic nature of the material itself.

The impurities generally present are

a) Transition metals such as iron, chromium, cobalt, copper etc.

b) The hydroxy ions (OH-) that enter into the fibre material at the time of fabrication.

The photons absorbed by the impurities may be lost as heat or may be reemitted as light energy
of different wavelengths and different phase from the one that is propagated. Hence it results
in a loss. Intrinsic absorption occurs by the pure material itself even if the material is free from
impurities and inhomogeneities. Intrinsic absorption though quite less compared to the loss due
to the impurities, it cannot be eliminated.
Scattering: Glass is a heterogeneous mixture of oxides of silicon, phosphorus, germanium etc.
Structural inhomogeneities in the core index will set in the fibre material during solidification
of glass from its molten state. It will also result in a fluctuation of the molecular density. These
inhomogeneities act as scattering centers. Since their dimensions are smaller than  the
wavelength of the light propagated through the fibre, the energy loss that occurs due to such
1
scattering resemble Rayleigh scattering that is proportional to . The losses due to these
4
scattering cannot be eliminated by any process. There are other structural inhomogeneities &

23
defects that set in during fabrication of the fibre that contribute to the loss due to scattering.
Their sources are trapped gas bubbles, unreacted starting materials etc. However, these can be
reduced to a great extent by improved methods of manufacturing.
Other losses: a) Due to dimensional irregularities and imperfections in the fibres (that are
called microscopic bends) (Figure 1.21) the light may not sustain total internal reflection. The
energy will escape from the core.

Figure 1.21: Signal attenuation in optical fibre due to microscopic bending

b) Macroscopic bends occur during wrapping the fibre on a spool or negotiating a curve during
cable laying. Fibres can withstand bends of curvature up to about 10cm without significant
loss. For higher curvature (smaller radius of curvature) than this, the loss increases
exponentially.

Amplification is therefore needed in communication applications at regular intervals in order

to compensate for the losses that occur despite all precautions. An optical repeater is used to
boost the signal.

DISTORTION IN OPTICAL FIBRES

A light pulse launched into a fibre decreases in amplitude, as it travels along the fibre, due to
losses in the fibre. It also spreads during its travel. The pulse received at the output is wider
than input pulse, as shown in Figure 1.22. Such distortion arises due to dispersion effects.

Figure 1.22: Broadening of the signal due to distortion

24
There are three mechanisms which contribute to the distortion (signal spreading) of the light
pulse in a fibre.
(i) Material dispersion: The material dispersion is due to the dependence of the refractive
indices of glass and consequently the group velocity of the optical signal. A LED emits a broad
spectrum of light. Whenever a LED is used as a source, the broad spectrum contains a number
of wavelengths. These different wavelengths of light are travelling through optical fibre at
different speeds because the refractive indices of the glass vary with wavelengths. The short
wavelength waves travel slower than long wavelength waves in a material. Hence, narrow
pulses of light tend to broaden as they travel down the optical fibre. This is known as material
dispersion (Fig. 1.23 (a)). Material dispersion is present in both single mode and multimode
fibres. The material dispersion is given by the equation
λ (Δλ) d2 𝑛
D𝑚 = L 1.20
c dλ2

where λ is the peak wavelength, Δλ is the spectral width, L is the length of the core, and
n is the refractive index of the core.
To cite an example, an LED operating at 820 nm and having a spectral width of 38 nm results
in a dispersion of about 3 ns/km in a certain fibre. In the same fiber, dispersion can be reduced
to 0.3 ns/km using a laser diode operating at 1140 nm and having a 3 nm spectral width. Thus,
material dispersion can be reduced using a more and more monochromatic source.

Figure 1.23: (a) Material dispersion (b) Waveguide dispersion (c) Intermodal dispersion

(ii) Waveguide dispersion: Waveguide dispersion arises from the guiding properties of the
fibre. Pulses at different wavelengths, through propagating in the same mode, travel at slightly

25
different angles. This is known as waveguide dispersion (Fig. 1.23 (b)). It is present in both
single mode and multimode fibres

(iii) Intermodal dispersion: A ray of light launched into a fibre follows different zigzag paths.
When numerous modes are propagating in a fibre, they travel with different net velocities with
respect to fibre axis. Parts of the wave arrive at the output before other parts leading to a spread
of the input pulse. This is known as intermodal dispersion (Fig. 1.23 (c)). It does not depend
on the spectral width of the source. A light pulse from an ideal monochromatic source (Δλ =0)
would still exhibit spreading. In single- mode fibres, since there in only one mode, there is no
intermodal dispersion.

APPLICATIONS OF OPTICAL FIBRES

i) Fibre Optic Networking: A Fibre optic network is a telecommunication network with

optical fibre as the primary transmission medium. It is designed in such a way that it makes
full use of the unique features of optical fibres. Over the years, optical fibre has become the
preferred medium for provision of the major infrastructure for voice, video and data
transmission, because it offers far greater bandwidth and is less bulky than copper cables.

Figure (1.24) shows the structure of a simple optical network. It consists of optical nodes
interconnected with optical fibre links. An optical node is a multifunctional element which
basically acts as a transceiver unit capable of receiving, transmitting and processing the optical
signal. A signal carried on a dedicated wavelength from source to a destination node is known
as a light path (i.e. λ1 and λ2 are two light paths in this particular case). The data can be sent
over these light paths once the connections are set up.

Figure 1.24: Structure of Fibre Optic Network

26
ii) Fibre Optic Communication: Optical communication is communication at a distance
using light to carry information. An optical communication system uses a transmitter, which
encodes a message into an optical signal, a channel (optical fibre), which carries the signal to
its destination, and a receiver, which reproduces the message from the received optical signal
(Fig.1.25). Optical communication has several advantages – can carry large data in digital form,
interference and noise free.

Figure 1.25: Simplified block diagram of optical communication system

Optical fibres are also used in sensors, flexible fibrescope (endoscope) and other industrial
applications.

QUESTIONS

1.1 LASER
1 Mention the characteristics of a laser beam.
2 Explain the following terms with reference to lasers:
(a) spontaneous emission
(b) stimulated emission
(c) metastable state
(d) population inversion
(e) pumping
(f) active medium
(g) resonant cavity.
3 Explain the principle of a laser.
4 Explain construction and operation of ruby laser with necessary diagrams.
5 Explain construction and operation of He-Ne laser with necessary diagrams.
6 Write a note on semiconductor lasers.

27
 7 Mention any four applications of laser.
8 Explain LASER Cooling and its application
1.2 OPTICAL FIBRES
11 What is a critical angle? Define total internal reflection
12 With necessary diagram, derive an expression for angle of acceptance and numerical
aperture.
13 Define fractional refractive index change  and get the relation between  & numerical
aperture NA.
14 What is skip distance? With neat diagram, derive an expression for it.
15 What are different types of optical fibres? Briefly explain them with diagrams.
16 What are the different types of attenuations possible in optical fibres? Explain them.
Explain different types of distortion in optical fibres.

17 Write a note on Fiber optic networking

18 Explain Fiber optic communication

PROBLEMS

1.1 LASER
1 A three level laser of the type shown in figure,
emits laser light at a wavelength 550 nm, near
the centre of the visible band. If the optical
mechanism is shut off, what will be the ratio
of the population of the upper level E2 to that
of the lower level E1 at 300 K ? At what
temperature for the condition of (a) would the ratio of populations be half
?
Ans: (a) 1.77 x 10-38 (b) 37800 K
2 A pulsed ruby laser has a ruby rod (Al2O3 doped with Cr2O3) as an active
medium, which is 6 cm long and 1 cm in diameter. There is one chromium
ion (active centre, with energy levels of the type shown in the figure) for every
3500 aluminium ions. The ruby laser light has a wavelength of 694.4 nm.
Suppose that all the chromium ions are in metastable state (E2) and none are
in ground state (E1). How much energy is there in a single laser pulse if all

28
 these ions come down to ground state in a
single stimulated emission chain reaction
episode ? Density of Al2O3 is 3700 kg/m3. Molar
mass of Al2O3 is 0.102 kg/mol.
Ans: Total energy per pulse= 16.9 J

3 A ruby laser emits light at a wavelength of 694.4 nm. If a laser pulse is

emitted for 12.0 ps and the energy release per pulse is 150 mJ, (a) what is
the length of the pulse, and (b) how many photons are there in each pulse
?
(a) 3.6 x 10-3 m (b) 5.25 x 1017
4 It is entirely possible that techniques for modulating the frequency or amplitude
of a laser beam will be developed so that such a beam can serve as a carrier
for television signals, much as microwave beams do now. Assume also that
laser systems will be available whose wavelengths can be precisely tuned to
anywhere in the visible range (400 nm to 700 nm). If a television channel
occupies a bandwidth of 10 MHz, how many channels could be accommodated
with this laser technology ? Comment on the intrinsic superiority of visible
light to microwaves as carriers of information. Ans: 3.27 x 107
5 A He-Ne laser emits light at a wavelength of 632.8 nm and has an output
power of 2.3 mW. How many photons are emitted each minute by this laser
when operating ? Ans: 4.4 x 1017 /min
6 An atom has two energy levels with a transition wavelength of 582 nm. At
300 K, 4.0 x 1020 atoms are in the lower state. (a) How many occupy the
upper state under conditions of thermal equilibrium ? (b) Suppose, instead, that
7.0 x 1020 atoms are pumped into upper state, with 4.0 x 1020 atoms in the lower
state. How much energy could be released in a single laser pulse ?
Ans: (a) 6.6 x 10-16  0 (b) 240 J

7 Calculate the ratio of, (i) Einstein’s coefficients (ii) rate of stimulated to
spontaneous emissions, for a system at 300 K in which radiations of wavelength
1.39 µm are emitted. [Ans: The ratio of [A21/B12] is 6.2 x 10-15, and ratio of rate of
stimulated to spontaneous emissions 10-15]

29
1.2 OPTICAL FIBRE
8 A step index optical fibre 63.5 m in core-diameter has a core of refractive index
1.53 and a cladding of index 1.39. Determine (a) the numerical aperture for the
fibre, (b) the critical angle for core-cladding interface, (c) the acceptance cone
half-angle (the maximum entrance angle) (d) the number of reflections in 1.0 m
length of the fibre for a ray at the maximum entrance angle, (e) the number of
reflections in 1.0 m length of the fibre for a ray at half the maximum entrance
angle.
Ans: a) 0.639 b) 65.29° (c) 39.71° (d) 7.25 x 103 (e) 358 x 103
9 A glass optical fibre of refractive index 1.450 is to be clad with another to ensure total
internal reflection that will contain light traveling within 5° of the fibre-axis. What
maximum index of refraction is allowed for the cladding? Ans: 1.444
10 The numerical aperture of an optical fibre is 0.2 when surrounded by air.
Determine the refractive index of its core. The refractive index of the cladding is
1.59. Also find the acceptance cone half-angle when the fibre in water. Refractive
index of water is 1.33.
Ans: 1.6, 8.65°
11 The angle of acceptance of an optical fibre is 30° when kept in air. Find the angle of
acceptance when it is in a medium of refractive index 1.33. Ans: 22°

30
 2 QUANTUM PHYSICS

OBJECTIVES:
• To learn certain experimental results that can be understood only by particle theory
of electromagnetic waves.
• To learn the particle properties of waves and the wave properties of the particles.
• To understand the uncertainty principle.
BLACKBODY RADIATION AND PLANCK’S HYPOTHESIS

A black body is an object that absorbs all incident radiation. A small hole cut into a cavity is
the most popular and realistic example. None of the incident radiation escapes. The radiation
is absorbed in the walls of the cavity. This causes a heating of the cavity walls. The oscillators
in the cavity walls vibrate and re-radiate at wavelengths corresponding to the temperature of
the cavity, thereby producing standing waves. Some of the energy from these standing waves
can leave through the opening. The electromagnetic radiation emitted by the black body is
called black-body radiation.

Figure 2-1: A physical model of a blackbody.

The black body is an ideal absorber of incident radiation.

• A black-body reaches thermal equilibrium with the surroundings when the incident
radiation power is balanced by the power re-radiated.
• The emitted "thermal" radiation from a black body characterizes the equilibrium
temperature of the black-body.
• The nature of radiation from a blackbody does not depend on the material of which the
walls are made.
Basic laws of radiation
(1) All objects emit radiant energy.

31
(2) Hotter objects emit more energy (per unit area) than colder objects. The total power of the
emitted radiation is proportional to the fourth power of temperature. This is called Stefan’s
Law and is given by,
P =  A e T4 2-1
where P is power radiated from the surface of the object (W), T is equilibrium surface
temperature (K), σ is Stefan-Boltzmann constant (= 5.670 x 10−8 W/m2K4 ), A is surface area
of the object (m2) and e is emissivity of the surface (e =1 for a perfect blackbody).
(3) The peak of the wavelength distribution shifts to shorter wavelengths as the black body
temperature increases. This is Wien’s Displacement Law and is given by,
λm T = constant = 2.898 × 10−3 m.K , or λm  T−1 2-2
where λm is the wavelength corresponding to peak intensity and T is equilibrium temperature
of the blackbody.

Figure 2-2: Intensity of blackbody radiation versus wavelength at two

temperatures.
(4) Rayleigh-Jeans Law: This law tries to explain the distribution of energy from a black
body. The intensity or power per unit area I (,T)d, emitted in the wavelength interval  to
+d from a blackbody is given by,
2  c kB T
I(  ,T ) = 2-3
4
kB is Boltzmann’s constant, c is speed of light in vacuum, T is equilibrium blackbody
temperature. It agrees with experimental measurements only for long wavelengths. It predicts
an energy output that diverges towards infinity as wavelengths become smaller and is known
as the ultraviolet catastrophe.

32
 Figure 2-3: Comparison of experimental results and the curve predicted
by the Rayleigh–Jeans law for the distribution of blackbody radiation
5) Planck‘s Law:
Max Planck developed a theory of blackbody radiation that leads to an equation for I (,T) that
is in complete agreement with experimental results. To derive the law, Planck made two
assumptions concerning the nature of the oscillators in the cavity walls:
(i) The energy of an oscillator is quantized hence it can have only certain discrete values:
En = n h f 2-4
where n is a positive integer called a quantum number, f is the frequency of cavity
oscillators, and h is a constant called Planck’s constant. Each discrete energy value
corresponds to a different quantum state, represented by the quantum number n.
(ii) The oscillators emit or absorb energy only when making a transition from one quantum
state to another. Difference in energy will be integral multiples of hf.

Figure 2.4: Allowed energy levels for an oscillator with frequency f

33
Planck’s law explains the distribution of energy from a black body which is given by,
2 h c 2 1 2-5
I(  ,T ) =
 5 hc
λkB T
e −1
where I (,T) d is the intensity or power per unit area emitted in the wavelength interval d
from a blackbody, h is Planck’s constant, kB is Boltzmann's constant, c is speed of light in
vacuum and T is equilibrium temperature of blackbody .
The Planck‘s Law gives a distribution that peaks at a certain wavelength, the peak shifts to
shorter wavelengths for higher temperatures, and the area under the curve grows rapidly with
increasing temperature. This law is in agreement with the experimental data.
The results of Planck's law:
▪ The denominator [exp(hc/λkT)] tends to infinity faster than the numerator (λ–5), thus
resolving the ultraviolet catastrophe and hence arriving at experimental observation:
I (λ, T) → 0 as λ → 0.
hc
▪ For very large λ, exp( hckT ) − 1   kT  I(  ,T ) → 2  c −4 k T

i.e. I (λ, T) → 0 as λ → .
From a fit between Planck's law and experimental data, Planck’s constant was derived to be h
= 6.626 × 10–34 J-s.
PHOTOELECTRIC EFFECT

Ejection of electrons from the surface of certain metals when it is irradiated by an

electromagnetic radiation of suitable frequency is known as photoelectric effect.

E
V

Figure 2.5: (a) Apparatus (b) circuit for studying Photoelectric Effect (T – Evacuated
glass/ quartz tube, E – Emitter Plate / Photosensitive material / Cathode, C – Collector Plate
/ Anode, V – Voltmeter, A - Ammeter)
Experimental Observations:

34
Figure 2.6: Photoelectric current versus applied potential difference for two light intensities

1. When plate E is illuminated by light of suitable frequency, electrons are emitted from E
and a current is detected in A (Figure 2.5).
2. Photocurrent produced vs potential difference graph shows that kinetic energy of the most
energetic photoelectrons is,
Kmax = e Vs 2-6
where Vs is stopping potential
3. Kinetic energy of the most energetic photoelectrons is independent of light intensity.
4. Electrons are emitted from the surface of the emitter almost instantaneously
5. No electrons are emitted if the incident light frequency falls below a cutoff frequency.
6. Kinetic energy of the most energetic photoelectrons increases with increasing light
frequency.
Classical Predictions:

1. If light is really a wave, it was thought that if one shine of light of any fixed wavelength,
at sufficient intensity on the emitter surface, electrons should absorb energy continuously
from the em waves and electrons should be ejected.
2. As the intensity of light is increased (made it brighter and hence classically, a more
energetic wave), kinetic energy of the emitted electrons should increase.
3. Measurable / larger time interval between incidence of light and ejection of photoelectrons.
4. Ejection of photoelectron should not depend on light frequency
5. In short experimental results contradict classical predictions.
6. Photoelectron kinetic energy should not depend upon the frequency of the incident light.
Einstein’s Interpretation of electromagnetic radiation:

35
1. Electromagnetic waves carry discrete energy packets (light quanta called photons now).
2. The energy E, per packet depends on frequency f: E = hf.
3. More intense light corresponds to more photons, not higher energy photons.
4. Each photon of energy E moves in vacuum at the speed of light: c = 3 x 108 m/s and each
photon carries a momentum, p = E/c.
Einstein’s theory of photoelectric effect:
A photon of the incident light gives all its energy hf to a single electron (absorption of energy
by the electrons is not a continuous process as envisioned in the wave model) and the kinetic
energy of the most energetic photoelectron,
Kmax = hf −  (Einstein’s photoelectric equation) 2-7
 is called the work function of the metal. It is the minimum energy with which an electron is
bound in the metal.
All the observed features of photoelectric effect could be explained by Einstein’s photoelectric
equation:
1. Equation shows that Kmax depends only on frequency of the incident light.
2. Almost instantaneous emission of photoelectrons due to one -to –one interaction between
photons and electrons.
3. Ejection of electrons depends on light frequency since photons should have energy greater
than the work function  in order to eject an electron.
4. The cutoff frequency fc is related to  by fc =  /h. If the incident frequency f is less
than fc , there is no emission of photoelectrons.
The graph of kinetic energy of the most energetic photoelectron Kmax vs frequency f is a
straight line, according to Einstein’s equation.

36
Figure 2.7: A representative plot of Kmax versus frequency of incident light for three different
metals

COMPTON EFFECT

When X-rays are scattered by free/nearly free electrons, they suffer a change in their
wavelength which depends on the scattering angle. This scattering phenomenon is known as
Compton Effect.
Classical Predictions: Oscillating electromagnetic waves (classically, X-rays are em waves)
incident on electrons should have two effects: i) oscillating electromagnetic field causes
oscillations in electrons. Each electron first absorbs radiation as a moving particle and then re-
radiates in all directions as a moving particle and thereby exhibiting two Doppler shifts in the
frequency of radiation. ii) radiation pressure should cause the electrons to accelerate in the
direction of propagation of the waves. Because different electrons will move at different speeds
after the interaction, depending on the amount of energy absorbed from electromagnetic waves,
the scattered waves at a given angle will have all frequencies (Doppler- shifted values).
Compton’s experiment and observation: Compton measured the intensity of scattered X-
rays from a solid target (graphite) as a function of wavelength for different angles. The
experimental setup is shown in Figure 2.8. Contrary to the classical prediction, only one
frequency for scattered radiation was seen at a given angle. This is shown in the Figure 2.9.
The graphs for three nonzero angles show two peaks, one at o and the other at ’ >o . The
shifted peak at ’ is caused by the scattering of X-rays from free electrons. Shift in wavelength
was predicted by Compton to depend on scattering angle as

𝒉 2-8
𝝀′ − 𝝀 = 𝒎𝒄
(𝟏−𝒄𝒐𝒔 𝜽)
where m is the mass of the electron, c is velocity of light, h is Planck’s constant.
ℎ
This is known as Compton shift equation, and the factor 𝑚𝑐
is called the Compton
ℎ
wavelength and 𝑚𝑐
= 2.43 pm for electron.

37
 Figure 2.8 Schematic diagram of Compton’s apparatus. The wavelength is measured with a
rotating crystal spectrometer for various scattering angles θ.

Figure 2.9: Scattered x-ray intensity versus wavelength for Compton scattering at  = 0°,
45°, 90°, and 135° showing single frequency at a given angle

Derivation of the Compton shift equation:

Compton could explain the experimental result by treating the X-rays not as waves but rather
as point like particles (photons) having energy E = hfo = hc/o , momentum p = hf/c = h/ and
zero rest energy. Photons collide elastically with free electrons initially at rest and moving
relativistically after collision.
Let o , po = h/o and Eo = hc/o be the wavelength, momentum and energy of the incident
photon respectively. ’, p’ = h/’ and E’ = hc/’ be the corresponding quantities for the
scattered photon.
We know that, for the electron, the total relativistic energy 𝐸 = √𝑝2 𝑐 2 + 𝑚2 𝑐 4
Kinetic energy K = E − m c2
1
And momentum p =  mv. where
=
1 − vc 2
2

v and m are the speed and mass of the electron respectively.

38
 Figure 2.10: Quantum model for X-ray scattering from an electron

In the scattering process, the total energy and total linear momentum of the system must
be conserved.
For conservation of energy we must have, Eo = E’ + K
ie, Eo = E’ + (E − m c2)
Or Eo − E’ + m c2 = 𝐸 = √𝑝2 𝑐 2 + 𝑚2 𝑐 4
Squaring both the sides, (𝐸𝑜 − 𝐸′)2 + 2(𝐸𝑜 − 𝐸′) 𝑚𝑐 2 + 𝑚2 𝑐 4 = 𝑝2 𝑐 2 + 𝑚2 𝑐 4
For conservation of momentum, x-component: 𝑝𝑜 = 𝑝′ 𝑐𝑜𝑠 𝜃 + 𝑝 𝑐𝑜𝑠 𝜙
y-component: 0 = 𝑝′ 𝑠𝑖𝑛 𝜃 − 𝑝 𝑠𝑖𝑛 𝜙
Rewriting these two equations
𝑝𝑜 − 𝑝′ 𝑐𝑜𝑠 𝜃 = 𝑝 𝑐𝑜𝑠 𝜙
𝑝′ 𝑠𝑖𝑛 𝜃 = 𝑝 𝑠𝑖𝑛 𝜙
Squaring both the sides and adding,
𝑝𝑜2 − 2𝑝𝑜 𝑝′ 𝑐𝑜𝑠 𝜃 + 𝑝′2 = 𝑝2
Substituting this 𝑝2 in the equation :
(𝐸𝑜 − 𝐸′)2 + 2(𝐸𝑜 − 𝐸′) 𝑚𝑐 2 = 𝑝2 𝑐 2 , one gets
(𝐸𝑜 − 𝐸′)2 + 2(𝐸𝑜 − 𝐸′) 𝑚𝑐 2 = (𝑝𝑜2 − 2𝑝𝑜 𝑝′ 𝑐𝑜𝑠 𝜃 + 𝑝′2 )𝑐 2
Substituting photon energies and photon momenta one gets
ℎ𝑐 ℎ𝑐 2 ℎ𝑐 ℎ𝑐 ℎ𝑐 2 ℎ𝑐 ℎ𝑐 ℎ𝑐 2
( 𝜆𝑜
− 𝜆′
) +2( 𝜆𝑜
− 𝜆′
) 𝑚𝑐 2 = ( 𝜆𝑜
) − 2( 𝜆𝑜
) ( 𝜆′ ) 𝑐𝑜𝑠 𝜃 + ( 𝜆′ )

Simplifying one gets

39
 ℎ𝑐 2 ℎ𝑐 ℎ𝑐 ℎ𝑐 2 1 1 ℎ𝑐 2 ℎ𝑐 ℎ𝑐
( 𝜆 ) − 2 ( 𝜆 ) ( 𝜆′ ) + ( 𝜆′ ) + 2 ℎ𝑐 ( 𝜆𝑜
− 𝜆′
) 𝑚𝑐 2 = ( 𝜆𝑜
) − 2( 𝜆𝑜
) ( 𝜆′ ) 𝑐𝑜𝑠 𝜃
𝑜 𝑜

ℎ𝑐 2
+ ( 𝜆′ )
ℎ𝑐 ℎ𝑐
i.e., − + ( 𝜆1𝑜 − 1
𝜆′
) 𝑚𝑐 2 = − 𝑐𝑜𝑠 𝜃
𝜆𝑜 𝜆′ 𝜆𝑜 𝜆′
′ ℎ𝑐
OR, (𝜆𝜆−𝜆𝜆𝑜′ ) 𝑚𝑐 2 = (1 − 𝑐𝑜𝑠 𝜃)
𝑜 𝜆𝑜 𝜆′

Compton shift:
𝒉
𝝀′ − 𝝀𝒐 = (𝟏 − 𝒄𝒐𝒔 𝜽)
𝒎𝒄

PHOTONS AND ELECTROMAGNETIC WAVES [DUAL NATURE OF LIGHT]

• Light exhibits diffraction and interference phenomena that are only explicable in terms of
wave properties.
• Photoelectric effect and Compton Effect can only be explained taking light as photons /
particle.
• This means true nature of light is not describable in terms of any single picture, instead
both wave and particle nature have to be considered. In short, the particle model and the
wave model of light complement each other.

DE BROGLIE HYPOTHESIS - WAVE PROPERTIES OF PARTICLES

We have seen that light comes in discrete units (photons) with particle properties (energy E
and momentum p) that are related to the wave-like properties of frequency and wavelength.
Louis de Broglie postulated that because photons have both wave and particle characteristics,
perhaps all forms of matter have wave-like properties, with the wavelength λ related to
momentum p in the same way as for light.
𝒉 𝒉 2-9
de Broglie wavelength: 𝝀 = =
𝒑 𝒎𝒗
where h is Planck’s constant and p is momentum of the quantum particle, m is mass of the
particle, and v is speed of the particle. The electron accelerated through a potential difference
of V, has a non-relativistic kinetic energy 1
2
𝑚 𝑣 2 = 𝑒 ∆𝑉 where e is electron
charge.
Hence, the momentum (p) of an electron accelerated through a potential difference of V is

𝒑 = 𝒎 𝒗 = √𝟐 𝒎 𝒆 ∆𝑽 2-10

40
 𝐸
Frequency of the matter wave associated with the particle is , where E is total relativistic
ℎ

energy of the particle

Davisson and Germer experiment

This is an experiment on diffraction of accelerated electrons by crystals to establish the wave

nature of electrons. The regular spacing of the atoms in a crystal act as a grating for an electron
beam producing a diffraction pattern by electron scattering. The result of this experiment
resembles the result of the x ray diffraction giving experimental evidence for de Broglie
hypothesis.

Figure 2.11: Schematic of Davisson-Germer experiment (left). Polar plot of intensities

after scattering for incident electron energy of 54 eV. (right).

A beam of electrons from a heated filament accelerated to a potential V is collimated and

allowed to strike a single crystal of nickel. Electrons are scattered in all directions by the atoms
in the crystal. The intensity of the scattered electron beam is measured by a detector which can
be moved to any angle 𝜙 relative to the incident beam and is shown in the polar plot of  verses
the intensity ( r, the radius vector). The most intense reflection of electron beam at an angle
𝜙 = 50° , for an accelerating potential 54 V is observed.
An electron of mass m accelerated to a potential V has
1
kinetic energy, 𝑚𝑣 2 = 𝑒 𝑉 where , v = velocity.
2

And the momentum, 𝑝 = 𝑚 𝑣 = √2 𝑚 𝑒 𝑉

ℎ ℎ ℎ
 de Broglie wavelength, 𝜆 = 𝑝 = 𝑚𝑣 =
√2 𝑚 𝑒 𝑉

41
Substituting V = 54 V, we get the value for the de Broglie wavelength as
 = 0.167nm.
Wavelength can also be obtained, in this experiment, using Bragg’s law of diffraction.
According to which the wavelength is given by the following relationship:
𝑑 𝑠𝑖𝑛𝜙 = 𝑛𝜆
Substituting n = 1 (for the first order diffraction maximum), 𝜙 = 50° (scattering angle
corresponding to the first order diffraction maximum), 𝑑 = 0.215 𝑛𝑚 (inter-atomic spacing in
nickel), we get  = 0.165nm
The values of the wavelength from both the approaches agree very well. This verifies de
Broglie’s hypothesis and establishes the wave nature of electrons.

Davisson-Germer experiment and G P Thomson’s electron diffraction experiment confirmed

de Broglie relationship p = h /. Subsequently it was found that atomic beams, and beams of
neutrons, also exhibit diffraction when reflected from regular crystals. Thus de Broglie's
formula seems to apply to any kind of matter. Now the dual nature of matter and radiation is
an accepted fact and it is stated in the principle of complementarity. This states that wave and
particle models of either matter or radiation complement each other.

THE QUANTUM PARTICLE

Quantum particle is a model by which particles having dual nature are represented. We must
choose one appropriate behavior for the quantum particle (particle or wave) in order to
understand a particular behavior.
To represent a quantum wave, we have to combine the essential features of both an ideal
particle and an ideal wave. An essential feature of a particle is that it is localized in space. But
an ideal wave is infinitely long (non-localized) as shown in Figure 2.11.

Figure 2.11: Section of an ideal wave of single frequency

Now to build a localized entity from an infinitely long wave, waves of same amplitude, but
slightly different frequencies are superposed (Figure 2.12).

42
 Figure 2.12: Superposition of two waves Wave 1 and Wave 2

If we add up large number of waves in a similar way, the small localized region of space where
constructive interference takes place is called a wave packet, which represents a quantum
particle (Figure 2.13).

Figure 2.13: Wave packet

Mathematical representation of a wave packet:

Superposition of two waves of equal amplitude, but with slightly different frequencies, f1 and
f2, traveling in the same direction are considered. The waves are written as
𝑦1 = 𝐴 𝑐𝑜𝑠(𝑘1 𝑥 − 𝜔1 𝑡) and 𝑦2 = 𝐴 𝑐𝑜𝑠(𝑘2 𝑥 − 𝜔2 𝑡)
where 𝑘 = 2𝜋/𝜆 , 𝜔 = 2𝜋𝑓
The resultant wave y = y1 + y2
𝛥𝑘 𝛥𝜔 𝑘1 +𝑘2 𝜔1 +𝜔2
𝑦 = 2𝐴 [𝑐𝑜𝑠 ( 2 𝑥 − 2
𝑡) 𝑐𝑜𝑠 ( 2
𝑥 − 2
𝑡)]

where k = k1 – k2 and  = 1 – 2.

Figure 2.14: Beat pattern due to superposition of wave trains y1 and y2

43
The resulting wave oscillates with the average frequency, and its amplitude envelope (in square
brackets, shown by the blue dotted curve in Figure 2.14) varies according to the difference
frequency. A realistic wave (one of finite extent in space) is characterized by two different
speeds. The phase speed, the speed with which wave crest of individual wave moves, is given
by
𝜔
𝑣𝑝 = 𝑓 𝜆 or 𝑣𝑝 = (2.11)
𝑘

The envelope of group of waves can travel through space with a different speed than the
individual waves. This speed is called the group speed or the speed of the wave packet which
is given by
(𝛥𝜔
2
) 𝛥𝜔
𝑣𝑔 = = (2.12)
(𝛥𝑘
2
) 𝛥𝑘

For a superposition of large number of waves to form a wave packet, this ratio is 𝑣𝑔 =
𝑑𝜔
𝑑𝑘

In general these two speeds are not the same.

Relation between group speed (vg) and phase speed (vp):
𝜔
𝑣𝑃 = = 𝑓𝜆  𝜔 = 𝑘 𝑣𝑃
𝑘
𝑑𝜔 𝑑(𝑘𝑣𝑃 ) 𝑑𝑣𝑃
But 𝑣𝑔 = = = 𝑘 + 𝑣𝑃
𝑑𝑘 𝑑𝑘 𝑑𝑘

Substituting for k in terms of λ, we get

𝑑𝑣𝑃
𝑣𝑔 = 𝑣𝑃 − 𝜆 ( ) (2.13)
𝑑𝜆

Relation between group speed (vg) and particle speed (u):

𝐸 2𝜋 2𝜋 2𝜋𝑝
𝜔 = 2𝜋𝑓 = 2𝜋 and 𝑘 = = =
ℎ 𝜆 ℎ⁄𝑝 ℎ
2𝜋
𝑑𝜔 𝑑𝐸 𝑑𝐸
ℎ
𝑣𝑔 = = 2𝜋 =
𝑑𝑘 ℎ
𝑑𝑝 𝑑𝑝

For a classical particle moving with speed u, the kinetic energy E is given by
𝑝2 2 𝑝 𝑑𝑝 𝑑𝐸 𝑝
𝐸 = 1
2
𝑚 𝑢2 = and 𝑑𝐸 = or = = 𝑢
2𝑚 2𝑚 𝑑𝑝 𝑚
𝑑𝜔 𝑑𝐸
𝑣𝑔 = = = 𝑢 (2.14)
𝑑𝑘 𝑑𝑝

i.e., we should identify the group speed with the particle speed, speed with which the energy
moves. To represent a realistic wave packet, confined to a finite region in space, we need the
superposition of large number of harmonic waves with a range of k-values.

44
DOUBLE–SLIT EXPERIMENT REVISITED

One way to confirm our ideas about the electron’s wave–particle duality is through an
experiment in which electrons are fired at a double slit. Consider a parallel beam of mono-
energetic electrons incident on a double slit as in Figure 3.15. Let’s assume the slit widths are
small compared with the electron wavelength so that diffraction effects are negligible. An
electron detector screen (acts like the “viewing screen” of Young’s double-slit experiment) is
positioned far from the slits at a distance much greater than d, the separation distance of the
slits. If the detector screen collects electrons for a long enough time, we find a typical wave
interference pattern for the counts per minute, or probability of arrival of electrons. Such an
interference pattern would not be expected if the electrons behaved as classical particles, giving
clear evidence that electrons are interfering, a distinct wave-like behavior.

Figure 2.15: (a) Schematic of electron beam interference experiment, (b) Photograph of a
double-slit interference pattern produced by electrons
If we measure the angle θ at which the maximum intensity of the electrons arrives at the
detector screen, we find they are described by exactly the same equation as that for light:
𝑑 𝑠𝑖𝑛 𝜃 = 𝑚 𝜆 , where m is the order number and λ is the electron wavelength. Therefore,
the dual nature of the electron is clearly shown in this experiment: the electrons are detected
as particles at a localized spot on the detector screen at some instant of time, but the
probability of arrival at the spot is determined by finding the intensity of two interfering
waves.
UNCERTAINTY PRINCIPLE

It is fundamentally impossible to make simultaneous measurements of a particle’s position

and momentum with infinite accuracy. This is known as Heisenberg uncertainty principle.
The uncertainties arise from the quantum structure of matter.

45
For a particle represented by a single wavelength wave existing throughout space,  is precisely
known, and according to de Broglie hypothesis, its p is also known accurately. But the position
of the particle in this case becomes completely uncertain.
This means  = 0, p =0; but x = 
In contrast, if a particle whose momentum is uncertain (combination of waves / a range of
wavelengths are taken to form a wave packet), so that x is small, but  is large. If x is
made zero,  and thereby p will become .
In short ( x ) ( px) ≥ h / 4 (2.15)
where x is uncertainty in the measurement of position x of the particle and px is uncertainty
in the measurement of momentum px of the particle.
One more relation expressing uncertainty principle is related to energy and time which is given
by
( E ) ( t ) ≥ h / 4 (2.16)
where E is uncertainty in the measurement of energy E of the system when the
measurement is done over the time interval t.
QUESTIONS

1. Explain (a) Stefan’s law (b) Wien’s displacement law (c) Rayleigh-Jeans law.
2. Sketch schematically the graph of wavelength vs intensity of radiation from a blackbody.

3. Explain Planck’s radiation law.

4. Write the assumptions made in Planck’s hypothesis of blackbody radiation.

5. Explain photoelectric effect.

6. What are the observations in the experiment on photoelectric effect?
7. What are the classical predictions about the photoelectric effect?

8. Explain Einstein’s photoelectric equation.

9. Which are the features of photoelectric effect-experiment explained by Einstein’s

photoelectric equation?

10. Sketch schematically the following graphs with reference to the photoelectric effect: (a)
photoelectric current vs applied voltage (b) kinetic energy of most-energetic electron vs
frequency of incident light.

11. Explain Compton effect.

46
12. Explain the experiment on Compton effect.
13. Derive the Compton shift equation.
14. Explain the wave properties of the particles.
15. How Davison and Germer experiment validated the de Broglie hypothesis? Explain.

15. Explain a wave packet and represent it schematically.

16. Explain (a) group speed (b) phase speed, of a wave packet.

17. Show that the group speed of a wave packet is equal to the particle speed.

18. (a) Name any two phenomena which confirm the particle nature of light.
(b) Name any two phenomena which confirm the wave nature of light.
19. Explain Heisenberg uncertainty principle.

20. Write the equations for uncertainty in (a) position and momentum (b) energy and time.

21. Mention two situations which can be well explained by the uncertainty relation.

PROBLEMS

1 Find the peak wavelength of the blackbody radiation emitted by each of the following.
A. The human body when the skin temperature is 35°C
B. The tungsten filament of a light bulb, which operates at 2000 K
C. The Sun, which has a surface temperature of about 5800 K.
Ans: 9.4 μm, 1.4 μm, 0.50 μm
2 A 2.0- kg block is attached to a spring that has a force constant of k = 25 N/m. The
spring is stretched 0.40 m from its equilibrium position and released.
A. Find the total energy of the system and the frequency of oscillation according to
classical calculations.
B. Assuming that the energy is quantized, find the quantum number n for the system
oscillating with this amplitude.
C. Suppose the oscillator makes a transition from the n = 5.4 x 1033 state to the state
corresponding to n = 5.4 x 1033 – 1. By how much does the energy of the
oscillator change in this one-quantum change.
Ans: 2.0 J, 0.56 Hz, 5.4 x 1033, 3.7 x 10–34 J
3 The human eye is most sensitive to 560 nm light. What is the temperature of a black
body that would radiate most intensely at this wavelength?
Ans: 5180 K

47
 4 A blackbody at 7500 K consists of an opening of diameter 0.050 mm, looking into an
oven. Find the number of photons per second escaping the hole and having
wavelengths between 500 nm and 501 nm.
Ans: 1.30 x 1015/s
5 The radius of our Sun is 6.96 x 108 m, and its total power output is 3.77 x 1026 W. (a)
Assuming that the Sun’s surface emits as a black body, calculate its surface
temperature. (b) Using the result, find max for the Sun.
Ans: 5750 K, 504 nm
6 Calculate the energy in electron volts, of a photon whose frequency is (a) 620 THz, (b)
3.10 GHz, (c) 46.0 MHz. (d) Determine the corresponding wavelengths for these
photons and state the classification of each on the electromagnetic spectrum.
Ans: 2.57 eV, 1.28 x 10–5 eV, 1.91 x 10–7 eV, 484 nm, 9.68 cm, 6.52 m
7 An FM radio transmitter has a power output of 150 kW and operates at a frequency of
99.7 MHz. How many photons per second does the transmitter emit?
Ans: 2.27 x 1030 photons/s
8 A sodium surface is illuminated with light having a wavelength of 300 nm. The work
function for sodium metal is 2.46 eV. Find
A. The maximum kinetic energy of the ejected photoelectrons and
B. The cutoff wavelength for sodium.
Ans: 1.67 eV, 504 nm
9 Molybdenum has a work function of 4.2eV. (a) Find the cut off wavelength and cut off
frequency for the photoelectric effect. (b) What is the stopping potential if the incident
light has wavelength of 180 nm?
Ans: 296 nm, 1.01 x 1015 Hz, 2.71 V
10 Electrons are ejected from a metallic surface with speeds up to 4.60 x 105 m/s when light
with a wavelength of 625 nm is used. (a) What is the work function of the surface? (b)
What is the cut-off frequency for this surface?
Ans: 1.38 eV, 3.34 x 1014 Hz

11 The stopping potential for photoelectrons released from a metal is 1.48 V larger
compared to that in another metal. If the threshold frequency for the first metal is
40.0 % smaller than for the second metal, determine the work function for each
metal.
Ans: 3.70 eV, 2.22 eV

48
12 Two light sources are used in a photoelectric experiment to determine the work function
for a metal surface. When green light from a mercury lamp ( = 546.1 nm) is used, a
stopping potential of 0.376 V reduces the photocurrent to zero. (a) Based on this what is
the work function of this metal? (b) What stopping potential would be observed when
using the yellow light from a helium discharge tube ( = 587.5 nm)?
Ans: 1.90 eV, 0.215 V
13 X-rays of wavelength o = 0.20 nm are scattered from a block of material. The scattered
X-rays are observed at an angle of 45° to the incident beam. Calculate their wavelength.
What if we move the detector so that scattered X-rays are detected at an angle larger than
45°? Does the wavelength of the scattered X-rays increase or decrease as the angle 
increase?
Ans: 0.200710 nm, INCREASES
14 Calculate the energy and momentum of a photon of wavelength 700 nm.
Ans: 1.78 eV, 9.47 x 10–28kg.m/s
15 A 0. 00160 nm photon scatters from a free electron. For what photon scattering
angle does the recoiling electron have kinetic energy equal to the energy of the
scattered photon?
Ans: 70°
16 A 0.880 MeV photon is scattered by a free electron initially at rest such that the
scattering angle of the scattered electron is equal to that of the scattered photon (
= ). (a) Determine the angles  & . (b) Determine the energy and momentum
of the scattered electron and photon.
Ans: 43°, 43°, 0.602 MeV, 3.21 x 10–22 kg.m/s, 0.278 MeV, 3.21 x 10–22
kg.m/s
17 Calculate the de- Broglie wavelength for an electron moving at 1.0 x 107 m/s.
Ans: 7.28 x 10–11 m
18 A rock of mass 50 g is thrown with a speed of 40 m/s. What is its de Broglie
wavelength?
Ans: 3.3 x 10–34 m
19 A particle of charge q and mass m has been accelerated from rest to a nonrelativistic
speed through a potential difference of V. Find an expression for its de Broglie
wavelength.
h
Ans: λ =
√2 m q Δv
20 (a) An electron has a kinetic energy of 3.0 eV. Find its wavelength. (b) Also find the
wavelength of a photon having the same energy.
Ans: 7.09 x 10–10 m, 4.14 x 10–7 m
21 In the Davisson-Germer experiment, 54.0 eV electrons were diffracted from a nickel
lattice. If the first maximum in the diffraction pattern was observed at = 50.0°, what
was the lattice spacing a between the vertical rows of atoms in the figure?

49
 Ans: 2.18 x 10–10 m
22 Consider a freely moving quantum particle with mass m and speed u. Its energy is E= K=
mu2/2. Determine the phase speed of the quantum wave representing the particle and
show that it is different from the speed at which the particle transports mass and energy.
Ans: vGROUP = u ≠ vPHASE
23 Electrons are incident on a pair of narrow slits 0.060 m apart. The ‘bright bands’ in the
interference pattern are separated by 0.40 mm on a ‘screen’ 20.0 cm from the slits.
Determine the potential difference through which the electrons were accelerated to give
this pattern.
Ans: 105 V
24 The speed of an electron is measured to be 5.00 x 103 m/s to an accuracy of 0.0030%.
Find the minimum uncertainty in determining the position of this electron.
Ans: 0.383 mm
25 The lifetime of an excited atom is given as 1.0 x 10-8 s. Using the uncertainty
principle, compute the line width f produced by this finite lifetime?
Ans: 8.0 x 106 Hz
26 Use the uncertainty principle to show that if an electron were confined inside an
atomic nucleus of diameter 2 x 10–15 m, it would have to be moving relativistically,
while a proton confined to the same nucleus can be moving nonrelativistically.
Ans: vELECTRON  0.99996 c, vPROTON  1.8 x 107 m/s
27 Find the minimum kinetic energy of a proton confined within a nucleus having a
diameter of 1.0 x 10–15 m.
Ans: 5.2 MeV

50
 3 QUANTUM MECHANICS

OBJECTIVES:
• To learn the application of Schrödinger equation to a bound particle and to learn the
quantized nature of the bound particle, its expectation values and physical
significance.
• To understand the tunnelling behaviour of a particle incident on a potential barrier.
• To understand the behaviour of quantum oscillator.

AN INTERPRETATION OF QUANTUM MECHANICS

Experimental evidences proved that both matter and electromagnetic radiation exhibit wave
and particle nature depending on the phenomenon being observed. Making a conceptual
connection between particles and waves, for an electromagnetic radiation of amplitude E, the
probability per unit volume of finding a photon in a given region of space at an instant of time
as;

PROBABILITY
∝ 𝐸2
𝑉

Figure 3.1: Wave packet

Taking the analogy between electromagnetic radiation and matter-the probability per unit
volume of finding the particle is proportional to the square of the amplitude of a wave
representing the particle, even if the amplitude of the de Broglie wave associated with a particle
is generally not a measurable quantity. The amplitude of the de Broglie wave associated with
a particle is called probability amplitude, or the wave function, and is denoted by .
In general, the complete wave function  for a system depends on the positions of all the
particles in the system and on time. This can be written as
(r1,r2,…rj,…,t) = (rj) e–it
where rj is the position vector of the jth particle in the system.
For any system in which the potential energy is time-independent and depends only on the
position of particles within the system, the important information about the system is contained

51
within the space part of the wave function. The wave function  contains within it all the
information that can be known about the particle. | |2 is always real and positive, and is
proportional to the probability per unit volume, of finding the particle at a given point at some
instant. If  represents a single particle, then ||2 - called the probability density - is the
relative probability per unit volume that the particle will be found at any given point in the
volume.
One-dimensional wave functions and expectation values: Let  be the wave function for a
particle moving along the x axis. Then P(x) dx = ||2dx is the probability to find the particle
in the infinitesimal interval dx around the point x. The probability of finding the particle in the
arbitrary interval a ≤ x ≤ b is
𝑏
𝑃𝑎𝑏 = ∫𝑎 |𝜓|2 𝑑𝑥 (3.1)
The probability of a particle being in the interval a ≤ x ≤ b is the area under the probability
density curve from a to b. The total probability of finding the particle is one. Forcing this
condition on the wave function is called normalization.
+∞
∫−∞ |𝜓|2 𝑑𝑥 = 1 (3.2)

Figure 3.2: An arbitrary probability density curve for a particle

All the measurable quantities of a particle, such as its position, momentum and energy can be
derived from the knowledge of . e.g., the average position at which one expects to find the
particle after many measurements is called the expectation value of x and is defined by the
equation

+∞
〈𝑥〉 ≡ ∫−∞ 𝜓 ∗ 𝑥 𝜓 𝑑𝑥 (3.3)

The important mathematical features of a physically reasonable wave function (x) for a
system are
• (x) may be a complex function or a real function, depending on the system.

52
 • (x) must be finite, continuous and single valued everywhere.
• The space derivatives of, must be finite, continuous and single valued
everywhere.
•  must be normalizable.

THE SCHRÖDINGER EQUATION

The appropriate wave equation for matter waves was developed by Schrödinger. Schrödinger
equation as it applies to a particle of mass m confined to move along x axis and interacting
with its environment through a potential energy function U(x) is

ℏ2 𝑑2 𝜓
− +𝑈𝜓 = 𝐸𝜓 (3.4)
2 𝑚 𝑑𝑥 2

where E is a constant equal to the total energy of the system (the particle and its environment)
and ħ = h/2. This equation is referred to as the one dimensional, time-independent
Schrödinger equation.
Application of Schrödinger equation:

1. Particle in an infinite potential well (particle in a box)

2. Particle in a finite potential well
3. Tunnelling
4. Quantum oscillator

PARTICLE IN AN INFINITE POTENTIAL WELL (PARTICLE IN A “BOX”)

Figure 3.3: (a) Particle in a potential well of infinite height, (b) Sketch of potential well

Consider a particle of mass m and velocity v, confined to bounce between two impenetrable
walls separated by a distance L, as shown in Figure 3.3(a). Figure 3.3(b) shows the potential
energy function for the system.
U(x) = 0, for 0 <x<L,
U (x) =  , for x≤ 0, x≥L

53
Since U (x)=  , for x< 0, x>L , (x) = 0 in these regions. Also (0) =0 and (L) =0. Only
those wave functions that satisfy these boundary conditions are allowed. In the region 0 <x<L,
where U = 0, the Schrödinger equation takes the form
𝑑2𝜓 2𝑚
+ 𝐸 𝜓 = 0
𝑑𝑥 2 ℏ2

𝑑2 𝜓 2𝑚𝐸 √2𝑚𝐸
Or = − 𝑘2 𝜓 , where 𝑘 2 = or 𝑘 =
𝑑𝑥 2 ℏ2 ℏ

The most general form of the solution to the above equation is

(x) = Asin(kx) + B cos(kx)
where A and B are constants determined by the boundary and normalization conditions.
Applying the first boundary condition,
i.e., at x = 0,  = 0 leads to
0 = A sin 0 + B cos 0 or B = 0 ,
And at x = L ,  = 0 ,
0 = A sin(kL) + B cos(kL) = A sin(kL) + 0 ,
Since A  0 , sin(kL) = 0 . k L = nπ; ( n = 1, 2, 3, ……….. )
𝑛𝜋𝑥
Now the wave function reduces to 𝜓𝑛 (𝑥) = 𝐴 𝑠𝑖𝑛 ( )
𝐿

To find the constant A, apply normalization condition

+∞ 𝐿 𝑛𝜋𝑥 2
∫−∞ |ψ|2 dx = 1 or ∫0 𝐴2 [𝑠𝑖𝑛 ( 𝐿
)] 𝑑𝑥 = 1 .
𝐿1
𝐴2 ∫0 2
[1 − 𝑐𝑜𝑠(
2𝑛𝜋𝑥
𝐿
)] 𝑑𝑥 = 1

2
Solving we get 𝐴 = √𝐿

2 𝑛𝜋𝑥
Thus 𝜓𝑛 (𝑥) = √𝐿 𝑠𝑖𝑛 ( ) is the wave function for particle in a box.
𝐿

√2𝑚𝐸
Since 𝑘 = and kL = nπ
ℏ

√2𝑚𝐸
We get, 𝐿 = 𝑛𝜋.
ℏ
ℎ2
∴ 𝐸𝑛 = ( 8 𝑚 𝐿2) 𝑛2 , n = 1, 2, 3, . . . . .
(3.5)

Each value of the integer n corresponds to a quantized energy value, En .

ℎ2
The lowest allowed energy (n = 1), 𝐸1 = .
8 𝑚 𝐿2

This is the ground state energy for the particle in a box. Excited states correspond to n = 2, 3,
4,…which have energies given by 4E1 , 9E1 , 16E1…. respectively. Energy level diagram, wave

54
function and probability density sketches are shown in Figure 3.4 and 3.5 respectively. Since
ground state energy E1 ≠0, the particle can never be at rest.

Figure 3.4 Energy level diagram for a particle in potential well of infinite height

Figure 3.5: Sketch of (a) wave function, (b) Probability density for a particle in potential well
of infinite height

A PARTICLE IN A POTENTIAL WELL OF FINITE HEIGHT

55
 Figure 3.6: Potential well of finite height U and length L

Consider a particle with the total energy E, trapped in a finite potential well of height U such
that
U(x) = 0 , 0 <x<L,
U(x) = U , x≤ 0, x≥L
Classically, for energy E<U, the particle is permanently bound in the potential well. However,
according to quantum mechanics, a finite probability exists that the particle can be found
outside the well even if E<U. That is, the wave function is generally nonzero in the regions I
and III. In region II, where U = 0, the allowed wave functions are again sinusoidal. But the
boundary conditions no longer require that the wave function must be zero at the ends of the
well.
Schrödinger equation outside the finite well in regions I & III
𝑑2 𝜓 2𝑚 𝑑2 𝜓 2𝑚
= (𝑈 − 𝐸) 𝜓 or = 𝐶 2 𝜓 where 𝐶2 = (𝑈 − 𝐸)
𝑑𝑥 2 ℏ2 𝑑𝑥 2 ℏ2

General solution of the above equation is

(x) = AeCx + B e−Cx
where A and B are constants.
A must be zero in Region III and B must be zero in Region I, otherwise, the probabilities
would be infinite in those regions. For solution to be finite,
I = AeCx for x≤ 0
III = Be-Cx for x≥L
This shows that the wave function outside the potential well decay exponentially with distance.
Schrodinger equation inside the square well potential in region II, where U = 0
𝑑2 𝜓𝐼𝐼 2𝑚 2𝑚𝐸
+ ( 𝐸) 𝜓𝐼𝐼 = 0 , = 𝑘2
𝑑𝑥 2 ℏ2 ℏ2

General solution of the above equation

𝜓𝐼𝐼 = 𝐹 𝑠𝑖𝑛[𝑘𝑥] + 𝐺 𝑐𝑜𝑠[𝑘𝑥]

56
To determine the constants A, B, F, G and the allowed values of energy E, apply the four
boundary conditions and the normalization condition:
𝑑𝜓 𝑑𝜓𝐼𝐼
At x = 0 , I(0) = II(0) and [ 𝑑𝑥𝐼 ] = [ ]
𝑥=0 𝑑𝑥 𝑥=0
𝑑𝜓𝐼𝐼 𝑑𝜓𝐼𝐼𝐼
At x = L , II(L) = III(L) and [ ] = [ ]
𝑑𝑥 𝑥=𝐿 𝑑𝑥 𝑥=𝐿
+∞
∫ |𝜓|2 𝑑𝑥 = 1
−∞

Figure 3.7 shows the plots of wave functions and their respective probability densities.

Figure 3.7: Sketch of (a) wave function, (b) Probability density for a particle in potential well
of finite height

It is seen that wavelengths of the wave functions are longer than those of wave functions of
infinite potential well of same length and hence the quantized energies of the particle in a finite
well are lower than those for a particle in an infinite well.

TUNNELLING THROUGH A POTENTIAL ENERGY BARRIER

Consider a particle of energy E approaching a potential barrier of height U, (E<U). Potential

energy has a constant value of U in the region of width L and is zero in all other regions. This
is called a square barrier and U is called the barrier height. Since E<U, classically the regions
II and III shown in the figure are forbidden to the particle incident from left. But according to
quantum mechanics, all regions are accessible to the particle, regardless of its energy.

57
 Figure 3.8: Tunnelling through a potential barrier of finite height

By applying the boundary conditions, i.e. and its first derivative must be continuous at
boundaries (at x = 0 and x = L), full solution to the Schrödinger equation can be found which
is shown in figure. The wave function is sinusoidal in regions I and III but exponentially
decaying in region II. The probability of locating the particle beyond the barrier in region III
is nonzero. The movement of the particle to the far side of the barrier is called tunneling or
barrier penetration. The probability of tunneling can be described with a transmission
coefficient T and a reflection coefficient R.
The transmission coefficient represents the probability that the particle penetrates to the other
side of the barrier, and reflection coefficient is the probability that the particle is reflected by
the barrier. Because the particles must be either reflected or transmitted we have, R + T = 1.

An approximate expression for the transmission coefficient, when T<< 1 is

√ 2 𝑚 (𝑈−𝐸)
T ≈ e−2CL , where 𝐶 = . (3.6)
ℏ

THE SIMPLE HARMONIC OSCILLATOR

Consider a particle that is subject to a linear restoring force 𝐹 = −𝑘𝑥, where k is a constant
and x is the position of the particle relative to equilibrium (at equilibrium position x=0).
Classically, the potential energy of the system is,
1 1
𝑈 = 𝑘𝑥 2 = 𝑚𝜔2 𝑥 2
2 2
where the angular frequency of vibration is 𝜔 = √𝑘/𝑚.
The total energy E of the system is,
1 2 1
𝐸 = 𝐾𝑖𝑛𝑒𝑡𝑖𝑐 𝐸𝑛𝑒𝑟𝑔𝑦 + 𝑃𝑜𝑡𝑒𝑛𝑡𝑖𝑎𝑙 𝐸𝑛𝑒𝑟𝑔𝑦 = 𝐾 + 𝑈 = 𝑘𝐴 = 𝑚𝜔2 𝐴2
2 2

58
where A is the amplitude of motion. In the classical model, any value of E is allowed, including
E= 0, which is the total energy when the particle is at rest at x=0.
A quantum mechanical model for simple harmonic oscillator can be obtained by substituting
1
𝑈 = 2 𝑚𝜔2 𝑥 2 in Schrödinger equation:

ℏ2 𝑑 2 𝑦 1
− + 𝑚𝜔2 𝑥 2 𝑦 = 𝐸𝑦
2𝑚 𝑑𝑥 2 2

The solution for the above equation is

2
𝑦 = 𝐵𝑒 −𝐶𝑥
1
where 𝐶 = 𝑚𝜔/2ℏ and 𝐸 = 2 ℏ𝜔. The constant B can be determined from normalization

condition.
In quantum model, the energy levels of a harmonic oscillator are quantized. The energy of a
state having an arbitrary quantum number n is given by
1
𝐸𝑛 = (𝑛 + 2) ℏ𝜔; 𝑛 = 0, 1, 2 …. (3.7)
1
The state n = 0 corresponds to the ground state, whose energy is 𝐸0 = 2 ℏ𝜔 the state n = 1
3
corresponds to the first excited state, whose energy is 𝐸1 = ℏ𝜔 and so on. The energy-level
2

diagram for this system is shown in Figure 3.9. The separations between adjacent levels are
equal and given by ∆𝐸 = ℏ𝜔.

Figure 3.9: Energy-level diagram for a simple harmonic oscillator, superimposed on the
potential energy function.
QUESTIONS

1 What is a wave function? What is its physical interpretation?

2 What are the mathematical features of a wave function?

59
3 By solving the Schrödinger equation, obtain the wave-functions for a
particle of mass m in a one-dimensional “box” of length L.
4 Apply the Schrödinger equation to a particle in a one-dimensional
“box” of length L and obtain the energy values of the particle.
5 Sketch the lowest three energy states, wave-functions, probability
densities for the particle in a one-dimensional “box”.
6 The wave-function for a particle confined to moving in a one-
dimensional box is
ψ(x) = A sin(nπx L
) . Use the normalization condition on  to show

that 𝐴 = √2𝐿 .
7 The wave-function of an electron is ψ(x) = A sin(nπx L
) . Obtain an
expression for the probability of finding the electron between x = a
and x = b.
8 Sketch the potential-well diagram of finite height U and length L,
obtain the general solution of the Schrödinger equation for a particle
of mass m in it.
9 Sketch the wave-functions and the probability densities for the lowest
three energy states of a particle in a potential well of finite height.

10 Give a brief account of tunnelling of a particle through a potential

energy barrier.
11 Give a brief account of the quantum mechanical treatment of a simple
harmonic oscillator.
PROBLEMS

1 A particle wave function is given by the equation 𝐲 (𝐱) = 𝐀 𝒆−𝒂𝒙𝟐

(A) What is the value of A if this wave function is normalized?
(B) What is the expectation value of x for this particle?
Ans: A = (2a/π)¼ , x = 0

2 A free electron has a wave function 𝛙(𝐱) = 𝑨 𝐞𝐱𝐩[𝒊(𝟓. 𝟎 × 𝟏𝟎𝟏𝟎 )𝒙]

where x is in meters. Find (a) its de Broglie wavelength, (b) its momentum, and (c) its
kinetic energy in electron volts.
Ans: 1.26 x 10–10m, 5.27 x 10–24kg.m/s, 95.5 eV

3 An electron is confined between two impenetrable walls 0.20 nm apart. Determine the
energy levels for the states n =1 ,2 , and 3.
Ans: 9.2 eV, 37.7 eV, 84.8 eV

4 A 0.50 kg baseball is confined between two rigid walls of a stadium that can be modeled
as a “box” of length 100 m. Calculate the minimum speed of the baseball. If the baseball

60
 is moving with a speed of 150 m/s, what is the quantum number of the state in which the
baseball will be?
Ans: 6.63 x 10–36 m/s, 2.26 x 1037

5 A proton is confined to move in a one-dimensional “box” of length 0.20 nm. (a) Find
the lowest possible energy of the proton. (b) What is the lowest possible energy for an
electron confined to the same box? (c) Account for the great difference in results for
(a) and (b).
Ans: 5.13 x 10–3 eV, 9.41 Ev

6 (A) Using the simple model of a particle in a box to represent an atom, estimate the
energy (in eV) required to raise an atom from the state n =1 to the state n =2.
Assume the atom has a radius of 0.10 nm and that the moving electron carries the
energy that has been added to the atom.
(B) Atoms may be excited to higher energy states by absorbing photon energy.
Calculate the wavelength of the photon that would cause the transition from the
state n =1 to the state n =2.
Ans: 28.3 eV, 43.8 nm

7 A 30-eV electron is incident on a square barrier of height 40 eV. What is the probability
that the electron will tunnel through the barrier if its width is (A) 1.0 nm? (B) 0.10 nm?
Ans: 8.5 x 10–15, 0.039
8 An electron with kinetic energy E = 5.0 eV is incident on
a barrier with thickness L = 0.20 nm and height U = 10.0
eV as shown in the figure. What is the probability that
the electron (a) will tunnel through the barrier? (b) will
be reflected?
Ans: 0.0103, 0.990

9 A quantum simple harmonic oscillator consists of an electron bound by a restoring

force proportional to its position relative to a certain equilibrium point. The
proportionality constant is 8.99 N/m. What is the longest wavelength of light that can
excite the oscillator?
Ans: 600 nm

10 A quantum simple harmonic oscillator consists of a particle of mass m bound by a restoring

force proportional to its position relative to a certain equilibrium point. The proportionality
constant is k. What is the longest wavelength of light that can excite the oscillator? Ans:
𝑚
2𝜋𝑐√ 𝑘

61
 4 MOLECULES AND SOLIDS

OBJECTIVES:

• To understand the energy states and spectra of molecules

• To understand the cohesion of solid metals using bonding in solids
• To comprehend the electrical properties of metals, semiconductors and
insulators
• To understand the effect of doping on electrical properties of semiconductors
• To understand superconductivity and its engineering applications

ENERGY STATES AND SPECTRA OF MOLECULES

Consider an individual molecule in the gaseous phase of a substance. The energy E of the
molecule can be divided into four categories: (1) electronic energy, due to the interactions
between the molecule’s electrons and nuclei; (2) translational energy, due to the motion of the
molecule’s center of mass through space; (3) rotational energy, due to the rotation of the
molecule about its center of mass; and (4) vibrational energy, due to the vibration of the
molecule’s constituent atoms:
E = Eel + Etrans + Erot + Evib (4.1)

Because the translational energy is unrelated to internal structure, this molecular energy is
unimportant in interpreting molecular spectra. Although the electronic energies can be studied,
significant information about a molecule can be determined by analyzing its quantized
rotational and vibrational energy states. Transitions between these states give spectral lines in
the microwave and infrared regions of the electromagnetic spectrum, respectively.
ROTATIONAL MOTION OF MOLECULES

Let’s consider the rotation of a diatomic molecule around its center of mass (Figure 6.4a). A
diatomic molecule aligned along a y axis has only two rotational degrees of freedom,
corresponding to rotations about the x and z axes passing through the molecule’s center of
mass. If  is the angular frequency of rotation about one of these axes, the rotational kinetic
energy of the molecule about that axis can be expressed as
1
Erot = I 2
2 (4.2)

In this equation, I is the moment of inertia of the molecule about its center of mass, given by
 mm 
I =  1 2  r2 =  r2 (4.3)
 m1 + m2 

62
where m1 and m2 are the masses of the atoms that form the molecule, r is the atomic separation,
and  is the reduced mass of the molecule
m1m2
=
m1 + m2 (4.4)

Figure 4.1: Rotation of a diatomic molecule around its center of mass. (a) A diatomic
molecule oriented along the y axis. (b) Allowed rotational energies of a diatomic molecule
expressed as multiples of E1 = ℏ2/I.
The magnitude of the molecule’s angular momentum about its center of mass is L=Iω, which
can attain quantized values given by,

L = J ( J + 1) J = 0,1, 2, ... (4.5)

where J is an integer called the rotational quantum number. Combining Equations 4.5 and
4.2, we obtain an expression for the allowed values of the rotational kinetic energy of the
molecule:
2
Erot = EJ = J ( J + 1) J = 0, 1, 2, ... (4.6)
2I
The allowed rotational energies of a diatomic molecule are plotted in Figure 4.1b. The allowed
rotational transitions of linear molecules are regulated by the selection rule ΔJ =±1. From
Equation 4.6, the energies of the absorbed photons are given by,
2
h2
Ephoton = J= J J = 1, 2, 3, ... (4.7)
I 4 2 I

where J is the rotational quantum number of the higher energy state.

VIBRATIONAL MOTION OF MOLECULES

If we consider a molecule to be a flexible structure in which the atoms are bonded together by
“effective springs” as shown in Figure 4.2a, we can model the molecule as a simple harmonic

63
oscillator as long as the atoms in the molecule are not too far from their equilibrium positions.
Figure 4.2b shows a plot of potential energy versus atomic separation for a diatomic molecule,
where r0 is the equilibrium atomic separation. For separations close to r0, the shape of the
potential energy curve closely resembles a parabola. According to classical mechanics, the
frequency of vibration for the system is given by

1 k
f = (4.8)
2 

where k is the effective spring constant and  is the reduced mass given by Equation 4.4. The
vibrational motion and quantized vibrational energy can be altered if the molecule acquires
energy of the proper value to cause a transition between quantized vibrational states. The
allowed vibrational energies are
 1
Evib =  v +  hf v = 0, 1, 2, ... (4.9)
 2

where v is an integer called the vibrational quantum number.

Figure 4.2 (a) Effective-spring model of a diatomic molecule. (b) Plot of the potential energy
of a diatomic molecule versus atomic separation distance.

Figure 4.3 Allowed vibrational energies of a diatomic molecule, where f is the frequency of
vibration of the molecule

64
Substituting Equation 4.8 into Equation 4.9 gives the following expression for the allowed
vibrational energies:

 1 h k
Evib =  v +  v = 0, 1, 2, ... (4.10)
 2  2 

The selection rule for the allowed vibrational transitions is Δv = ±1. The photon energy for
transition is given by,

h k
Ephoton = Evib = (4.11)
2 

The vibrational energies of a diatomic molecule are plotted in Figure 4.3. At ordinary
temperatures, most molecules have vibrational energies corresponding to the v = 0 state
because the spacing between vibrational states is much greater than kBT, where kB is
Boltzmann’s constant and T is the temperature.
MOLECULAR SPECTRA

In general, a molecule vibrates and rotates simultaneously. To a first approximation, these

motions are independent of each other, so the total energy of the molecule is the sum of
Equations 4.6 and 4.9:

 1 2
E =  v +  hf + J ( J + 1)
 2 2I (4.12)

The energy levels of any molecule can be calculated from this expression, and each level is
indexed by the two quantum numbers v and J. From these calculations, an energy-level diagram
like the one shown in Figure 4.4a can be constructed. For each allowed value of the vibrational
quantum number v, there is a complete set of rotational levels corresponding to J = 0, 1, 2, . . .
. The energy separation between successive rotational levels is much smaller than the
separation between successive vibrational levels. The molecular absorption spectrum in Figure
4.4b consists of two groups of lines: one group to the right of center and satisfying the selection
rules ΔJ = +1 and Δv = +1, and the other group to the left of center and satisfying the selection
rules ΔJ = -1 and Δv = +1. The energies of the absorbed photons can be calculated from
Equation 4.12:
2
Ephoton = E = hf + ( J + 1) J = 0,1, 2, ... ( J = +1) (4.13)
I

65
 2
Ephoton = E = hf − J J = 1, 2, 3, ... ( J = −1) (4.14)
I

where J is the rotational quantum number of the initial state.

Figure 4.4: (a) Absorptive transitions between the v = 0 and v = 1 vibrational states of a
diatomic molecule. (b) Expected lines in the absorption spectrum of a molecule.
The experimental absorption spectrum of the HCl molecule shown in Figure 4.5. One
peculiarity is apparent, however: each line is split into a doublet. This doubling occurs because
two chlorine isotopes were present in the sample used to obtain this spectrum. Because the
isotopes have different masses, the two HCl molecules have different values of I.

Figure 4.5: Experimental absorption spectrum of the HCl molecule

The second function determining the envelope of the intensity of the spectral lines is the
Boltzmann factor. The number of molecules in an excited rotational state is given by
−ℏ2 𝐽(𝐽+1)
𝑛 = 𝑛0 𝑒 2𝐼𝑘𝐵 𝑇

66
where n0 is the number of molecules in the J = 0 state.
Multiplying these factors together indicates that the intensity of spectral lines should be
described by a function of J as follows:
−ℏ2 𝐽(𝐽+1)
𝐼𝑛𝑡𝑒𝑛𝑠𝑖𝑡𝑦 ∝ (2𝐽 + 1)𝑒 2𝐼𝑘𝐵 𝑇
(4.15)

BONDING IN SOLIDS

A crystalline solid consists of a large number of atoms arranged in a regular array, forming a
periodic structure.
Ionic Solids: Many crystals are formed by ionic bonding, in which the dominant interaction
between ions is the Coulomb force. Consider a portion of the NaCl crystal shown in Figure
4.6a. The red spheres are sodium ions, and the blue spheres are chlorine ions. As shown in
Figure 4.6b, each Na+ ion has six nearest-neighbor Cl- ions. Similarly, in Figure 4.6c, each Cl-
ion has six nearest-neighbor Na+ ions. Each Na+ ion is attracted to its six Cl- neighbors. The
corresponding potential energy is -6kee2/r, where ke is the Coulomb constant and r is the
separation distance between each Na+ and Cl-. In addition, there are 12 next-nearest-neighbor
Na+ ions at a distance of √2r from the Na+ ion, and these 12 positive ions exert weaker repulsive
forces on the central Na+. Furthermore, beyond these 12 Na+ ions are more Cl2 ions that exert
an attractive force, and so on. The net effect of all these interactions is a resultant negative
electric potential energy

e2
U attractive = − ke (4.16)
r

where α is a dimensionless number known as the Madelung constant. The value of α depends
only on the particular crystalline structure of the solid (α = 1.747 for the NaCl structure). When
the constituent ions of a crystal are brought close together, a repulsive force exists because of
electrostatic forces and the exclusion principle. The potential energy term B/rm in Equation
4.17 accounts for this repulsive force. The repulsive forces occur only for ions that are very
close together.
Therefore, we can express the total potential energy of the crystal as
e2 B
U total = − ke + (4.17)
r rm

where m in this expression is some small integer.

67
 Figure 4.6: (a) Crystalline structure of NaCl. (b) Each positive sodium ion is surrounded by
six negative chlorine ions. (c) Each chlorine ion is surrounded by six sodium ions

Figure 4.7: Total potential energy versus ion separation distance for an ionic solid, where U0
is the ionic cohesive energy and r0 is the equilibrium separation distance between ions
A plot of total potential energy versus ion separation distance is shown in Figure 4.7. The
potential energy has its minimum value U0 at the equilibrium separation, when r = r0.
e2  1
U 0 = − ke 1 − 
r0  m  (4.18)

This minimum energy U0 is called the ionic cohesive energy of the solid, and its absolute value
represents the energy required to separate the solid into a collection of isolated positive and
negative ions.

Covalent Solids: Solid carbon, in the form of diamond, is a crystal whose atoms are covalently
bonded. In the diamond structure, each carbon atom is covalently bonded to four other carbon
atoms located at four corners of a cube as shown in Figure 4.8(a). The crystalline structure of
diamond is shown in Figure 4.8 (b). The basic structure of diamond is called tetrahedral (each
carbon atom is at the center of a regular tetrahedron), and the angle between the bonds is 109.5°.
Other crystals such as silicon and germanium have the same structure. Covalently bonded

68
solids are usually very hard, have high bond energies and high melting points, and are good
electrical insulators.

Figure 4.8: (a) Each carbon atom in a diamond crystal is covalently bonded to four other
carbon atoms so that a tetrahedral structure is formed. (b) The crystal structure of diamond,
showing the tetrahedral bond arrangement
Metallic Solids: Metallic bonds are generally weaker than ionic or covalent bonds. The outer
electrons in the atoms of a metal are relatively free to move throughout the material, and the
number of such mobile electrons in a metal is large. The metallic structure can be viewed as a
“sea” or a “gas” of nearly free electrons surrounding a lattice of positive ions (Figure 4.9). The
bonding mechanism in a metal is the attractive force between the entire collection of positive
ions and the electron gas.

Light interacts strongly with the free electrons in metals. Hence, visible light is absorbed and
re-emitted quite close to the surface of a metal, which accounts for the shiny nature of metal
surfaces. Because the bonding in metals is between all the electrons and all the positive ions,
metals tend to bend when stressed.

Figure 4.9: Highly schematic diagram of a metal

69
FREE-ELECTRON THEORY OF METALS

Quantum based free electron theory of metals is centered on wave nature of electrons. In this
model, one imagines that the outer-shell electrons are free to move through the metal but
are trapped within a three-dimensional box formed by the metal surfaces. Therefore,
each electron is represented as a particle in a box and is restricted to quantized energy
levels. Each energy state can be occupied by only two electrons (one with spin up & the
other with spin down) as a consequence of exclusion principle. In quantum statistics, it is
shown that the probability of a particular energy state E being occupied by an electrons is
given by

1
f (E) = (4.19)
 E − EF 
exp   + 1
 kT 

where f(E) is called the Fermi-Dirac distribution function and EF is called the Fermi
energy. Plot of f(E) versus E is shown in figure 4.10.

Figure. 4.10: Plot of Fermi-Dirac distribution function f(E) Vs energy E at (a) T = 0K and (b)
T > 0K
At zero kelvin (0 K), all states having energies less than the Fermi energy are occupied, and
all states having energies greater than the Fermi energy are vacant. i.e. Fermi energy is the
highest energy possessed by an electron at 0 K (Figure 4.10a). As temperature increases (T >
0K), the distribution rounds off slightly due to thermal excitation and probability of Fermi level
being occupied by an electron becomes half (Figure 4.10b). In other words, Fermi energy is
that energy state at which probability of electron occupation is half. The Fermi energy EF also
depends on temperature, but the dependence is weak in metals.

70
Density of states: From particle in a box problem, for a particle of mass m is confined to move
in a one-dimensional box of length L, the allowed states have quantized energy levels given
by,

h2 
2 2
En = 2
n =
2
2
n2 n = 1, 2, 3 . . . (4.20)
8mL 2mL

An electron moving freely in a metal cube of side L, can be modeled as particle in a three-
dimensional box. It can be shown that the energy for such an electron is

2
2
E=
2mL 2 (n 2
x + n y2 + nz2 ) (4.21)

where m is mass of the electron and nx, ny, nz are quantum numbers(positive integers). Each
allowed energy value is characterized by a set of three quantum numbers (nx, ny, nz - one
for each degree of freedom). Imagine a three-dimensional quantum number space
whose axes represent nx, ny, nz. The allowed energy states in this space can be represented
as dots located at positive integral values of the three quantum numbers as shown in the
Figure 4.11.

Figure 4.11: Representation of the allowed energy states in a quantum number space (dots
represent the allowed states)
Eq. 5.21 can be written as

E
nx2 + ny2 + nz2 = = n2 (4.22)
Eo

71
 2
2
E
where Eo = 2
and n =
2mL Eo

Eq. 4.22 represents a sphere of radius n. Thus, the number of allowed energy states
having energies between E and E+dE is equal to the number of points in a spherical
shell of radius n and thickness dn. In this quantum number space each point is at the corners
of a unit cube and each corner point is shared by eight unit cubes and as such the contribution
of each point to the cube is 1/8 th. Because a cube has eight corners, the effective point per unit
cube and hence unit volume is one. In other words, number of points is equal to the volume
of the shell. The “volume” of this shell, denoted by G(E)dE.

1 1
G(E) dE =   ( 4 n 2 dn ) =    n dn
2

8 2

 E   E  1 2  E
G ( E ) dE = 12    d    using the relation n =
E 
 o   o  
E Eo

 E  − 12 −1 −3 1
G ( E ) dE = 1
2   Eo
1
2 E 2
dE = 1
4  Eo 2
E 2
dE
 o
E

−3
 2 2  2
1
G( E ) dE = 4  
1
2 
E 2
dE
 2mL 

3
2 m 2 L3 12
G ( E ) dE = E dE , L3 = V
2 2 3

Number of states per unit volume per unit energy range, called density of states, g(E) is
given by

g(E) = G(E)/V

3
2
G( E ) 2 m 1
g ( E ) dE = dE = E 2
dE
V 2 2 3

3
4 2 m 2 1 h
g ( E ) dE = E 2
dE =
h3 2

72
Finally, we multiply by 2 for the two possible spin states of each particle.

3
8 2 m 2 1
g ( E ) dE = E 2
dE (4.23)
h3

g(E) is called the density-of-states function.

Electron density: For a metal in thermal equilibrium, the number of electrons N(E) dE,
per unit volume, that have energy between E and E+dE is equal to the product of the
density of states and the probability that a state is occupied. that is,

N(E)dE = [ g(E)dE ] f(E)

3 1
8 2 m 2
E 2 dE
N ( E ) dE = (4.24)
h3  E − EF 
exp   + 1
 kT 

Plots of N(E) versus E for two temperatures are given in figure 4.12.

Figure 4.12: Plots of N(E) versus E for (a) T = 0K (b) T = 300K

If ne is the total number of electrons per unit volume, we require that

 3  1
8 2 m 2
E 2 dE
ne =  N ( E ) dE =  (4.25)
h3  E − EF 
 + 1
0 0
exp 
 kT 

At T = 0K, the Fermi-Dirac distribution function f(E) = 1 for E <EF and f(E) = 0 for E >EF.
Therefore, at T = 0K,

3 3 3
8 2 m 8 2 m 16 2  m
2 EF 2 2

 ( ) EF
1 3 3
ne = E 2
dE = 2
3
2
= EF 2 (4.26)
h3 0
h3 3 h3

Solving for Fermi energy at 0K, we obtain

73
 2
h 2  3 ne  3
EF ( 0 ) =   (4.27)
2 m  8 

The average energy of a free electron in a metal at 0K is Eav = (3/5)EF.

BAND THEORY OF SOLIDS

When a quantum system is represented by wave function, probability density ||2 for that
system is physically significant while the probability amplitude  not. Consider an atom such

as sodium that has a single s electron outside of a closed shell. Both the wave functions  S ( r )
+

and  S ( r ) are valid for such an atom [ S ( r ) and  S ( r ) are symmetric and anti symmetric
− + −

wave functions]. As the two sodium atoms are brought closer together, their wave functions
begin to overlap. Figure 4.13 represents two possible combinations : i) symmetric - symmetric
and ii) symmetric – antisymmetric . These two possible combinations of wave functions
represent two possible states of the two-atom system. Thus, the states are split into two
energy levels. The energy difference between these states is relatively small, so the two states
are close together on an energy scale.
When two atoms are brought together, each energy level will split into 2 energy levels. (In
general, when N atoms are brought together N split levels will occur which can hold 2N
electrons). The split levels are so close that they may be regarded as a continuous band of
energy levels. Figure 4.14 shows the splitting of 1s and 2s levels of sodium atom when :
(a) two sodium atoms are brought together (b)five sodium atoms are brought together (c)
a large number of sodium atoms are assembled to form a solid. The close energy levels
forming a band are seen clearly in (c).

Figure. 4.13: The wave functions of two atoms combine to form a composite wave function :
a) symmetric-symmetric b) symmetric-antisymmetric

74
 Figure 4.14: Splitting of 1s and 2s levels of sodium atoms due to interaction between them
Some bands may be wide enough in energy so that there is an overlap between the
adjacent bands. Some other bands are narrow so that a gap may occur between the allowed
bands, and is known as forbidden energy gap. The 1s, 2s, and 2p bands of solid sodium
are filled completely with electrons. The 3s band (2N states) of solid sodium has only
N electrons and is partially full; The 3p band, which is the higher region of the overlapping
bands, is completely empty as shown in Figure 4.15

Figure 5.15: Energy bands of a sodium crystal

ELECTRICAL CONDUCTION IN METALS, INSULATORS AND
SEMICONDUCTORS

Good electrical conductors contain high density of free charge carriers, and the density
of free charge carriers in insulators is nearly zero. In semiconductors free-charge-carrier
densities are intermediate between those of insulators and those of conductors.
Metals: Metal has a partially filled energy band (Figure 4.16 (a)). At 0K Fermi level is
the highest electron-occupied energy level. If a potential difference is applied to the
metal, electrons having energies near the Fermi energy require only a small amount of
additional energy to reach nearby empty energy states above the Fermi-level. Therefore,

75
electrons in a metal experiencing a small force (from a weak applied electric field) are free to
move because many empty levels are available close to the occupied energy levels. The model
of metals based on band theory demonstrates that metals are excellent electrical conductors.
Insulators: Consider the two outermost energy bands of a material in which the lower band is
filled with electrons and the higher band is empty at 0 K (Figure 4.16 (b)). The lower, filled
band is called the valence band, and the upper, empty band is the conduction band. The energy
separation between the valence and conduction band, called energy gap Eg, is large for
insulating materials. The Fermi level lies somewhere in the energy gap. Due to larger energy
gap compare to thermal energy kT (26meV) at room temperature, excitation of electrons from
valence band to conduction band is hardly possible. Since the free-electron density is nearly
zero, these materials are bad conductors of electricity.
Semiconductors: Semiconductors have the same type of band structure as an insulator, but the
energy gap is much smaller, of the order of 1 eV. The band structure of a semiconductor is
shown in Figure 4.16c. Because the Fermi level is located near the middle of the gap for a
semiconductor and Eg is small, appreciable numbers of electrons are thermally excited from
the valence band to the conduction band. Because of the many empty levels above the thermally
filled levels in the conduction band, a small applied potential difference can easily raise the
energy of the electrons in the conduction band, resulting in a moderate conduction. At T = 0
K, all electrons in these materials are in the valence band and no energy is available to excite
them across the energy gap. Therefore, semiconductors are poor conductors at very low
temperatures. Because the thermal excitation of electrons across the narrow gap is more
probable at higher temperatures, the conductivity of semiconductors increases rapidly with
temperature. This is in sharp contrast with the conductivity of metals, where it decreases with
increasing temperature. Charge carriers in a semiconductor can be negative, positive, or both.
When an electron moves from the valence band into the conduction band, it leaves behind a
vacant site, called a hole, in the otherwise filled valence band.

Figure 4.16: Band structure of (a) Metals (b) Insulators (c) Semiconductors
In an intrinsic semiconductor (pure semiconductor) there are equal number of conduction
electrons and holes. In the presence of an external electric field, the holes move in
the direction of field and the conduction electrons move opposite to the direction of

76
the field. Both these motions correspond to the current in the same direction (Figure
4.17).

Figure 4.17: Movement of electrons and holes in an intrinsic semiconductor

Doped Semiconductors (Extrinsic semiconductors): Semiconductors in their pure form are
called intrinsic semiconductors while doped semiconductors are called extrinsic
semiconductors. Doping is the process of adding impurities to a semiconductor. By doping
both the band structure of the semiconductor and its resistivity are modified. If a
tetravalent semiconductor (Si or Ge) is doped with a pentavalent impurity atom (donor
atom), four of the electrons form covalent bonds with atoms of the semiconductor and
one is left over (Figure 4.18). At zero K, this extra electron resides in the donor-levels,
that lie in the energy gap, just below the conduction band. Since the energy Ed between
the donor levels and the bottom of the conduction band is small, at room temperature,
the extra electron is thermally excited to the conduction band. This type of
semiconductors are called n-type semiconductors because the majority of charge carriers
are electrons (negatively charged).
If a tetravalent semiconductor is doped with a trivalent impurity atom (acceptor atom),
the three electrons form covalent bonds with neighboring semiconductor atoms, leaving
an electron deficiency (a hole) at the site of fourth bond (Figure 4.19). At zero K, this
hole resides in the acceptor levels that lie in the energy gap just above the valence
band. Since the energy Ea between the acceptor levels and the top of the valence band
is small, at room temperature, an electron from the valence band is thermally excited
to the acceptor levels leaving behind a hole in the valence band. This type of
semiconductors are called p-type semiconductors because the majority of charge carriers
are holes (positively charged).

77
 Figure 4.18: n-type semiconductor – two dimensional representation and band structure
When conduction in a semiconductor is the result of acceptor or donor impurities, the material
is called an extrinsic semiconductor. The typical range of doping densities for extrinsic
semiconductors is 1013 to 1019 cm-3, whereas the electron density in a typical semiconductor is
about 1021 cm-3.

Figure 4.19: p-type semiconductor: two-dimensional representation and band structure

HALL EFFECT

Hall effect is a process in which a transverse electric field is developed in a solid material when
the material carrying an electric current is placed in a magnetic field that is perpendicular to
the current. The Hall effect was discovered by Edwin Herbert Hall in 1879. When a current-
carrying conductor or a semiconductor is introduced to a perpendicular magnetic field, a

78
voltage can be measured at the right angle to the current path. This effect of obtaining a
measurable voltage is known as the Hall effect.

Consider a semiconductor (assumed to be n-type) in the form of a rectangular strip of width w,

thickness t and electron density n. Let a current  flow along its length in X direction and a
transverse magnetic field B be applied across its thickness t along the Y direction (Figure 4.20).

Figure 4.20 : Hall Effect in n-type semiconductor

The moving electrons experience a force 𝐹𝑀 due to the magnetic field. Due to 𝐹𝑀 , the electrons
tend to move in the Z direction leaving behind the positive charges.

𝐹𝑀 = 𝑒 𝑣𝐷 𝐵

where, 𝑣𝐷 is the drift speed of the electrons and 𝑒 is the charge on the electron.

This separation of charges results in an electric field EH across the width of the specimen (in Z
direction). EH exerts a force on the electrons given by

𝐹𝐸 = − 𝑒 𝐸𝐻

Under equilibrium conditions 𝑒 𝐸𝐻 = 𝑒 𝑣𝐷 𝐵  𝐸𝐻 = 𝑣𝐷 𝐵

VH I
We have EH = and vD =
w ne wt

Substituting these values, we get

B RH  B
VH = or VH =
net t

79
 1
Where, the quantity = RH is called the Hall coefficient of the specimen.
ne

 V H  t 
 RH =    (4.29)
 B   

The hall coefficient is positive if the number of positive charges is more than the negative
charges. Similarly, it is negative when electrons are more than holes.

Applications of Hall Effect:

1. Magnetic field sensing equipment (Gauss Meter)

2. For the measurement of direct current, Hall effect Tong Tester is used.
3. It is used in phase angle measurement.
4. Proximity detectors
5. Hall effect Sensors and Probes
6. For detecting wheel speed and accordingly assist the anti-lock braking system.
RESISTIVITY MEASUREMENT BY FOUR PROBE METHOD

A material's electrical resistivity is a measure of how strongly it opposes the flow of current.
The Ω-m is the SI unit of electrical resistivity. The electric resistance (R) of a material is given
by R = V/I where V is electrical potential difference across the material and I is the current
through the material. The resistance depends on the dimension of the material. For a wire R =
L/A, where L is the length of the area, A is the cross sectional area of the wire and  is the
electrical resistivity of the material of the wire. Thus, for a wire, the resistivity,

𝑅×𝐴
𝜌= 𝐿

When two probes are used for measurement of voltage and current, and hence for the
calculation of resistance in the case of a semiconductor, the probe resistance, the contact
resistance, the spreading resistance, and the sheet resistance (resistance of a square piece of a
thin material with contacts made to two opposite sides of the square) due to the semiconductor
will come into effect. Using four probes one can eliminate the probe resistance, contact
resistance (the electrical resistance that arises at the contact point when components are
connected) and the spread resistance (refers to the phenomenon in which current spreads
through a material or device, resulting in a decrease in resistance. in the measurement).

80
The current is passed through the outer probes and the voltage is measured across the inner
probes. The resistivity measured using the four probes may vary with the geometry (thickness
and shape) of the semiconductor sample and placement of the probes on the surface of the
sample. It may also vary with the probe gap, nature of the surface of the sample, the size of the
sample.

Figure 4.21: Experimental setup for resistivity measurement.

Mathematical calculations show that the resistivity of a semi-infinite sample is given by

𝑉
𝜌0 = × 2𝜋𝑆
𝐼

where I is the current through the outer probes, V is the voltage across the inner probes, S is the
distance between the probes (which is taken to be the same here) and 2πS is the geometric
factor of the semi-infinite sample.

For a finite rectangular sample of thickness W, a dimension correction function f (W/S) is

introduced in the resistivity expression as,

𝜌0
𝜌=
𝑓(𝑊 ⁄𝑆)

2𝜋𝑆 𝑉
i.e., 𝜌 = 𝑓(𝑊⁄𝑆) × (4.30)
𝐼

The resistivity is estimated form the above expression.

PHOTOVOLTAIC EFFECT AND SOLAR CELLS

Solar cells, also referred to as photovoltaic cells, are pivotal in the realm of renewable energy.
Their functionality hinges on the photovoltaic effect, where semiconductor materials within

81
the cell absorb photons from sunlight. These absorbed photons energize electrons, enabling
them to flow as an electric current. This process occurs without moving parts, noise, or
greenhouse gas emissions, rendering solar cells an environmentally friendly and sustainable
energy source. The significance of solar cells lies in their contribution to mitigating climate
change and reducing dependence on finite fossil fuels. By harnessing the virtually infinite
energy of the sun, solar cells offer a clean alternative to traditional energy sources. They aid in
shrinking carbon footprints, thereby combating global warming and environmental
degradation. Moreover, solar cells have versatile applications, ranging from powering
residential homes and commercial buildings to providing electricity in remote locations
without access to the grid. They also find use in spacecraft, satellites, and portable electronic
devices, showcasing their adaptability and reliability in various settings.

Solar spectrum and Air Mass (AM)

The solar spectrum and air mass are crucial concepts in understanding how sunlight interacts
with the Earth's atmosphere and influences the performance of solar energy systems. The solar
spectrum refers to the distribution of electromagnetic radiation emitted by the sun across
different wavelengths. Sunlight contains a broad range of wavelengths, from ultraviolet (UV)
to infrared (IR), with visible light occupying the middle portion of the spectrum. Each
wavelength carries a specific amount of energy, and the distribution of this energy determines
the spectral composition of sunlight. However, as sunlight travels through the Earth's
atmosphere, it encounters various molecules and particles that can scatter and absorb certain
wavelengths. This interaction alters the solar spectrum reaching the Earth's surface. For
instance, shorter wavelengths like UV are more prone to scattering by molecules such as
oxygen and nitrogen, while longer wavelengths like IR can be absorbed by greenhouse gases
like water vapor and carbon dioxide.

Air mass (AM) quantifies the path length of sunlight through the Earth's atmosphere before
reaching the surface. It is expressed numerically as the ratio of the actual path length to the
shortest possible path length through the atmosphere (when the sun is directly overhead). Air
mass values vary depending on the angle of the sun relative to the observer's location. For
example, AM1 corresponds to solar radiation perpendicular to the Earth's surface at sea level,
while higher AM values represent sunlight traveling through a thicker atmospheric layer at
greater angles. Understanding the solar spectrum and air mass is crucial for designing and
optimizing solar energy systems. The standard spectrum for space applications is referred to as

82
AM0. It has an integrated power of 1366.1 W/m2. The AM1.5 Global spectrum is designed for
flat plate modules and has an integrated power of 1000 W/m2.

(Source: https://g2voptics.com/)

Figure 4.22. Solar spectrum (Red: AM1.5)

Solar Cell: p-n junction under illumination

Figure 4.23: Schematic of a solar cell

At the heart of a solar cell is a semiconductor material, often silicon, with additional elements
added to create either a positive (p-type) or negative (n-type) charge. When sunlight strikes the
solar cell, it excites electrons in the semiconductor material, causing them to break free from
their atoms. This process generates electron-hole pairs. However, for these electron-hole pairs
to produce an electric current, they need to be separated and directed towards an external
circuit. This separation occurs at the junction between the p-type and n-type regions of the solar
cell, known as the p-n junction. At this junction, the free electrons from the n-type region are
attracted to the positive charge in the p-type region, while the holes from the p-type region are

83
attracted to the negative charge in the n-type region. This movement of charge creates an
electric field across the junction.

When an external circuit is connected to the solar cell, the separated electrons and holes can
flow in opposite directions through the circuit, generating an electric current. This flow of
electrons constitutes electricity, which can be harnessed to power electrical devices or stored
in batteries for later use.

Figure 4.24: Solar cell under illumination

Figure 4.25: Energy level diagram showing carrier transport under illumination of a p-n
junction
Solar Cell Parameters
(i) Maximum Power Point Power (PMPP): The semiconductor material of the solar cell has its
internal resistance. This resistance varies with the light intensity and attains a minimum value
at maximum intensity. At this saturation value the power output is maximum. This maximum
power output is termed as maximum power point power and denoted as PMPP. At this point
maximum power transfer takes from the solar cell to the load, and it is given by,
PMPP = I × V

84
PMPP is measured by finding the product of voltage and current at the maximum power point.
(ii) Short Circuit Current (ISC) : When the solar cell terminals are shorted (RL = 0) together
maximum current flows through the terminals. This maximum current is called short-circuited
current and denoted as ISC.
(iii) Open Circuit Voltage (VOC) : The voltage measured at the terminals of the solar cell without
load (RL = ) is called open circuit voltage and denoted as VOC. At both the cases of open
circuit or short circuit the power dissipated by the solar cell is zero.
(iv) Conversion Efficiency (η) : In a solar cell light energy is converted in to electrical energy.
In this process of conversion not all input solar radiation is converted in to electric current. The
conversion efficiency denoted in percentage and it is given by,
𝑂𝑢𝑡𝑝𝑢𝑡 𝑃𝑜𝑤𝑒𝑟
𝜂=
𝐼𝑛𝑝𝑢𝑡 𝑝𝑜𝑤𝑒𝑟
𝑃𝑀𝑃𝑃
𝜂=
𝐴𝐶 𝐸
where AC is the surface area of the solar cell, E is the light intensity in watts/cm2.
(v) Fill Factor: The fill factor (FF) of a solar cell is a parameter used to quantify its efficiency
in converting sunlight into electrical energy. It represents the ratio of the maximum power
output of the solar cell to the product of its open-circuit voltage (Voc) and short-circuit current
(Isc). Mathematically, the fill factor (FF) is defined as:
𝑀𝑎𝑥𝑖𝑚𝑢𝑚 𝑝𝑜𝑤𝑒𝑟 𝑜𝑢𝑡𝑝𝑢𝑡
𝐹𝐹 =
𝑉𝑂𝐶 𝐼𝑆𝐶
The fill factor essentially measures how effectively a solar cell can utilize the available sunlight
to produce electricity. It takes into account losses within the solar cell, including those due to
recombination of charge carriers, series resistance, and shunt resistance.
Ideally, a solar cell would have a fill factor of 1, indicating perfect efficiency. However, in
practice, fill factors for commercial solar cells typically range from 0.5 to 0.8, depending on
various factors such as the materials used, manufacturing processes, and operating conditions.

85
 (Source: https://www.alternative-energy-tutorials.com/)

Figure 4.26: I-V and P-V curve for a typical solar cell
Solar cell materials
The Shockley-Queisser limit, named after scientists William Shockley and Hans-Joachim
Queisser, is a theoretical maximum efficiency limit for a single-junction solar cell. It
establishes the maximum efficiency a solar cell can achieve based on fundamental principles
of thermodynamics and semiconductor physics. It takes into account factors such as the
bandgap energy of the semiconductor material used in the solar cell, the energy of photons in
sunlight, and the loss mechanisms within the cell. According to the Shockley-Queisser limit,
the maximum efficiency of a single-junction solar cell operating under one sun illumination
(AM1.5G spectrum) at room temperature is approximately 33.7%. For single-junction solar
cells, the bandgap energy should be such that it matches the solar spectrum to achieve
maximum absorption of photons. Typically, bandgap energies in the range of 1.1 to 1.7 electron
volts (eV) are considered suitable for solar cells.

86
 (Source: https://www.universitywafer.com/what-is-the-shockley-queisser-limit.html)

Figure 4.27: Shockley-Queisser limit

Choosing the right material for solar cells involves a strategic approach that considers several
factors to optimize performance, cost-effectiveness, and sustainability.
Efficiency: Prioritize materials with high conversion efficiency to maximize electricity
generation per unit area. Silicon-based solar cells offer proven high efficiency, but emerging
materials like perovskites show potential for even greater efficiency gains.
Cost-effectiveness: Balance efficiency with cost to ensure affordability and scalability. Silicon
remains a popular choice due to its abundance, but thin-film technologies like cadmium
telluride (CdTe) and copper indium gallium selenide (CIGS) offer lower manufacturing costs
per watt.
Availability: Consider the availability and accessibility of raw materials to ensure long-term
sustainability and reduce supply chain risks. Choose materials with ample global reserves and
minimal geopolitical constraints.
Stability and Reliability: Select materials with proven long-term stability and reliability under
various environmental conditions to ensure consistent performance over the solar cell's
lifetime.
Toxicity and Environmental Impact: Assess the environmental impact and toxicity of
materials throughout their lifecycle, from extraction and manufacturing to disposal or
recycling. Choose materials with minimal environmental footprint and recyclability to promote
sustainability.
Technological Feasibility: Evaluate the technological readiness and scalability of materials
for large-scale manufacturing. Consider factors such as ease of fabrication, compatibility with
existing infrastructure, and potential for integration into commercial production processes.

87
SUPERCONDUCTIVITY-PROPERTIES AND APPLICATIONS

Superconductor is a class of metals and compounds whose electrical resistance decreases to

virtually zero below a certain temperature Tc called the critical temperature. The critical
temperature is different for different superconductors. Mercury loses its resistance completely
and turns into a superconductor at 4.2K. Critical temperatures for some important
elements/compounds are listed below.

Element/Compound Tc (K)
La 6.0
NbNi 10.0
Nb3Ga 23.8

Figure 4.28: Plot of Resistance Vs Temperature for normal metal and a superconductor

Meissner Effect: In the presence of magnetic field, as the temperature of superconducting

material is lowered below Tc, the field lines are spontaneously expelled from the interior of the
superconductor(B = 0, Figure 6.24). Therefore, a superconductor is more than a perfect
conductor; it is also a perfect diamagnet. The property that B = 0 in the interior of a
superconductor is as fundamental as the property of zero resistance. If the magnitude of the
applied magnetic field exceeds a critical value Bc, defined as the value of B that destroys a
material’s superconducting properties, the field again penetrates the sample. Meissner effect
can be explained in the following way.

88
 Figure 4.29: A superconductor in the form of a long cylinder in the presence of an external
magnetic field.

A good conductor expels static electric fields by moving charges to its surface. In effect, the
surface charges produce an electric field that exactly cancels the externally applied field inside
the conductor. In a similar manner, a superconductor expels magnetic fields by forming surface
currents. Consider the superconductor shown in Figure 5.24. Let’s assume the sample is
initially at a temperature T>Tc so that the magnetic field penetrates the cylinder. As the cylinder
is cooled to a temperature T<Tc, the field is expelled. Surface currents induced on the
superconductor’s surface produce a magnetic field that exactly cancels the externally applied
field inside the superconductor. As expected, the surface currents disappear when the external
magnetic field is removed.

BCS Theory: In 1957, Bardeen, Cooper and Schrieffer gave a successful theory to explain the
phenomenon of superconductivity, which is known as BCS theory. According to this theory,
two electrons can interact via distortions in the array of lattice ions so that there is a net
attractive force between the electrons. As a result, the two electrons are bound into an entity
called a Cooper pair, which behaves like a single particle with integral spin. Particles with
integral spin are called bosons. An important feature of bosons is that they do not obey the
Pauli exclusion principle. Consequently, at very low temperatures, it is possible for all bosons
in a collection of such particles to be in the lowest quantum state and as such the entire
collection of Cooper pairs in the metal is described by a single wave function. There is an
energy gap equal to the binding energy of a Cooper pair between this lowest state and the next
higher state. Under the action of an applied electric field, the Cooper pairs experience an
electric force and move through the metal. A random scattering event of a Cooper pair from a

89
lattice ion would represent resistance to the electric current. Such a collision would change the
energy of the Cooper pair because some energy would be transferred to the lattice ion. There
are no available energy levels below that of the Cooper pair (it is already in the lowest state),
however, and none available above because of the energy gap. As a result, collisions do not
occur and there is no resistance to the movement of Cooper pairs.

Types of Superconductors

Type - I Superconductors: Type I superconductors are those superconductors that lose their
superconductivity very easily or abruptly when placed in the external magnetic field. As you
can see from the graph of the intensity of magnetization (M) versus applied magnetic field (H),
when the Type I superconductor is placed in the magnetic field, it suddenly or easily loses its
superconductivity at the critical magnetic field (Hc) (point A).

Figure 4.30: Graph of the intensity of magnetization (M) versus applied magnetic field (H)

After Hc, the Type I superconductor will become a conductor. Type I superconductors are also
known as soft superconductors because they lose their superconductivity easily. Type I
superconductors are perfectly diamagnetic in nature and obey the Meissner effect. Lead (Pb)
at 7.196 K, Lanthanum (La) at 4.88 K and Tantalum (Ta) at 4.47 K are Type-I superconductors.

Type-II Superconductors: Type II superconductors are those superconductors that lose their
superconductivity gradually but not easily or abruptly when placed in the external magnetic
field. As seen from the graph of the intensity of magnetization (M) versus applied magnetic
field (H), when the Type II superconductor is placed in the magnetic field, it gradually loses
its superconductivity. Type II superconductors start to lose their superconductivity at the lower
critical magnetic field (Hc1) and completely lose their superconductivity at the upper critical
magnetic field (Hc2).

90
 Figure 4.31: Graph of the intensity of magnetization (M) versus applied magnetic field (H)

The state between the lower critical magnetic field (Hc1) and upper critical magnetic field (Hc2)
is known as vortex state or intermediate state. After Hc2, the Type II superconductor will
become a conductor.
Type II superconductors are also known as hard superconductors because they lose their
superconductivity gradually but not easily. Type II superconductors obey the Meissner effect
but not completely. Example of Type II superconductors: YBCO (Yttrium barium copper
oxide), niobium nitride (NbN), Barium bismuth (BaBi3). Type II superconductors are used for
strong field superconducting magnets.
Applications: Most important and basic application of superconductors is in high field
solenoids which can be used to produce intense magnetic field. Superconducting magnets are
used in magnetic resonance imaging (MRI) technique. Magnetic levitation, based on Meissner
effect, is another important application of superconductors. This principle is used in maglev
vehicles. Detection of a weak magnetic field and lossless power transmission are some other
important applications of superconductors.

QUESTIONS

1. Obtain an expression for rotational energy of a diatomic molecule. Sketch schematically

these rotational energy levels.
2. Obtain expressions for rotational transition photon energies and frequencies.
3. Obtain an expression for vibrational energy of a diatomic molecule. Sketch schematically
these vibrational energy levels. Obtain expression for vibrational transition photon
energies.
4. Write expression for total energy (vibrational and rotational) of a molecule. Sketch
schematically these energy levels of a diatomic molecule for the lowest two
vibrational energy values, indicating the possible transitions. Write the expressions

91
 for the energy of the photon in the molecular energy transitions. Write the
expression for the frequency separation of adjacent spectral lines.
5. Explain the expression for the total potential energy of a crystal. Sketch
schematically the plot of the same.
6. Define (a) ionic cohesive energy (b) atomic cohesive energy, of a solid.
7. Write the expression for Fermi-Dirac distribution function. Sketch schematically the
plots of this function for zero kelvin and for temperature above zero kelvin.
8. Derive an expression for density-of-states.
9. Assuming the Fermi-Dirac distribution function , obtain an expression for the density
of free-electrons in a metal with Fermi energy EF, at zero K and, hence obtain
expression for Fermi energy EF in a metal at zero K. [ Given: density-of-states
3
8 2  m 2 12
function g( E ) dE = E dE ]
h3
10. Explain the formation of energy bands in solids with necessary diagrams.
11. Distinguish between conductors, insulators and semiconductors on the basis of band
theory
12. Indicate the position of (a) donor levels (b) acceptor levels, in the energy band
diagram of a semiconductor.
13. What is the difference between p-type and n-type semiconductors? Explain with band
diagram.
14. With necessary diagrams, explain doping in semiconductors.
15. Why the electrical conductivity of an intrinsic semiconductor increases with increasing
temperature?
16. Explain Hall effect and derive an expression for Hall coefficient.
17. Explain measurement of resistivity of a semiconductor by four-probe method.
18. What are the advantages of four-probe method?
19. Define (i) Fill factor, (ii) Open circuit voltage, (iii) Short circuit current, (iv) Efficiency of
a solar cell.
20. Give representative I-V plot of a solar cell under illumination and indicate Voc, Isc,
maximum power point.
21. What are superconductors? Draw a representative graph of Resistance Vs Temperature for
a superconductor.
22. Explain Meissner effect.
23. Explain briefly the BCS theory of superconductivity in metals.
24. Classify and explain types of superconductors.
PROBLEMS

1. An HCl molecule is excited to its first rotational energy level, corresponding

to J = 1. If the distance between its nuclei is ro = 0.1275 nm, what is the angular
speed of the molecule about its center of mass ?
Ans: 5.691012 rad/s

92
 2. The rotational spectrum of the HCl molecule contains lines with wavelengths of
0.0604, 0.0690, 0.0804, 0.0964, and 0.1204 mm. What is the moment of inertia of the
molecule?
Ans: 2.72x10-47 kg.m2
3. The frequency of photon that causes v = 0 to v = 1 transition in the CO molecule
is 6.42 x 1013 Hz. Ignore any changes in the rotational energy. (A) Calculate the force
constant k for this molecule. (B) What is the maximum classical amplitude of
vibration for this molecule in the v = 0 vibrational state ?
Ans: A) 1.85103 N/m B) 0.00479 nm
4. Consider a one-dimensional chain of alternating positive and negative ions. Show that
the potential energy associated with one of the ions and its interactions with the
rest of this hypothetical crystal is

e2
U(r ) = − k e 
r
where the Madelung constant is  = 2 ln 2 and r is the inter-ionic spacing.
Hint: Use the series expansion
x2 x3 x4
ln (1 + x ) = x − + − + ...
2 3 4
5. Each atom of gold (Au) contributes one free-electron to the metal. The concentration of free-
electron in gold is 5.90 x 1028/m3. Compute the Fermi Energy of gold.
Ans: 5.53 eV
6. Sodium is a monovalent metal having a density of 971 kg/m 3 and a molar mass of
0.023 kg/mol. Use this information to calculate (a) the density of charge carriers
and (b) the Fermi energy.
Ans: 2.54 x 1028/m3, 3.15 eV
7. Calculate the energy of a conduction electron in silver at 800 K, assuming the probability
of finding an electron in that state is 0.950. The Fermi energy is 5.48 eV at this
temperature.
Ans: 5.28 eV
8. Show that the average kinetic energy of a conduction electron in a metal at zero
K is (3/5) EF
Suggestion: In general, the average kinetic energy is
1
ne 
E AV = E N( E ) dE

where the density of particles


ne =  N( E ) dE
0
3 1
8 2 m 2
E dE
2
N( E ) dE =
h3  E − EF 
exp   + 1
 kT 

93
9. (a) Consider a system of electrons confined to a three-dimensional box. Calculate the
ratio of the number of allowed energy levels at 8.50 eV to the number at 7.00 eV. (b)
Copper has a Fermi energy of 7.0 eV at 300 K. Calculate the ratio of the number of
occupied levels at an energy of 8.50 eV to the number at Fermi energy. Compare
your answer with that obtained in part (a).
Ans: (a) 1.10 (b) 1.4610-25
10. Most solar radiation has a wavelength of 1 μm or less. What energy gap should the material
in solar cell have in order to absorb this radiation ? Is silicon (Eg= 1.14 eV) appropriate?
Ans: 1.24 eV or less; yes
11. The energy gap for silicon at 300 K is 1.14 eV. (a) Find the lowest-frequency photon that can
promote an electron from the valence band to the conduction band. (b) What is the wavelength
of this photon?
Ans: 2.7x1014 Hz, 1090 nm
12. A light-emitting diode (LED) made of the semiconductor GaAsP emits red light ( λ=
650nm). Determine the energy-band gap in the semiconductor.
Ans: 1.91 eV

13. Consider a semiconductor in the form of a rectangular strip of thickness 10 µm. Let
a current of 1 mA flow along its length and a transverse magnetic field of strength 1T
be applied across its thickness. If Hall voltage is 2mV, then calculate charge carrier
density.
Ans: 3.1 x 1023m-3
14. The Hall coefficient of certain Silicon specimen was found to be -7.35 x 105 m3C-1.
Calculate the charge carrier density. Mention type of the charge carrier.
Ans: 8.455 x 1022 m-3; electrons

94
 5 DIELECTRICS

Objectives:

• To learn polarization concepts in dielectric materials and their mechanisms.

• To study frequency and temperature effects on dielectric polarization behavior.
• To understand dielectric losses and breakdown mechanisms' impacts.
• To know about dielectric material applications and ferroelectric properties.

INTRODUCTION

In the realm of electrical engineering, dielectrics stand as a crucial class of materials, distinct
in their properties and applications. These materials do not conduct electricity like metals do.
Instead, when placed them in an electric field of sufficient magnitude, something interesting
happens. The positive and negative charges inside them move a little bit. That means the centres
of the positive charges are displaced slightly along the direction of the applied field and that of
the negative charges displaced in the opposite direction. This produces local electric dipole
throughout the material. An electric dipole is composed of two opposite charges of equal
magnitudes, +q and –q, separated by a certain distance 𝑟⃗ apart as shown in Figure 5.1. The
electric dipole moment (𝑝⃗) is defined as the total charge (q) of one kind (positive or negative,
as both are equal) multiplied by the distance (𝑟⃗) between the two kinds of charges i.e., 𝑝⃗ = q𝑟⃗.

Fig. 5.1: An electric dipole.

Dielectric materials are characterized by their non-conductivity, lacking free charge carriers
within them. When subjected to an electric field, dielectrics alter the field and themselves
undergo significant changes, enabling them to store electrical charges. For a material to be a
good dielectric, it must be an insulator. The function of an insulating material is to obstruct the
flow of electric current while that of a dielectric material is to store electrical energy. Thus,
insulating materials and dielectric materials differ in their functions. The dielectric material
may be polar or nonpolar.

95
Polar dielectrics: In this case of dielectrics the center of the gravity of the positive charges in
the molecule does not coincident with the center of gravity of the negative charges, and thus,
they possess a permanent electric dipole moment. When an electric field is applied all the
molecules in the polar dielectric almost align itself in the direction of the applied electric field.
Example of a polar dielectric is water.

Fig. 5.2: Polar dielectric

Non-polar dielectrics: In this case of dielectrics the center of gravity of positive charges
coincide with the center of gravity of negative charges, hence their dipole moment is zero.
When a non-zero electric field is applied all the molecules in the non-polar dielectric align
themselves in the direction of the applied electric field and produce net dipole moment.
Example of a non-polar dielectric is methane.

Fig. 5.3: Non-polar dielectric

POLARIZATION IN A DIELECTRIC MATERIAL

Polarization in a dielectric material refers to the process by which the material develops an
internal electric field when placed in an external electric field. This phenomenon arises due to
the alignment or reorientation of electric dipoles within the dielectric material. When an
external electric field is applied to a dielectric, it exerts forces on the electric charges within
the material, causing them to shift slightly. Positive charges tend to move in the direction of

96
the field, while negative charges move in the opposite direction. This displacement of charges
creates an induced electric dipole moment in each atom or molecule of the dielectric. As a
result, the dielectric becomes polarized, meaning that its overall electric field no longer aligns
perfectly with the external field. Instead, the induced dipoles within the material oppose the
external field to some extent. This polarization effect reduces the net electric field experienced
by the dielectric material.

Upon the application of external electric field, polarization can occur through various
mechanisms, including electronic (or atomic) polarization (due to the displacement of electron
clouds in the atom), ionic (or displacement) polarization (due to the displacement of ions
within the material), and orientational (or dipolar) polarization (due to the rotation of
permanent dipoles), which will be discussed in detail in section 5.3. The combined effect of
these mechanisms determines the overall polarization response of the dielectric material.
Polarization is a crucial concept in dielectric materials because it influences their electrical
properties, such as capacitance, permittivity, and energy storage capabilities. Understanding
polarization is essential for designing and optimizing the performance of devices and systems
that utilize dielectric materials, such as capacitors, insulators, and electrical transmission lines.

The important parameters which characterize the dielectric materials are described below:

Dielectric Constant (𝝐𝒓 ):

A dielectric is primarily characterized by its dielectric constant. Dielectric constant of a

dielectric is defined and measured as the ratio of capacitance of a capacitor containing the
dielectric medium to the capacitance of the same capacitor with air as the medium.
𝐶
𝜖𝑟 =
𝐶0
where C0 is the capacitance with air as the medium between the plates and C is the capacitance
with dielectric as medium. 𝜖𝑟 is called dielectric constant or relative permittivity. It is a
dimensionless quantity, which is always greater than unity in case of dielectrics, and it is
independent of the size or shape of the dielectric. In fact, 𝜖𝑟 gives the measure of the ability of
a substance to store electrical energy when placed in an electric field. At times another quantity
known as the permittivity of the medium (𝜖) is used. It is given by,
𝜖 = 𝜖0 𝜖𝑟

97
where 𝜖0 = 8.854 × 10-12 F/m represents the permittivity of free space. Permittivity is a material
property that affects the Coulomb force between two point charges in the material. Permittivity
of the medium is a measure of the degree to which a medium can resist the flow of charge.

⃗⃗⃗):
Dielectric Polarization (𝑷

The dielectric polarization (also called polarization or polarization density) 𝑃⃗⃗ at any point of
the dielectric is defined as the electric dipole moment per unit volume at that point. Polarization
is a macroscopic property of the material or in other words, polarization takes place in all the
molecules of a dielectric, that is, it is a bulk property. This causes the formation of an electric
dipole moment in the entire volume of the dielectric and in each separate polarizing particle
such as atom, ion, molecule, and so on and 𝑃⃗⃗ is given by,

𝑃⃗⃗ = ∑𝑖 𝑛𝑖 ⃗⃗⃗⃗
𝑝𝑖 = 𝑁𝑝⃗

where ni represents number of individual particles (atom, ion, molecules etc), pi is the dipole
moment of these particles, N is the number of particles per unit volume of the dielectric and p
is the net dipole moment of the dielectric.

Electric susceptibility (χ):

How easily a dielectric material can be polarized when subjected to an electric field is measured
by the parameter called electric susceptibility. Thus, the electric susceptibility indicates the
degree of polarization of a dielectric material in response to an applied electric field. In a
homogeneous isotropic dielectric material the polarization 𝑃⃗⃗ is proportional to the applied weak
electric field 𝐸⃗⃗ . Hence, the polarization is written as,

𝑃⃗⃗ = 𝜖0 𝜒𝐸⃗⃗

where 𝜖0 is the permittivity of free space and χ is the electric susceptibility of the material. Thus,
greater the electric susceptibility, the greater the ability of a material to polarize in response to
the applied electric field, and thereby reduce the total electric field inside the material (and
hence store energy).
The susceptibility 𝜒 is related to its relative permittivity 𝜖𝑟 (dielectric constant) as
𝜖𝑟 = 1 + 𝜒

⃗⃗⃗):
Electric displacement field or Displacement vector (𝑫

98
The electric displacement field is a vector field that describes the displacement effects of an
electric field on the charges within a dielectric material, such as polarisation charges or bound
charges. It is defined by the equation,
⃗⃗ = 𝜖0 𝐸⃗⃗ + 𝑃⃗⃗
𝐷
It has a unit of coulombs per square meter (C/m²). The electric displacement field has no real
physical meaning but is used for easier calculations involving dielectric materials.
Since 𝑃⃗⃗ = 𝜖0 𝜒𝐸⃗⃗ and 𝜖𝑟 = 1 + 𝜒 we have,

⃗⃗ = 𝜖0 𝐸⃗⃗ + 𝜖0 𝜒𝐸⃗⃗ = (1 + 𝜒)𝜖0 𝐸⃗⃗ = 𝜖𝑟 𝜖0 𝐸⃗⃗ = 𝜖𝐸⃗⃗

𝐷

Polarizability (α):

There is another important property connected with dielectrics, that is, polarizability.
Polarizability usually refers to the tendency of matter, when subjected to an electric field, to
acquire an electric dipole moment in proportion to that applied field. When the dielectric is
subjected to external electric field, an electric dipole moment is induced on every particle
(atom, ion, dipole), which is given by
⃗⃗⃗⃗= α𝐸⃗⃗
𝑝

where 𝑝⃗ is the induced dipole moment, 𝐸⃗⃗ is the electric field, and α is the constant of
proportionality, called the polarizability of that particle. Polarizability reflects the properties of
an individual particle of matter and not of a certain very large volume of it. It is a microscopic
electrical parameter of a dielectric. In cgs system, the polarizability α is expressed as cm3 and
its SI unit is Fm2. For anisotropic molecules, polarizability is different in different directions.

COMPONENTS OF POLARIZABILITY

Polarization of a dielectric takes place due to the polarizability of the dielectric medium on the
application of the electric field. There are three main components of polarizability:

Electronic (or atomic) polarizability (αel)

In all circumstances, the application of an electric field causes some distortion of the electronic
cloud of the atom relative to the nucleus. Hence electronic polarization results from the
displacement of the electron clouds of atoms with respect to heavy ‘fixed’ nuclei to a distance
that is less than the dimensions of the atoms. It occurs in all dielectrics for any state of
aggregation. The phenomenon is illustrated in Figure.

99
Fig. 5.4: Electronic polarization a) Atoms are not polarized in the absence of the electric field,
b) Electronic polarization results from the distortion of electron cloud by an applied electric
field.

When an external static electric field 𝐸⃗⃗ is applied across the dielectric, the atoms having
electron cloud which is assumed to be a spherical region of uniform charge of radius R, will
get polarised with electronic (or atomic) polarizability,

𝛼𝑒𝑙 = 4𝜋𝜖0 𝑅 3

On the other hand, when an alternating electric field of angular frequency ω is applied across
the dielectric then electronic (or atomic) polarizability is given by,

𝑍𝑒 2 ⁄𝑚
𝛼𝑒𝑙 (𝜔) =
(𝜔02 − 𝜔 2 )

where ω0 is the natural frequency of oscillation of electrons, m is the electron mass, e is the
electronic charge and Z is the atomic number.

The frequency 𝜔0 lies in the UV region. As 𝜔 → 𝜔0 , atoms of the dielectric starts absorbing
energy from the source and at 𝜔 = 𝜔0 , the maximum absorption of energy takes place at
natural frequency. This phenomenon is commonly called resonance absorption.

Ionic (or displacement) polarizability (αion)

Ionic polarizability αion is due to the displacement of adjacent ions of opposite sign. The cations
(positive ions) are displaced parallel to the local field, and the anions (negative ions) are
displaced in the opposite direction. These effects are most important in alkali halides and other
ionic solids.

100
 Fig. 5.5: Illustrating polarization of ions in the electric field 𝐸⃗⃗ .

The torque produced by an electric filed lines up the dipole parallel to the field at absolute zero
temperature. The field produces forces on the two charges of opposite sign so that the distance
between them is changed by some amount. The balance between the electrostatic force and the
interatomic force due to stretching or compression gives the value of the change in the distance
between two ions of opposite charge. From this change in the distance, the ionic dipole moment
and hence ionic polarizability αion can be calculated.

Let us treat the ions as rigid ions and by the application of electric field, the center of mass of
each unit cell is not altered. Let ⃗⃗⃗⃗⃗
𝑢+ and 𝑢
⃗⃗⃗⃗⃗
− be the displacement of the positive ions of mass

M+ and negative ions of mass M- respectively with respect to their equilibrium positions. Let,
1 1 1
+ 𝑀 = 𝑀 where M is reduced mass of ion pair.
𝑀+ −

If an alternating electric field 𝐸 = 𝐸0 𝑒 −𝑖𝜔𝑡 of angular frequency ω is applied along x-

direction. Then ionic polarizability,

𝑒 2 ⁄𝑀
𝛼𝑖𝑜𝑛 = 2
̅ − 𝜔2)
(𝜔

where 𝜔
̅ is the natural frequency of the lattice vibration.

𝑒2
If 𝜔 << 𝜔
̅ then 𝛼𝑖𝑜𝑛 ≅ 𝑀𝜔̅2

𝜔
̅𝑚𝑎𝑥 = 𝜔𝐷 is called Debye frequency, which is in the IR region. Most of the ionic solids
exhibit strong interaction in the IR region.

101
 Dipolar (or orientational) polarizability (αdip)

The orientation polarization is characteristic of polar dielectrics, which consist of molecules

having permanent dipole moment. Dipolar (or orientational) polarizability (αdip) occurs in
substances which have asymmetric molecules whose permanent dipole moments can be aligned
(or oriented in a specific direction) by the electric field. In the absence of external electric field,
the orientation of dipoles is random resulting in a complete cancellation of each other’s effect,
as illustrated in Fig. 5.6 (a). When the electric field is applied the molecular dipoles rotate about
their axis of symmetry to align with the applied field. In case of electronic and ionic
polarizations, the force due to the external field is balanced by a restoring force due to coulomb
attraction, but for orientation polarization, restoring forces do not exist. However, the dipole
alignment is counteracted by thermal agitation. The higher the temperature, the greater is the
thermal agitation. The dipoles can turn only through a small angle, as illustrated in Fig. 5.6 (b).

Fig. 5.6: Orientation polarization a) molecular dipoles are randomly oriented when E = 0 and
b) when the electric field E is applied the dipoles are partially aligned.

Even in case of liquids or gases, where molecules are free to rotate, a complete alignment
cannot be achieved due to the randomizing effect of the temperature T. Thus, orientation
polarization is strongly temperature dependent. This type of polarization occurs in gases,
liquids and amorphous viscous substances. In case of solids, the molecules are fixed in their
positions and their rotation is highly restricted by the lattice forces, leading to a great reduction
in their contribution to orientation polarization. Because of this reason, while the dielectric
constant of water is about 80, that of solid ice is about only 10. As the process of orientation
polarization involves rotation of molecules, it takes relatively longer time than the electronic
and ionic polarizations.

102
For a system of N permanent dipoles with dipole moment 𝑝⃗, subjected to an external electric
field 𝐸⃗⃗ , the dipolar (or orientational) polarizability is given by,

𝑝2
𝛼𝑑𝑖𝑝 =
3𝑘𝐵 𝑇

where kB is Boltzmann constant and T is the temperature.

Total Polarizability (tot):

The total polarization of a polar dielectric is given by

P = N(αel + αion + αdip)E

Hence, the total polarizability in a dielectric material is given by,

αtot = αel + αion + αdip

𝑒 2 ⁄𝑀 𝑝2
i.e., 𝛼𝑡𝑜𝑡 = 4𝜋𝜖0 𝑅 3 + (𝜔̅2−𝜔2) + 3𝑘
𝐵𝑇

It is possible for one or more of the contributions to the polarization to be either absent or
negligible in magnitude relative to the others. For instance, orientation polarization does not
exist in non-polar dielectrics. Similarly, ionic polarization will not be found in covalently
bonded materials. Electronic polarization will be negligible compared to orientation
polarization in polar dielectrics.

Usually, αion << αel, therefore αtot = αel + αdip

𝑝2
𝛼𝑡𝑜𝑡 = 𝛼𝑒𝑙 + 3𝑘
𝐵𝑇

This is known as Langevin-Debye equation and is of great importance to scientists in

interpreting molecular structure.

Space-charge polarization:

Space-charge polarization in dielectrics is the accumulation of charges at interfaces due to an

applied electric field. It occurs whenever there is accumulation of charge at an interface
between two materials or between two regions within a material. This process takes a longer
time and typically occurs at low frequencies. Space charge polarization is also known as
interfacial or migrational polarization. Key contributors to space-charge polarization are:

103
 a) Material heterogeneity, where differences in electrical conductivity and permittivity
cause charge carriers to accumulate at interfaces between regions with varying
properties.
b) Electrode effects, including differences in work functions and contact potentials, lead
to space-charge accumulation at the dielectric-electrode interface.
c) Defects and impurities, such as trapping sites and ionic impurities, also play a
significant role by providing locations where charges can accumulate.
d) Grain boundaries in polycrystalline materials act as barriers to charge movement,
causing accumulation. (Note: Grains refer to the individual crystalline regions in a
polycrystalline material. Grain boundaries are the interfaces between these grains
where the crystal structure changes direction.)

Fig. 5.7: a) Dielectric material sandwiched between the electrodes. b) Migration and
accumulation of positive charges at the interfaces (here negative charges are fixed ions).
c) Electrons and holes within grains drift and become trapped at the grain boundaries to produce
space-charge polarization.

FREQUENCY DEPENDENCE OF POLARIZATION

In many practical situations, dielectric materials are exposed to alternating electric field (ac
field, which changes direction over time). As the field direction reverses, the electric dipoles
within the dielectric must reorient themselves to align with the field. The ability of these dipoles
to follow the changing field determines the total polarization P of the dielectric. With the
increase in frequency, polarization of the dielectric material decreases not continuously but in
big steps and these steps lie in the microwave, infrared, and ultraviolet regions. The dependence
of Polarizability with frequency is shown in Fig. 5.8.

104
 Fig. 5.8: Frequency dependence of polarizability.

As shown in Figure 5.8, the polarizability of dielectrics varies significantly with the frequency
of the applied electric field. This frequency dependence can be understood by analysing the
response of different polarization mechanisms within the material. At low frequencies, all types
of polarization are possible, allowing dipoles enough time to fully align with the field. The
average time it takes for dipoles to adjust to the field direction is known as the relaxation time
() and its reciprocal is the relaxation frequency (ν). If the electric field frequency is higher
than the relaxation frequency, dipoles can't keep up with the changes i.e., the dipoles cannot
reverse fast enough. Different types of polarizabilities become prominent in different frequency
ranges because of the relaxation times involved in different kinds of polarizabilities. Typically,
the frequency dependence of polarizability in dielectrics is characterized by four distinct
regions:

Low-Frequency (Static to Radio Frequency) region: At low frequencies, up to the radio

frequency (RF) range, dielectric materials exhibit all types of polarization namely, electronic,
ionic, dipolar and space-charge polarization. The polarizability in this range is relatively stable
and high because the dipoles within the dielectric have ample time to align with the oscillating
electric field. The response time of the dipoles is much shorter than the oscillation period of
the applied field, leading to a consistent polarization effect. Consequently, the dielectric
constant remains relatively high and nearly frequency-independent in this range.

105
Ultra-High Frequency (UHF) to Microwave Range: As the frequency increases into the
ultra-high frequency (UHF) and microwave ranges, dipolar relaxation processes begin to
dominate. In this frequency range, the polarizability starts to decrease because the dipoles
cannot reorient quickly enough to follow the rapidly oscillating field. This results in a decrease
in the dielectric constant.

Infrared (IR) Region: In the infrared region, the polarizability of dielectrics continues to
decrease. Ions do not follow the oscillations applied electric field, and they start to relax. In
this region, the oscillating electric field's frequency matches the natural vibrational frequencies
of the molecules within the material. These vibrations absorb energy efficiently, leading to
significant changes in the polarization state. The sharp peaks in polarizability in the IR region
are often due to vibrational resonances of the molecules.

Ultraviolet (UV) Region: At ultraviolet frequencies, electronic polarization becomes the

dominant mechanism. The polarizability significantly decreases because the electric field
oscillates too rapidly for the electrons to respond fully. In this region, the polarizability is
characterized by sharp peaks corresponding to electronic transitions within the material. These
peaks occur because the energy of the applied electric field matches the energy required to
excite electrons from lower energy states to higher energy states, leading to significant changes
in the electronic configuration and, consequently, the polarizability of the material. In this
optical region, the material's relative permittivity is equal to the square of its refractive index
i.e., 𝜀𝑟 = 𝑛2 .

Beyond the ultraviolet range, the electron cloud too fails to follow the field alternations and
electronic contribution to the polarization ceases. Consequently, the total polarization becomes
zero and the relative permittivity approaches unity i.e., 𝜀𝑟 = 1. Thus, polarizability and in turn
dielectric constant of the material changes enormously with the frequency of the applied
electric field. For example, water has a high static dielectric constant of about 80 at low
frequencies, but it decreases to 1.9 in the optical frequency region.

TEMPERATURE DEPENDENCE OF POLARIZATION

The electronic and ionic polarization do not depend on temperature and remain constant at all
temperatures. However, the orientation polarization is inversely proportional to the
temperature and decreases as the temperature increases.

We have, P = N(αel + αion + αdip)E

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 𝑁𝑝2 𝐸
i.e., 𝑃 = 𝑁(𝛼𝑒 + 𝛼𝑖 )𝐸 + 3𝑘
𝐵𝑇

𝑁𝑝2
𝑆𝑙𝑜𝑝𝑒 =
3𝑘𝐵
P

N(e+i)

1
𝑇

Fig. 5.9: The variation of total polarization as a function of 1/T.

For a particular electric field E, if polarization P is plotted as function of 1/T, a straight line
will be obtained, as shown in Fig. 5.9. The intercept of the line with y-axis at 1/T = 0 gives the
value of N(e+i) from which (e+i) can be evaluated. The dipole moment p can be computed
from the slope of the straight line, knowing the value of N, the number of molecular dipoles
per cubic meter.

LOCAL FIELD (OR INTERNAL FIELD) IN A SOLID DIELECTRIC MATERIAL

It is clear that in solids a molecule or atom experiences not only the external electric field, but
the electric fields produced by the dipoles as well. As a result of the long range of Coulomb
forces, the contribution from these dipoles cannot be neglected. This resultant electric field is
called local field and is responsible for polarizing individual molecules or atoms of solids.
When a dielectric specimen is kept in an electric field ⃗⃗⃗⃗⃗
𝐸0 , the induced polarization field ⃗⃗⃗⃗⃗
𝐸1 acts
in such a way as to decrease the average field in the dielectric. In general, the induced polarized
charges are non-uniform and therefore, the original field is modified differently at different
portions of the specimen. Let us consider the situation (Fig. 5.10) in which an ellipsoidal
dielectric is kept in a uniform electric field ⃗⃗⃗⃗⃗
𝐸0 with its principal axis along the field direction.

107
 Fig. 5.10: Ellipsoidal dielectric is kept in an uniform electric field.

In this case the induced polarized charges produce a uniform electric field which is exactly
opposite to the original field, this is called depolarizing field. Thus, electric field at a point A
in the ellipsoid (shown in the figure) depends on :
a) Applied electric field ⃗⃗⃗⃗⃗
𝐸0
b) Depolarizing field due to surface charges ⃗⃗⃗⃗⃗
𝐸1
c) Effect of all dipoles in the solid.

The net effect of (a) and (b) will be same throughout the material, they are together called as
macroscopic field. Hence, macroscopic field 𝐸⃗⃗ = ⃗⃗⃗⃗⃗
𝐸0 + ⃗⃗⃗⃗⃗
𝐸1 .
The depolarizing field ⃗⃗⃗⃗⃗
𝐸1 is directly proportional to polarization 𝑃⃗⃗ and it is given by the
𝛾𝑃 ⃗⃗
formula, ⃗⃗⃗⃗⃗
𝐸1 = − 𝜖 , where γ is the depolarizing factor, 𝜖0 is the permittivity of free space
0

and the negative sign indicates that ⃗⃗⃗⃗⃗

𝐸1 is opposite to 𝑃⃗⃗.

𝛾𝑃⃗⃗
Thus, macroscopic field, 𝐸⃗⃗ = ⃗⃗⃗⃗⃗
𝐸0 − 𝜖
0

Hence macroscopic field 𝐸⃗⃗ is the net electric field at a particular site inside the solid, and this
field along with contributions from all dipoles is known as local field 𝐸⃗⃗𝑙𝑜𝑐 .

Following Lorentz method (Refer Appendix-I), the electric field contributions from all dipoles
𝑃⃗⃗
is given by .
3𝜖0

Hence, the local electric field 𝐸⃗⃗𝑙𝑜𝑐 is written as,

⃗⃗
𝑃
𝐸⃗⃗𝑙𝑜𝑐 = 𝐸⃗⃗ + 3𝜖
0

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This equation is known as Lorentz equation, and is valid for cubic crystals and non-crystalline
materials, such as glasses. It does not apply to dipolar dielectrics in which the local field can
be quite complicated.

CLAUSIUS-MOSSOTTI EQUATION

The Clausius-Mossotti equation provides a bridge between the dielectric constant (macroscopic
parameter) of a material and the polarizability (microscopic parameter) of its constituent
molecules, atoms or ions. This is crucial for understanding how the internal structure and
composition of a material influence its overall electrical behaviour. It was derived using
macroscopic electrostatics by the Italian physicist Ottaviano Fabrizio Mossotti in 1850 and
independently by Rudolf Clausius in 1879.

The polarizability αi of ith atom is defined in terms of the local electric field 𝐸⃗⃗𝑙𝑜𝑐 at the atom
and the dipole moment 𝑝⃗ as,
𝑝⃗ = 𝛼𝑖 𝐸⃗⃗𝑙𝑜𝑐

If there are N atoms (or molecules) per unit volume of the solid and there are Ni atoms (or
molecules) having polarizability αi then 𝑁 = ∑𝑖 𝑁𝑖

Now, Polarization 𝑃⃗⃗ = ∑𝑖 𝑁𝑖 ⃗⃗⃗⃗

𝑝𝑖

= ∑𝑖 𝑁𝑖 𝛼𝑖 𝐸⃗⃗𝑙𝑜𝑐 𝑖

where 𝐸⃗⃗𝑙𝑜𝑐 𝑖 is the local field at the atoms of the ith species.

𝑃 ⃗⃗
Thus, 𝑃⃗⃗ = ∑𝑖 𝑁𝑖 𝛼𝑖 (𝐸⃗⃗ + 3𝜖 )
0

1
𝑃⃗⃗ (1 − 3𝜖 ∑𝑖 𝑁𝑖 𝛼𝑖 ) = 𝐸⃗⃗ ∑𝑖 𝑁𝑖 𝛼𝑖
0

𝐸⃗⃗ ∑𝑖 𝑁𝑖 𝛼𝑖
𝑃⃗⃗ = 1
(1− ∑ 𝑁𝛼)
3𝜖0 𝑖 𝑖 𝑖

Now, relative permittivity or dielectric constant, 𝜖𝑟 = 1 + 𝜒, where χ is the electrical

𝑃⃗⃗
susceptibility of the dielectric and is given by, 𝜒=𝜖 ⃗⃗
0𝐸

1
∑ 𝑁𝛼
𝜖0 𝑖 𝑖 𝑖
i.e., 𝜒= 1 ≡ 𝜖𝑟 − 1
(1− ∑ 𝑁𝛼)
3𝜖0 𝑖 𝑖 𝑖

109
 1
∑ 𝑁𝛼
𝜖0 𝑖 𝑖 𝑖 3
Now, 𝜒+3= 1 +3= 1 ≡ 𝜖𝑟 + 2
(1− ∑ 𝑁𝛼) (1− ∑ 𝑁𝛼)
3𝜖0 𝑖 𝑖 𝑖 3𝜖0 𝑖 𝑖 𝑖

Thus,

𝜒 𝜖𝑟 − 1 1
= = ∑ 𝑁𝑖 𝛼𝑖
𝜒 + 3 𝜖𝑟 + 2 3𝜖0
𝑖

This is famous Clausius-Mossotti relation between the dielectric constant (𝜖𝑟 ) and the
polarizability (α) for the crystal structures which follow the Lorentz local field relationship.
If α is the average polarizability of the atom or molecule then the polarizability per unit volume
is ∑𝑖 𝑁𝑖 𝛼𝑖 = 𝑁𝛼
Hence,
𝜖𝑟 − 1 𝑁𝛼
=
𝜖𝑟 + 2 3𝜖0
Further, in most of the optical materials and dielectrics, the dielectric constant is equal to the
square of its refractive index i.e., 𝜀𝑟 = 𝑛2 .
Hence,
𝑛2 − 1 𝑁𝛼
=
𝑛2 + 2 3𝜖0
This is known as Lorentz-Lorentz relation.
DIELECTRIC LOSS AND LOSS TANGENT

When an electric field, either AC or DC, is applied to a conductor, it loses some electrical
energy as heat, which is called power loss or I²R loss. In conductors, this loss is significant. In
dielectrics (insulating materials), DC voltage causes very little power loss due to their high
resistance. However, under AC voltage, the dipoles in the dielectrics tend to follow the field,
flipping back and forth as the field reverses its direction during each cycle. Dipoles experiences
some friction due to their collision with other molecules in the system. This means that some
energy is absorbed from the field, and appears in the form of heat, which raises the temperature
of the substance. Thus, when a dielectric material is subjected to an alternating voltage, the
electrical energy is absorbed by the material and is dissipated in the form of heat. This
dissipation of energy is called dielectric loss.

In the case of an ideal dielectric (perfect insulator), polarization is complete during each cycle
and there is no consumption of energy and the charging current leads the applied voltage by
90º. But for commercial dielectric (lossy dielectric), the phase angle is less than 90º by an angle

110
 and is called dielectric loss angle. Tan is taken as measure of dielectric loss and is known as
loss tangent (tan ). It represents the electrical power lost which is often in the form of heat.
Hence tan  is also called dissipation factor.
The lossy dielectric can be described with the aid of a complex relative permittivity 𝜀𝑟∗ given
by,
𝜀𝑟∗ = 𝜀𝑟′ − 𝑗𝜀𝑟"
where the real part 𝜀𝑟′ is called dielectric constant, which represents the stored energy and the
imaginary part 𝜀𝑟" is called dielectric loss, which represents the lost energy.
The dissipation factor or loss tangent (tan ) can also be written as,
𝜀𝑟"
tan 𝛿 =
𝜀𝑟′
The product 𝜀𝑟′ tan 𝛿 is known as the loss factor.

DIELECTRIC BREAKDOWN AND DIELECTRIC STRENGTH

When an electric field is applied to a dielectric and the electric field strength is continuously
increased then a stage will be reached where the field separates the electron cloud into single
electrons. Hence free electrons are generated so that the dielectric become a conductor. That
means when higher electric fields are applied, the insulator starts conducting and behaves as a
conductor. In such conditions, dielectric materials lose their dielectric properties. This
phenomenon is known as Dielectric Breakdown. It is an irreversible process, and it leads to the
failure of dielectric materials.

The dielectric strength of a material is a measure of the ability of that material to withstand
high electric fields. Maximum electric field that a dielectric can withstand before dielectric
breakdown occurs is called dielectric strength. Hence, dielectric strength is the limiting electric
field intensity, above which a breakdown occurs and the charge storage property of the
dielectric disappears.

APPLICATIONS OF DIELECTRIC MATERIALS

Dielectric materials can be solids, liquids, gases, and vacuum. Solid dielectrics are highly used
in electrical engineering. Some examples of solid dielectrics are porcelain, ceramics, glass,
paper, etc. Dry air, nitrogen, sulfur hexafluoride and the oxides of various metals are examples
of gaseous dielectrics. Distilled water, transformer oil are common examples of liquid
dielectrics.

111
Dielectric materials are crucial for two main applications: as insulators and in capacitors. For
insulation, dielectrics should have a low dielectric constant, minimal dielectric loss, high
resistance, and strong dielectric strength. They also need to be chemically stable, resist
moisture, and possess suitable mechanical properties.

Capacitors store energy using two metal plates separated by a dielectric. Based on the types of
dielectric used, capacitors are classified as:

1. Paper Capacitors: Use thin paper soaked in oil or wax.

2. Plastic Capacitors: Utilize films of polyester, PTFE, etc.

3. Ceramic Capacitors: Employ ceramic materials like steatite or barium titanate.

4. Mica Capacitors: Use laminated mica sheets.

5. Glass Capacitors: Thin glass plates with aluminium foil.

6. Electrolytic Capacitors: Have a metal anode with an oxide film dielectric and an
electrolyte as the cathode.

Liquid dielectrics (like mineral oil and synthetic oil) are used in transformers for insulation and
cooling. These materials help to transfer power between circuits and keep transformers from
overheating. They insulate high and low voltage windings and the transformer core, preventing
electrical short circuits that could cause failures or fires. By maintaining temperature and
providing high dielectric strength, these materials ensure reliable operation and prolong the
transformer's life by preventing thermal and electrical damage.

FERROELECTRIC MATERIAL

Ferroelectric materials constitute a very important group of dielectrics. They are anisotropic
crystals that exhibit spontaneous polarization. Spontaneous polarization is the dielectric
polarization, which occurs under the action of the internal processes and without the application
of external electric field. In the absence of an electric field, if the centers of gravity of the
positive and negative charges do not coincide, it results in a resultant dipole moment, which is
the cause of spontaneous polarization. The materials, which possess special structure that
permits spontaneous polarization, are called ferroelectrics and the phenomenon of spontaneous
polarization is called ferroelectricity. Ferroelectricity was first discovered in Rochelle salt
(NaKC4H4O6 ⋅ 4H2O). Barium titanate, potassium phosphate, and potassium niobate are other
examples of ferroelectrics.

112
The main characteristics of ferroelectric substances are as follows:

1. They possess very high values of relative permittivity r ranging from 1,000 to 10,000.

2. The static dielectric constant of ferroelectric material changes with temperature

according to the relation:
𝐶
𝜖𝑟 =
𝑇 − 𝑇𝑐
This equation is called Curie-Weiss law. Where C is a constant called Curie’s constant
and TC is the Curie temperature.

3. They possess spontaneous electric polarization, that is, polarization without the help
of an external electric field. However, the spontaneous polarization occurs only within
a definite temperature range and up to the Curie temperature TC.

4. In a ferroelectric, the dielectric polarization depends nonlinearly on the applied electric

field. In ordinary dielectrics, the polarization varies linearly with the applied electric
field. Because of this, ferroelectrics are known as nonlinear dielectrics. They exhibit
hysteresis under the action of an alternating voltage. The polarization versus electric
field curve is known as a ferroelectric hysteresis loop which is shown in Fig. 5.11.

Fig. 5.11: A typical ferroelectric hysteresis loop.

Applications of ferroelectric materials:

Ferroelectric materials are useful for fabricating capacitors with tunable capacitance. These
capacitors are used in medical ultrasound devices to create and detect ultrasound waves for
body imaging, in high-quality infrared cameras to sense tiny temperature changes, in fire

113
sensors, sonar, vibration sensors, and diesel engine fuel injectors. The unique hysteresis
property of ferroelectric materials allows them to store memory, making them ideal for
ferroelectric RAM in computers and Radio-frequency identification (RFID) cards.

QUESTIONS

1. What is meant by electric dipole moment?

2. What are polar and non-polar dielectrics?
3. Explain polarization in a dielectric material.
4. What do you understand by dielectric constant? Define dielectric susceptibility.
5. Define dielectric polarization and polarizability of a dielectric.
6. Explain displacement vector in dielectrics.
7. With relevant mathematical expressions explain electronic, ionic and orientational
polarizabilities.
8. Discuss the frequency dependence of various polarization processes in dielectric
materials.
9. What is space-charge polarization? Explain.
10. Discuss the effect of temperature on electronic, ionic and orientational polarization.
11. What is meant by local field in a dielectric and how it is calculated for a cubic structure.
12. Derive Clausius-Mosotti relation in dielectrics.
13. Write a note on dielectric loss. Explain loss tangent and loss factor.
14. Explain dielectric breakdown and dielectric strength.
15. What is the role of dielectrics in capacitors and transformers?
16. What is meant by spontaneous polarization?
17. What is ferroelectricity? Mention the main characteristics of ferroelectric materials.
18. Mention the applications of ferroelectric materials.

PROBLEMS

1. In a drop of water of radius 10-3m, the molecular dipoles are pointed in the same direction.
If the dipole moment of the water molecule is 6  10-30C.m, calculate the polarization.
Molecular weight of water (H2O) is 18 and density of water (H2O) is 1000 kg/m3.
(Ans: 8.40 × 10−10 C/m2)

2. Two parallel plates have equal and opposite charges. They are separated by a
dielectric material with dielectric constant 3. If the electric field intensity in the

114
 dielectric is 106 V/m, calculate the polarization in the dielectric. Permittivity of free
space 𝝐𝟎 = 𝟖. 𝟖𝟓𝟒 × 𝟏𝟎−𝟏𝟐 m-3 kg-1 s4 A2. (Ans: 𝟏𝟕. 𝟕 × 𝟏𝟎−𝟔 C/m2)

3. When NaCl crystal is subjected to an electric field of 50 V/cm, the resulting polarization
is 2.215 × 10-7 C/m2. Calculate relative permittivity of NaCl. (Ans: 6.006)

4. Calculate the induced dipole moment per unit volume (i.e., polarization) of helium gas
when it is placed in a field of 6  105 V/m. The polarizability of helium is 0.18  10-40 Fm2
and the concentration of helium atom is 2.6  1025 /m3. Also calculate the separation of
positive and negative charges in each atom.
(Ans: 2.808  10-10 C/m2, 3.375 × 10−17 𝑚)

5. If all the Carbon atoms of diamond are polarized alike, and produce a polarization
1.32  10-5 C/m2, calculate the shift of the center of negative cloud of 6 electrons on each
atom from the nucleus. The density of Carbon is 3500 kg/m3 and its atomic weight is 12.
(Ans: 7.82 × 10−17 𝑚)

6. The capacitance of a parallel plate capacitor increases from 0.085F to 0.195F when
a sheet of polythene is placed between the plates. Determine the dielectric constant
of the polythene. (Ans: 2.29)

7. Assuming that the polarizability of Kr atom is 2.18  10-40 Fm2, calculate its dielectric
constant at 0ºC and 1 atmosphere pressure. Given : 1 mole of gas occupies 22.4 L at NTP.
(Ans: 1.00066)

8. Calculate the electronic polarizability of argon atom. Given r = 1.0024 at NTP and N = 2.7
× 1025 atoms/m3. (Ans: 7.9 × 10-40 F.m2)

9. The number of atoms in hydrogen gas is 9.8 × 1026 atoms/m3. The radius of hydrogen atom
is 0.053 nm. Calculate its electronic polarizability and relative permittivity.
(Ans: 1.657 × 10-41 F.m2, 1.0018.)

10. The atomic weight and density of sulphur are 32 and 2.08 gm/cm 3 respectively. The
electronic polarizability of the atom is 3.28 × 10-40 F.m2. If sulphur solid has cubic
symmetry, what will be its relative permittivity? (Ans: 3.8)

11. Find the total polarizability of CO2, if its susceptibility is 9.85  10-4. Density of CO2 is
1.977 kg/m3 and its molecular weight is 44. (Ans: 3.22 × 10−40 𝐹𝑚2 )

115
12. Assuming that there are 1027 molecules/m3 in HCl vapour, calculate the orientational
polarization at room temperature if the vapour is subjected to an electric field of 106 V/m.
The dipole moment of HCl molecule is 3.46  10-30 C.m.
(𝐴𝑛𝑠: 9.64 × 10−7 𝐶/𝑚2)

13. The polarizability of NH3 molecule is found experimentally by the measurement of

dielectric constant as 2.42  10-39 Fm2 at 309K and 1.74  10-39 Fm2 at 448K
respectively. Calculate for each temperature the polarizability due to permanent
dipole moment and due to deformation of molecules.
(Ans: 𝜶𝒆𝒍 = 𝟐. 𝟐𝟖 × 𝟏𝟎−𝟒𝟎 𝑭𝒎𝟐 , 𝜶𝒅𝒊𝒑(𝟑𝟎𝟗) = 𝟐. 𝟏𝟗 × 𝟏𝟎−𝟑𝟗 𝑭𝒎𝟐 , 𝜶𝒅𝒊𝒑(𝟒𝟒𝟖) =
𝟏. 𝟓𝟏 × 𝟏𝟎−𝟑𝟗 𝑭𝒎𝟐 )

14. A dielectric material has r = 4.94 and n2 = 2.69. Calculate the ratio between
electronic and ionic polarizability of this material. (Ans: 1.73)

APPENDIX-I

Lorentz method of calculating local electric field ⃗⃗⃗⃗⃗⃗⃗⃗

𝐄𝐥𝐨𝐜 :

According to this method, construct a sphere centered at A with the atom for which the local
field must be calculated at the center. Convenient radius for the sphere is chosen such that large
number of dipoles exist inside the sphere. Assume that the sphere has been scooped out of the
material, leaving a cavity inside the solid with point A as center. The dielectric has been
uniformly polarized by applying uniform electric field and the dielectric medium outside the
cavity is assumed to be homogenous (continuum) while inside actual structure of the material.

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Now,

Electric field at point A Electric field at point A

Electric field at point A due to all dipoles due to all dipoles
[ due to all dipoles ] = outside the spherical + inside the spherical
in the solid ⃗⃗⃗⃗⃗2 ) ⃗⃗⃗⃗⃗3 )
[ cavity (𝐸 ] [ cavity (𝐸 ]

i.e., Total electric field at point A, ⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗

𝐸𝑙𝑜𝑐𝑎𝑙 = ⃗⃗⃗⃗⃗
𝐸0 + ⃗⃗⃗⃗⃗
𝐸1 + ⃗⃗⃗⃗⃗
𝐸2 + ⃗⃗⃗⃗⃗
𝐸3

= 𝐸⃗⃗ + ⃗⃗⃗⃗⃗
𝐸2 + ⃗⃗⃗⃗⃗
𝐸3

Let θ denote the polar angle with respect to the axis that is parallel to the polarization direction.
Let ds be the surface element and 𝑛̂ be unit normal (|𝑛̂| = 1) at the surface element ds. Radius
of the sphere is a. Now, the surface density of charges on the elemental area ds is,

𝜎 = −𝑃⃗⃗. 𝑛̂ = −𝑃 cos 𝜃

Area of the annular ring which subtends a semi-vertical angle dθ at point A is

𝑑𝑠 = 2𝜋𝑎 sin 𝜃 𝑎𝑑𝜃 = 2𝜋𝑎2 sin 𝜃 𝑑𝜃

Charge on the annular ring, 𝑑𝑞 = 𝜎 𝑑𝑠

= −𝑃 cos 𝜃 2𝜋𝑎2 sin 𝜃 𝑑𝜃

= −2𝜋𝑎2 𝑃 cos 𝜃 sin 𝜃 𝑑𝜃

The electric field at the point A due to the charges on the annular ring,

𝑑𝑞 2𝜋𝑎2 𝑃⃗⃗ cos 𝜃 sin 𝜃 𝑑𝜃 𝑃⃗⃗ cos 𝜃 sin 𝜃 𝑑𝜃

⃗⃗⃗⃗⃗2 =
𝑑𝐸 = − = −
4𝜋𝜖0 𝑎2 4𝜋𝜖0 𝑎2 2𝜖0

⃗⃗⃗⃗⃗2 perpendicular to the polarization vector 𝑃⃗⃗ and the

The components of the electric field 𝑑𝐸
electric filed resulted from the surface element ds of the ring distributed symmetrically with
respect to the axis of the cavity, cancel out each other, i.e., sinθ terms will cancel out. Thus
⃗⃗⃗⃗⃗2 parallel to the direction of 𝑃⃗⃗ i.e., 𝑑𝐸2 cos 𝜃 will contribute to the
only the component of 𝑑𝐸
net electric field. Therefore, total contribution of the annular ring at the point A to the electric
⃗⃗⃗⃗⃗2 cos 𝜃.
field = −𝑑𝐸

Hence the resultant electric field,

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 𝜋
⃗⃗⃗⃗⃗ ⃗⃗⃗⃗⃗2 cos 𝜃 𝑑𝜃
𝐸2 = − ∫0 𝑑𝐸

𝜋 𝑃⃗⃗ cos 𝜃 sin 𝜃𝑑𝜃

= − ∫0 (− ) cos 𝜃 𝑑𝜃
2𝜖0

𝜋 𝑃⃗⃗ cos2 𝜃 sin 𝜃𝑑𝜃

= ∫0 𝑑𝜃
2𝜖0

Take cos 𝜃 = 𝜇 then − sin 𝜃 𝑑𝜃 = 𝑑𝜇

𝑃 −1 ⃗⃗
⃗⃗⃗⃗⃗
𝐸2 = − 2𝜖 ∫1 𝜇 2 𝑑𝜇
0

1
𝑃⃗⃗ 𝜇3 𝑃⃗⃗ 2 𝑃⃗⃗
= 2𝜖 [ 3 ] = 2𝜖 [3] = 3𝜖
0 −1 0 0

𝑃⃗⃗
∴ ⃗⃗⃗⃗⃗
𝐸2 = 3𝜖 This is called Lorentz field.
0

Further, the electric field due to dipoles inside the spherical cavity depends on the crystal
structure. For an isotropic material or a material with cubic symmetry, the density of charges
inside the sphere is equal to zero. Hence ⃗⃗⃗⃗⃗
𝐸3 = 0.

Thus, ⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗
𝐸𝑙𝑜𝑐𝑎𝑙 = 𝐸⃗⃗ + ⃗⃗⃗⃗⃗
𝐸2 + ⃗⃗⃗⃗⃗
𝐸3 = 𝐸⃗⃗ + ⃗⃗⃗⃗⃗
𝐸2

⃗⃗⃗
i.e., ⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗
𝑬𝒍𝒐𝒄𝒂𝒍 = ⃗𝑬 ⃗⃗ + 𝑷
𝟑𝝐 𝟎

This equation is known as Lorentz equation.

This equation is valid for cubic crystals and non-crystalline materials, such as glasses. It does
not apply to dipolar dielectrics in which the local field can be quite complicated.

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 6 INTRODUCTION TO NANOSCIENCE

OBJECTIVES:

• To understand the concept of nanoscience.

• To comprehend the concept of quantum confinement.
• To get an insight into the preparation techniques
• To learn about advanced engineering materials.

INTRODUCTION

The concept of nanostructures and nanotechnology dates back to the history of the Nobel
Laureate Richard Feynman’s famous lecture in 1959 where he speculated the possibility of
manoeuvring things atom by atom. He proudly said, “There is plenty of room at the bottom”.
By this sentence, he strongly pointed out that there is a lot of scope and application of materials
at very small scale, i.e., at atomic or molecular level. Why cannot we write the entire 24
volumes of the Encyclopaedia Britannica on the head of a pin? One may wonder what it is so
special at the nanoscale? The answer to these questions is against the very notion that specific
physical properties of a given material are the characteristic of the material itself and are
irrespective of their size. This is no longer valid at the nanoscale. There will be a drastic change
in properties which are counter-intuitive and unbelievable. Gold, the yellow metal, is no more
yellow in any size or dimension. It may be purple red and orange. CdS under colloidal solution
may yield a rainbow spectrum of colour. Ceramic oxides are not always brittle. Nanoceramics
are ductile and malleable. What sounded as scientific fantasy or myth at that time, today has
turned into reality. Nanoscience and technology cut across disciplines without boundary.

For physicists and chemists, nano means in the range of dimension of a few atoms and
molecules. For biologists, the visualization is to the dimension of the size of a DNA or to the
scale of a cell. Scientists have now devised techniques to prepare nanoparticles which have
peculiar properties. Nanotechnology is now a portal opening onto a new world. This chapter
will provide a brief look at nanoscale and its visualization.

The building block of Carbon 60 (C60) molecule is a truncated icosahedron with 60

vortices and 32 faces. Among 32 faces, 12 are pentagons and 20 are hexagons. All the rings
are fused and the double bonds are conjugated. The combination of pentagon and hexagon is
very necessary as only hexagons like graphite cannot be folded up into a sphere. The basic

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requirement here is that the structure must be closed perfectly without gaps and overlaps. The
Buckministerfullerene has high symmetry. It is very easy to produce and most popularly
applied in a variety of fields ranging from Physics, Chemistry, Biology and Mathematics. The
new field of carbon chemistry emerged from the discovery of C60. The other two cousins of
zero-dimensional (0D) fullerene are, one-dimensional (1D) carbon nanotube (CNT) and two-
dimensional (2D) graphene.

Figure 6.1: Buckministerfullerene (Bucky ball)

Figure 6.2 : Representation of a single and multi walled nanotubes

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Figure 6.3 Graphene, a single layer of atoms arranged in a two-dimensional honeycomb lattice
nanostructure.

Graphene:

Graphene is a 2D nanomaterial possessing several distinct properties. Graphite can be viewed

where a number of 2D graphene crystals are weakly coupled together. Here carbon atoms are
arranged in planner and hexagonal form. It has a honeycomb structure and it acts as a precursor
for other members of carbon family like graphite, CNT and fullerene. Graphene sheets are held
together by van der Waals forces. Graphene has high spring constant of the order 1-5 N/m and
its Young’s modulus is of 0.5 TPa. These high values make graphene strong and rigid and helps
in using graphene as pressure sensor and resonators. The thermal conductivity of graphene is
100 times larger than that of graphite.

NANOSCIENCE AND NANOTECHNOLOGY

Nanoscience is the study of the phenomenon and manipulation of materials at nanoscale where
properties differ significantly from those at larger scale. A ten centimeter piece of any material,
say, copper would have similar properties as a one centimeter piece, or even a one millimeter
piece. However, at the other extreme, one or two isolated atoms of copper would show quite
different properties. Some bulk properties of matter lose their identity while others show a
drastic change in the context of atoms and molecules. The properties of nanoparticles are
therefore strongly dependent on the number of atoms or size of the cluster. Nanotechnology
deals with the design, characterization, production and application of structures, devices by
controlling the shape and size of the material at nanometer scale. Size effects constitute a
peculiar and fascinating aspect of nanomaterials. Nanoscience and nanotechnology explore and
benefit from quantum phenomenology in the ultimate limit of miniaturization. At length scales
comparable to atoms and molecules, quantum effects strongly modify properties of matter like
“colour”, reactivity, magnetic or electrical and other physical properties. The drastic change in
properties make nano a thrust area or driving force for developing high performance, low cost,
miniaturized solid-state devices. Nature also mimics nanoscience, for example, the minute
structures that make up the wings of a butterfly, a peacock feather, spider thread and a lotus
leaf. To be more specific, on the properties front, we have the following amazing properties:
(i) 6 nm copper is 5 times as hard as the bulk copper (ii) Nanoceramics are ductile and malleable
whereas bulk ceramics are rigid (iii) Nano size titanium sinters at lower temperature (600 °C),

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whereas bulk titanium sinters at 1400 °C (iv) Rutiles becomes ductile in the nano form (v)
particles of size 10–30 nm cannot scatter visible light, hence all particles of this size, no matter
what they are made of, are transparent (vi) different sized nano CdSe exhibit different colours
– a boon for band gap engineers; this is due to the quantum size effect. (vii) Electrical insulators
at nanosize conduct due to tunnelling current. (Viii) 3 nm CdS melts at 700 K compared to
bulk CdS at 1678 K.

Other wonders of nanoscience include: (i) scratch resistance optical glass, (ii) dirt repellent
trains, (iii) ceramic motor car engines and tools, (iv) cancer treatment due to targeted drug
delivery and (v) corrosion protecting surface. The widespread use of nanotechnology is due to
(i) small scale miniaturization (ii) faster and cheaper manufacture, (iii) higher reliability, (iv)
lower cost nanoelectronics and many others.

SURFACE TO VOLUME RATIO

It is well known that finer particles are more reactive than larger particles. Most common
examples are: fine sugar dissolves faster, fine coal particles burn stronger than bigger size. This
may be the reason why many Ayurvedic medicines are prepared after extensive grinding and
compounding. Homeopathic medicines are taken in the form of micro fine globules. The high
reactivity results from the availability of a greater surface area by reducing the size either by
grinding, pounding, milling and so on.

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 Figure 6.4: Illustration of increased Surface to volume ratio as we move towards nano.

EXPLANATION:
(a) Consider a Cube with length of each side = 1m
Since it has six faces, its surface area = 6 sq.m.
Its volume = 1 cubic meter

Surface Area to Volume Ratio =SVR= 6/1 = 6

(b)If we further cut into 27 (=33) pieces,

then the surface area of each piece
= (1/3) x (1/3) x 6 = (2/3) sq.m.
But there are 27 pieces, total surface area
= (2/3) x 27 = 18 sq.m.

Surface Area to Volume Ratio = 18/1 = 18.

(C) If we further cut into 109 (=(103)3 pieces,

then the surface area of each piece
= (1/103) x (1/103) x 6 = (6 /106) sq.m.
But there are 109 pieces, total surface area
= (6 /106)) x 109 = 6000 sq.m.

Surface Area to Volume Ratio = 6000/1 = 6000.

Original Volume V0= 1m3 (Fixed)

N= 109 pieces
Volume of small cubes Vs= (a x a x a) = a3

V0 = N Vs

(1 m x 1m x 1m ) =109 (a x a x a)

implies a3 = 10-9 gives a = 10-3 or a = 1mm

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Since the surface atom possesses more energy than the bulk atoms, they are chemically more
active. Particles on surfaces are very sensitive to the environment and physical chemical
properties get modified. The new surface is more reactive and acquires special features.
Minerals get activated on grinding. Grinding and pounding of solids increase dissolution rates
not only because of increase in surface area; it also supports structural change, defects
formation and accumulation of mechanical energy that is released during dissolution. As the
size becomes smaller, the surface to volume ratio increases and this increase begins to go up
rapidly as one reaches a smaller size range. It is therefore clear that nanomaterials possess size
dependent properties.

This can be categorized as:

(i) Thermal properties (melting point, sintering temperature, etc)

(ii) Chemical properties (reactions, catalytic properties, activation energy and dissolution)
(iii) Mechanical properties (strength, adhesion, hardness, scratch resistance)
(iv) Optical properties (absorption, scattering, band gap)
(v) Electrical properties (transport, tunnelling, resistance)
(vi) Magnetic properties (nanomagnetism, superparamagnetism)

These properties make them useful as sensors, transducers, and pharmaceutical applications.
Surface area to volume ratio is very large for nanomaterials. To understand this concept,
consider a spherical material of radius r then:

Surface area of the sphere 4𝜋𝑟 2 3

= =
Volume of the sphere 4 3 𝑟
3 𝜋𝑟

As the size of the sphere decreases, the above ratio increases. Alternatively, if the material is
cubic, as it is divided into small cubes, then also the surface area to volume ratio increases.
Hence, the nanomaterials possess large value of surface area to volume ratio as compared to
the bulk material.

QUANTUM CONFINEMENT

The drastic change in surface to volume ratio at nanorange results in change of the atomic and
electronic structure as a result, electrical, optical, magnetic, and transport properties changes.
If the size is in the nanorange only in one dimension, it leads to a thin film, i.e., 2D structures
and 1D confinement; for example, graphene. The basic idea behind quantum confinement is
keeping an electron trapped in a small area. It is due to the fact that the energy available to the

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electron is less than the potential barrier it has to cross. This is similar to a particle in a well in
quantum mechanics, known as quantum well. The second arrangement is a nanorod or
nanotube (with 1D structures and 2D confinement), popularly known as a quantum wire. An
example of a quantum wire is the carbon nanotube (CNT). Three-dimensional graphite has a
3D structure and 0D confinement, whereas fullerene has a 0D structure and 3D confinement.
The most important finding of quantum confinement is the quantum dot. The quantum dot is
treated as an artificial atom or ‘super-atom’ having three-dimensional confinements and zero
dimensional structures. Like a particle in a box, the allowed energy levels can be varied at the
will and pleasure of the experimenter by changing the size of the quantum dot cluster. This in
turn changes the material properties such as electrical and non-linear optical properties and so
on. On excitation, a smaller dot emits light of higher energy and intensity or smaller
wavelength. Hence, the emitted light is blue. As the dot enlarges in size, the emitted light is of
lower energy or larger wavelength, moving towards red. This can be verified experimentally
by taking a colloidal suspension of CdSe core with ZnS shell quantum dots of varying sizes.
Larger and smaller quantum dots exhibit red and blue colours, respectively. Cadmium sulphide,
which is orange in colour in its bulk form, for example, keeps on changing colour through
different shades of yellow and becomes white as its cluster size changes. Optical property
depends strongly upon the particle shape and size. Bulk gold (Au) is yellowish in reflected
light, but a thin gold film appears blue in transmission. Further, this blue colour changes to
purple, red and finally orange as the particle size is reduced down to 3 nm.

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 Figure 6.5: Effects of dimensionality of quantization on the electronic density of states.

Figure 6.6 Change in the idealized density of state while reducing the system dimensionality
from a 3D bulk crystal to a 2D layer and, finally via a 1D wire to a 0D quantum dot.

QUANTUM DOTS (QDs)

• QDs are quite interesting as they enable the study of semiconductors on small length
scale.

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 • In these materials, photon of energy greater than band gap causes an electron to be
promoted to a conduction band leaving a positive hole in the valance band.

• The electron and hole as a pair constitutes an exciton [A bound electron-hole pair (in
their lowest energy states), when a photon is absorbed by a semiconductor is known as
an exciton].

• The maximum length of separation between an electron and hole at which they are still
linked by Coulombic attraction forces is called the exciton Bohr radius also referred
as de Broglie wavelength of electron.

• As the particle size approaches the exciton Bohr radius the charge carriers are confined
in three dimensions.

• This phenomenon known as quantum confinement causes the continuous band of the
bulk to split into discrete quantized levels.

In a quantum dot, the excitons are squeezed, leading to Quantum Confinement, such that the
size of the QD crystal is on the same order as the size of the exciton Bohr radius. This unique
size property causes the band of energies to turn into discrete energy levels.

Figure 6.7: Splitting of valence band and conduction band into discrete energy levels due to
quantum confinement effect.

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Bound exciton energy of a Quantum dot (EQD): When the size of the semiconductor crystal
is smaller than the Exciton Bohr radius, the Coulomb interaction energy (between electron-
hole pair) ‘EQD’ increases due the following reason:

PREPARATION TECHNIQUES

There are various ways to categorize the synthesis method of nanostructured materials.
Depending on the phase of the starting material, there are two classes: via gas phase and via
condensed phase. Alternate classifications may be physical or chemical and top down or
bottom up approaches. Further, the crystallographic structure of the precursor also decides the
method of fabrication. Amorphous materials on crystallization yield 3D nanostructured
materials. Polycrystals on ball milling undergo severe plastic deformation and give rise to
nanomaterials. Single atoms may be electrodeposited in various ways or condensed to give
clusters and subsequently, on compaction yield nanoparticles. It should be noted that there
exists certain overlap between the different methods. Gas phase synthesis is sophisticated and
expensive compared to condensed phase. This method gives more insight into understanding
the basic aspects of the nanostructure. Condensed phase synthesis deals with chemical vapour
deposition (CVD) and physical vapour deposition (PVD) from atomic or molecular precursors.
Bulk precursors under mechanical attrition, grinding and pounding, laser ablation, evaporation
and so on, supports nanofabrication.

The nanomaterials are synthesized using a number of methods. These methods are generally
classified into two categories, namely

1. Top-down process
2. Bottom-up process

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 Figure 6.8 : Top-down and bottom-up processes

Top down approach:

The top down approach is physics friendly and deals with taking a bulk material and is crushed
into fine particles using the processes such as mechanical alloying, laser ablation, sputtering
etc. to produce the nanostructure. The size limit that can be created depends on the tool.

The examples of top-down process are

1. Ball milling
2. Laser ablation
3. Sputtering
4. Arc evaporation
5. Electron beam evaporation
6. Photolithography, etc.

The disadvantages in this method include (i) imperfection or defects in the crystal, (ii)
crystallographic damage, and (iii) surface contamination.

APPLICATIONS OF NANOTECHNOLOGY

Nanomaterials are found in both biological systems and man-made structures. Nature has been
using nanomaterials for millions of years. The large surface area to volume ratio increases the
chemical activity. Nanomaterials have the following applications.

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(i) Microelectronics: In microelectronics, the reduction in size of electronic components
leads to faster switching times. Nanotechnology includes fabrication of nanowires used in
semiconductors. Porous silicon emits visible light, so it finds application in optoelectronics.
Quantum dot lasers are nanoscaled objects, they emit good-quality laser beam compared to
semiconductor laser diodes. They are cheaper and the emitted wavelength depends on the
diameter of the dot.

(ii) Machine tools: Some nanocrystalline materials such as tungsten carbide, tantalum
carbide and titanium carbide are harder than conventional materials; they are more wear-
resistant and erosion resistant, so they are used in cutting tools and drill bits. Nanocrystalline
silicon nitride and silicon carbide are used in the manufacturing of high-strength springs, ball
bearings and valve lifters because of their excellent physical, chemical and mechanical
properties. Nanocrystalline ceramics such as zirconia (ZrO2) are softer than conventional
materials, so they can be easily pressed and sintered into various shapes at significantly lower
temperatures.

(iii) High-power magnets: The magnetic strength of a material is directly proportional to

the surface area per unit volume. The magnetic nanocrystalline yttrium – samarium – cobalt
possess very high magnetic properties due to large surface area. The typical applications of
high-power rare earth magnets are in submarines, generators, electric motors, automobile
alternators, magnetic resonance imaging (MRI) instruments and in ultrasensitive analytical
instruments.

(iv) In television or in a monitor: In television or in a monitor, the resolution depends

on the size of the pixel made of phosphors. The phosphor glows when a beam of electrons
strike them. The resolution of images in these instruments increases as the size of pixels
reduces. Materials like nanocrystalline selenide, zinc sulphide, lead telluride and cadmium
sulphide synthesized by the sol-gel method improve the resolution. The use of nanophosphors
may reduce the making cost of high resolution television. In new generation batteries, the
separator plates are made up of nanocrystalline materials prepared by the sol-gel method, and
they hold more energy. For example, batteries made of nanocrystalline nickel and metal
hydrides are long lasting and requires minimal recharging.

(v) Motor vehicles and air craft: The thermal energy generated in engines is wasted to a
large extent. This can be reduced by coating the cylinders with nanocrystalline ceramics such
as zirconia and alumina. By retaining more heat energy, combustion of the fuel takes place

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completely. In air crafts, by decreasing the grain size of the materials the fatigue strength
increases. By using nanomaterials, the fatigue life increases as much as 300%. The components
made of nanomaterials are stronger and operate at higher temperatures. So aircrafts can fly
faster using the same amount of aviation fuel.

(vi) Aerogels: Aerogels are nanocrystalline materials. They are porous and hence air is trapped
at the interstices. Using these materials for insulation at offices and homes leads to drastic
reduction in cooling and heating bills by saving power. These materials are also used as
materials for smart windows, so that the materials become darkened when the sun is too bright
and lightened when the sun is not shining brightly.

(vii) Energy efficiency: For illumination, energy consumption can be greatly reduced by
using quantum caged atoms or light emitting diodes (LEDs) instead of ordinary filament bulbs.
Nanostructures with a continuum of energy band gaps have an increased solar energy
conversion efficiency as compared to ordinary semiconductor solar cells. In hydrogen fuel
cells, nanostructured catalyst material is used on carbon-supported noble metal particles with
diameters between 1 and 5 nm. For hydrogen storage, materials with nanosized pores like
nanotubes, zeolites, etc. are under investigation.

(viii) Medical field: Nanomaterials are used in biology for the development of diagnostic
devices, drug delivery vehicles, analytical tools and in physical therapy applications. The
genetic sequence of a sample can be detected by tagging gold nanoparticles with short segments
of DNA. Magnetic nanoparticles are used to label molecules, structures or micro-organisms of
an antibody. Iron nanoparticles are used in cancer treatment. Nanotechnology is used to
reproduce or to repair damaged tissue.

(ix) Textiles: Clothes made of nanofibres are water and stain repellent and wrinkle-free. They
can be washed less frequently at low temperatures.

(x) Computer: Quantum computers use fast quantum algorithms and have quantum bit
memory space (qubit), so it involves in several computations at the same time.

(xi) Cosmetics: Sun screens based on mineral nanoparticles such as titanium dioxide offer
several advantages. They have high UV protection compared to the bulk material.

In addition to the above, we have quantum dots, suntan lotion, nanotubes, protective coatings.
Fullerenes (C60) are used as lubricants (molecular ball bearings), diamond seeding, diamond
production, xerographic materials, photochromic goggles, etc.

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MODERN ENGINEERING MATERIALS

Introduction

For all engineering applications materials are a necessity. A variety of materials including
metals, alloys, glasses, polymers, composites, etc. are used in many engineering applications.
As few applications demand better and more efficient materials, few emergent materials such
as nanomaterials like carbon nanotubes; biomaterials such as artificial tissue and surgical mesh;
materials for 3D printing; smart materials; etc. are gaining importance of late. Materials
scientists and engineers work together to compose new products by applying physics,
chemistry, and biology, at the forefront of technology. Some of the new engineering materials
like metallic glasses, shape memory alloys, and biomaterials are discussed in this section.

1. Metallic Glasses

Aluminum is considered the best choice for automobile and structural objects for its low
density and high specific strength, whereas, due to good strength and cost-effectiveness, steel
is the most preferred material for structural applications. Likewise, in some applications where
intricate design is required, materials like plastic are used. However, as individual materials,
both of these lack combined properties due to their arrangement of atoms. For example, due to
the anisotropic nature of crystalline metals, there is an inhomogeneity inside the material
because defects like point defects, dislocations, and stacking faults are prominent making them
weak and prone to failures. Metallic glasses are materials combining both the properties of
metals which are in general crystalline and glasses, which are in general amorphous. Examples
of metallic glasses are the alloys of Ni – Ge (Nickel-Germanium), Nickel – Niobium (Ni –
Nb), Magnesium – Zinc (Mg – Zn), Copper – Zirconium (Cu – Zr), and Hafnium – Vanadium
(Hf – V).

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.

Figure 6.9. The atomic arrangement of (a) single crystal, (b) polycrystal and (c) amorphous
structures.

1.1. Properties of metallic glasses.

a. Due to their lack of long-range ordering, there is inherent homogeneity, resulting in the
absence of defects. Also, do not possess long-range anisotropy.
b. These materials possess very high strength in the elastic region. They can have good
yielding strength, which is higher than that of steel.
c. Because of the good homogeneity of atoms in metallic glasses, very good corrosion
resistance is achieved along with good wear resistance.
d. Unlike ordinary silica glasses, metallic glasses are very tough materials.
e. The metallic glasses are very hard materials, and their fracture resistance is much better
compared to ceramics.
f. They have high corrosion resistance due to random ordering and have high elasticity
and ductility.
g. Because of the metallic atoms, these glasses possess significant magnetic effects. It
helps to easily magnetize or demagnetize these materials.
h. The electrical resistivity of metallic glasses is high, and it does not vary with
temperature.

1.2. Glass transition temperature

The glass transition temperature (Generally denoted as “Tg”) is an important parameter for
the preparation of metallic glasses. It is defined as a temperature at which the liquid-like
atomic structure is obtained into a solid, avoiding the route of crystallization. This is more

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 easily understood in the case of a polymer. If we cool a polymer from its liquid state,
initially it undergoes cooling and it gets a rubbery state and then after crossing the T g, it
becomes brittle. This kind of phenomenon occurs in amorphous metals too. In case of
metallic glasses, we can say that Tg is the temperature at which material gets soft from hard
upon heating or get hard upon cooling.

The typical values of glass transition temperature for metallic alloys is about 20 °C to 30
°C.

1.3. Applications of Metallic glasses

a. Metallic glasses are used as reinforcing elements in concrete, plastic and rubber.
b. Metallic glasses are used to make pressure vessels and to construct larger flywheels for
energy storage.
c. They are used to make accurate standard resistors, Magnetic resistance sensors and
computer memories.
d. These are used in tape recorder heads, cores of high-power transformers and magnetic
shields.
e. Metallic glasses are used as the core in motors.
f. These are used to make razor blades and different kinds of springs.
g. Metallic glasses can be used as superconductors to produce high magnetic fields and
magnetic levitation effect.
h. Metallic glasses are used to make containers for nuclear waste disposal and magnets
for fusion reactors.
i. Metallic glasses are used in marine cables, chemical filters, inner surfaces of reactor
vessels, etc.
j. Metallic glasses are very useful in making surgical instruments.

2. Shape Memory Alloys

Shape memory alloys (SMA) are intermetallic alloys with shape memory effect (SME) and
superelasticity (SE), both resulting from a reversible solid-state transformation. These
materials show the ability to return to their original shape or size (i.e., they appear to have
memory) when they are subjected to external agents like temperature, magnetic field, loading,
etc.

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The SME was first discovered by Chang and Read in 1951 in the Au-Cd (gold-cadmium) alloy
system. However, the effect became more well-known after the discovery of nickel-titanium
alloys. The nickel-titanium alloy was first discovered in 1961 and is popularly known as
NiTiNOL (i.e., Nickel-Titanium alloy developed at the Naval Ordinance Lab) which
exhibited a much greater SME than previous materials. The typical composition of NiTi is with
a nickel and titanium in a ratio of 55% to 45%.

Figure 4 Phase transformation of SMA

SMA's have two stable phases: The high-temperature phase is called austenite (parent phase).
Austenite has a cubic crystal structure. The low temperature is known as the martensite phase
and has a monoclinic crystal structure.

SME occurs because of the phase transformation of Martensite to Austenite beyond re-
crystallization temperature. In the absence of any applied load, upon heating an SMA, the
Martensite phase simply gets transformed to Austenite. During this phase transformation,
though there is a change in the microstructure of SMA, the macroscopic shape of the SMA
does not change. Again, on cooling the SMA, a reverse Martensite transformation takes place;
however, the Austenite now gets transformed to twinned Martensite. This transformation is
called self-accommodating transformation.

The Shape Memory Effect (SME) can be summarized as shown in Figure 6.10. At a
temperature below Mfo , SMA has twinned Martensitic microstructure (B). On loading SMA,
the de-twinning of Martensite starts, and it ends at some critical value of the stress (C). Further
loading of SMA results in permanent plastic strain in SMA. On complete unloading, SMA still
retains strain in it (D), which is recovered if it is heated beyond Afo (E). At Aso , the Martensite
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phase starts transforming into Austenite. Afo is the temperature required to complete this
transformation at zero stress level. The percentage of transformation strain recovered by SMA
is proportional to the Austenite volume fraction. On cooling SMA, Martensite transformation
starts from Mso , and for temperatures below Mfo Austenite, it gets completely transformed to
twinned Martensite (B). Cm and CA are material-dependent parameters of SMA, providing the
relationship between temperature and stress for Martensite and Austenite phases, respectively.
Their units are Pa/ K. CM is typically of higher magnitude than CA .

Figure 6.10 Shape memory effect

SME constitutes both stress induced transformation (twinned Martensite to de-twinned

Martensite) and temperature induced transformation (de-twinned Martensite to Austenite).
SME is a useful property of SMA for applications in the field of linear actuators as the
displacement range of an actuator can be easily controlled by controlling the temperature of
the SMA element.

2.1. Applications of SMA

Shape memory alloys have vast applications in our day-to-day life. The most widely used SMA
in engineering fields are in aerospace, automotive and biomedical applications. Some of them
are listed below:

a. SMAs are used in bioengineering applications such as dental wires such as those
used in dental braces, mending broken bones using metal plates, and medical
devices that help open clogged veins and arteries.

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 b. SMAs are used for vibration damping, particularly used in launch vehicles and jet
engines.
c. Another possible application of SMAs is in retrofitting buildings that are not
designed considering seismic conditions.
d. SMAs can also be used as actuators because of their ability to change shapes. They
have potential applications in aircraft and space vehicles because they are lighter
and can help save energy compared to bulky mechanical actuators.
e. The SMAs could automatically change the size of the exhaust nozzles depending
on the temperatures encountered during the various flight stages.
f. Other day-to-day applications include anti-scalding valves, fire security and
protection systems, self-adjusting eye-glass frames, sports equipment, etc.

3. Biomaterials

Biomaterials play an integral role in medicine today—restoring function and facilitating

healing for people after injury or disease. Biomaterials may be natural or synthetic and are used
in medical applications to support, enhance, or replace damaged tissue or a biological function.
The first historical use of biomaterials dates to antiquity, when ancient Egyptians used sutures
made from animal sinew. The modern field of biomaterials combines medicine, biology,
physics, and chemistry, and more recent influences from tissue engineering and materials
science. The field has grown significantly in the past decade due to discoveries in tissue
engineering, regenerative medicine, and more.

Metals, ceramics, plastic, glass, and even living cells and tissue all can be used in creating a
biomaterial. They can be reengineered into molded or machined parts, coatings, fibers, films,
foams, and fabrics for use in biomedical products and devices. These may include heart valves,
hip joint replacements, dental implants, or contact lenses. They often are biodegradable, and
some are bio-absorbable, meaning they are eliminated gradually from the body after fulfilling
a function.

Biomaterials have the following broad range of applications:

• Biosensors—injectable biosensors that allow for continuous monitoring of oxygen,

glucose and lactic acid in vivo

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 • Engineered Skin— electrospun collagen and collagen-synthetic composites have
shown improved collagen strength and elasticity while allowing for easy application.
• Biomanufacturing—Metals, polymers, and ceramics are studied for use in traditional
manufacturing (forging, milling, molds), as well as electrospinning and melt
electrowriting (polymers only) and additive manufacturing (3D printing) of solid cured
and bioprinted tissue engineering scaffolds.
• Biomaterials for bone regeneration—Resorbable metals (Mg alloys) and stiffness-
matched alloys (NiTi) in some cases may perform better than the current standards of
Ti-6Al-4V, CP Ti, Cobalt-Cromium, or stainless steel.
• Drug Delivery—implantable capsules enabling long-term delivery of contraceptive
compounds and other materials
• Biomimetic Elastomers—elastic polymers that mimic mechanical properties of the
tissue and key functions of proteins found in the body
• Microenvironments for Stem Cell Differentiation—engineering tissue construct
microenvironment to direct stem cell differentiation.
• Tendon Repair—Tissue-engineered constructs are being fabricated that will shorten
the recovery time associated with tendon repair and also improve function.

QUESTIONS

1. Why nanoscience is important?

2. Write a note on the surface to volume ratio. Mention its significance
3. Narrate the different applications of graphene.
4. What are quantum dots?
5. What do you mean by quantum confinement? From the quantum confinement
concept, how do properties change at the nanoscale?
6. What do you mean by ‘top down’ and ‘bottom up’ approach? Explain.
7. Mention some applications of nanomaterials
8. Write a short note on Shape Memory Alloys
9. Explain Shape Memory Effect.
10. Discuss the applications of modern engineering materials: 1. Metallic glasses 2.
Shape Memory Alloys 3. Biomaterials
11. How metallic glasses combine both the properties of both glasses and metals.

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