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Nano Scale Systems

1. Length Scales in Physics: Nanostructures:

Nanostructures refer to materials systems with length scale in the range from 1 to 100 nm
in at least one dimension. In a nanostructure, electrons are taken to be confined in the
nano scale dimension(s), but they are free to move in every dimension.

We all in general know that material has two basic structures which are subatomic (micro)
and bulk structure (macro). But in between these two domains, the Size below which a
solid does no longer behave bulk-like is called ‘Mesoscopic domain’. In this domain we can
consider a small condensed object i.e. a collection of atoms and this is the region of nano
materials.

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Here where in length scale we usually have
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Distance between two neighbour atoms in metal
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de Broglie wavelength of electron (carrier) in a metal
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de Broglie wavelength of Constituent in polycrystalline metal film

de Broglie wavelength of carrier in a semiconductor

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Thus we conclude on the basis of length scale in Physics that Nano Science in Mesoscopic
region covers basically from 1 to 100 nm i.e. from sub atomic dimension (one dimension)
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to wave length of matter wave in semiconducting region. This is nano structure or nano
scale dimension where matter does not behave like a bulk material.

The advantages of Nano Materials over Bulk Material are

i) The material properties of nanostructures are different from the bulk due to the high
surface area over volume ratio and possible appearance of quantum effects at the
nanoscale. The study of size and shape effects on material properties has attracted
enormous attention due to their scientific and industrial importance.

ii) The very large surface-to-volume ratio of nano materials is especially useful in their use
in the medical field, which permits the bonding of cells and active ingredients. This results
in the obvious advantage of an increase in the likelihood of successfully combatting
various diseases.

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iii) Nanotechnology is helping to considerably improve, even revolutionize, many
technology and industry sectors: information technology, homeland security, medicine,
transportation, energy, food safety, and environmental science, among many others.

2. 1D, 2D and 3D Nanostructures:

In the domain of nanostructure as mentioned in previous section, we should have a

definite dimensionality. Before addressing that we should note that the dimensionality of
the matter is directly related with the length or area or space covered by that matter. But
in nano structure, the dimension equal to the characteristics length (which is the mean
free path of electron in metal) is taken as zero dimension. So in zero dimension, the
length and also we should mention that in other dimensions, the measured
length must be less than

In reference of that we have several specific dimensions in Nano structure which are

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a) 0D: Nano Dot / Quantum Dot (with dimensions )

[Ex: Molecular P4Se3]

b) 1D: Nano Wire / Quantum Wire (with dimensions )

[Ex: Crystalline SiSe2]

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c) 2D: Nano Film / Thin Film / Quantum Well (with dimensions )

[Ex: Crystalline Ge4Se3]

d) 3D: Nano Rods / Nano Tube (with dimensions )

[Ex: Amorphous SiO2]

In most of the cases we are familiar with the nano tube, especially Carbon nanotube
which is a cylindrical structure formed from planes of graphite, called grapheme that has
pure bonding where the crystal structure of graphite is hexagonal.

The unit cell of graphite rod as a nano tube is tetragonal and has the dimensions
when all are greater than characteristics length. The single-
walled nanotube (SWNT) has diameter of 1.0 to 1.4 nm and length between 50 and
100 . Multi-walled nanotube (MWNT) comprises of two to tens of coaxial tubes with

.
outer diameter in the range 1.4 to 100 nm. It can be taken as the Russian doll with a

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number of similar looking dolls one within the other.
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For the hexagonal structure of nano tube, two basis vectors
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describe the lattice points and in that case, the
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translational vector is then given by

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And it has length

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(As )

where is the carbon-carbon bond length, . On

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the other hand, is the circumference of the cylinder

nano tube having diameter .

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 .
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3. Band Structure and Density of States of Materials at Nanoscale:

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The carbon nanotube is usually formed by wrapping of the grapheme sheet from graphite
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hexagonal structure. The real space lattice of graphene has two carbon atoms, A and B per
unit cell. These atoms form the C-C bond. The translation vector for the real lattice is
. The basis vector for the reciprocal space lattice is where
are obtained from .

From typical E vs. k curves for both metallic nanotube and semiconductor nanotube we
see that the Fermi energy in both cases lies at . Note that the valence band
and the conduction band are mirror images about Fermi level. Further, unlike
silicon the nanotube is a direct gap semiconductor where the extreme of the valence and
conduction bands occur at . This has important consequences for the optical
properties of NTs. It is possible to show that the minimum band gap in a cylindrical
semiconducting NT depends on its diameter and is given by

The band structure of the metal NT is also different from a 3-D metal. Here the energy of
the band at the Fermi surface is linearly proportional to k, i.e.

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where . Here a is the C-C bond length is the C-C bond
energy .

On the other hand we can now calculate the electronic density of states , for the 2-D
and 1-D systems following the methods used for the 3-D bulk material. The total number
of electrons, N, in a square section , of grapheme in 2D is given by the phase space
divided by . Including the spin, we should have

The energy is now given by Or,

The number of states between is

Hence the density of state

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Thus for the 2-D, is independent of E, and we can write down
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Again for the 1-D system with N atoms on a line of length L the number of states including
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spin is and
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. In general the

density of states can be expressed as

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The calculation of the phonon density of states is more complex. In general for a
given direction of propagation
and wavelength, there are three
polarizations and three
frequencies. The three
polarization eigenvectors are of
course orthonormal. The
frequencies corresponding to a
given direction and wavelength
are given by the dispersion
relations that depend on the
atomic bonding interactions.

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4. Size Effects in Nano Systems: Quantum Confinement:
A nano material which is not a bulk material as we have mentioned, but lies in mesoscopic
region, is a small system that ranges between 1 to 100 nanometres in size. Thus it cannot
be detected by the human eye and it can exhibit significantly different physical and
chemical properties in compare to the bulk material. Basically ‘size’ of a
material determines the surface to volume ratio, and can strongly affect the material
uptake and bio distribution, e.g. drug loaded through nano particles can be used for site
specific drug delivery only when uptake and blood circulation could be feasible.

Since a nano system is a collection of a

number of nano particles (constituents
particle), its size is very significant in that
sense, for small size of it, the volume
reduces to some extend and comparatively

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the surface area of it will become enlarged

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and most of the particle distribution, loaded
inside the system will occupy this surface
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er
area. This is the basic ‘size effect’ of a nano
system.
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This is the classical part of size effect, but since nano material is not a bulk material, it has
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dimension in nano scale which is very less than that in macro scale, another size effect
which is ‘quantum size effect’ is more significant for nano system. This so-called quantum
o
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size effect describes the physics of electron properties in solids for great reductions in
particle size. Materials reduced to the nanoscale can suddenly show very different
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properties compared to what they show on a macro scale because of such ‘quantum size
effect’.

Thus we should have two types of size effect or size dependent effect for nano system
which are a) Classical Effect or Surface Effect and b) Quantum Size Effect which is also
called ‘Quantum Confinement Effect’. On the other hand, several properties of a material
which are size dependent properties and may be affected in nano size either through
classical surface effect of through quantum confinement for modified electron properties
in nano size are

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i) Thermal Properties: Melting point may change in nano size in compare to that in macro
scale ii) Mechanical Properties: Adhesion or Capillarity may change in nano scale iii)
Optical Properties: Absorption or scattering of
photons when incident on nano material may have
exceptional character iv) Electromagnetic Properties:
Super paramagnetic properties can be observed in
nano scale material because of its size effect.

All these are several size effects as observed in nano

scale material which are not observed in macro scale
material. Thus it is obvious that for such several
exceptional effects in nano material, it has several
applications. As for example, the so called ‘quantum dot’ which is 0D Nano dot particle is
applied in medical science for site specific drug delivery through living organ.

Specially for Quantum Confinement related with the Quantum size effect which occurs for

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abrupt change of electron behaviour in nano size, we can mention that confinement
through the change of band structure in nano
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system. For the reduction of the number of
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atoms in a material like nano system, the
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delocalized energy states appear for

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confinement.

As for example, in band structure in nano

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system, electron – hole pairs become spatially

confined when the diameter of a particle
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approaches in nano scale which is comparable to the de Broglie wavelength of electron in

metal or conduction band. As a result the energy difference or energy gap between the
energy bands increases for decreasing of the particle size.

5. Quantum Confinement of Carriers in 3D, 2D, 1D Nanostructures and its

Consequences:

As the effect of quantum confinement occurs in nano size, suppose the length of a
semiconductor wafer is reduced to a few nano meter, excitation property of carrier to
higher energy state will be modified due to quantum confinement. Depending on the
dimension of confinement, three kind of confined structure can be defined which are
Quantum Well (QW), Quantum Wire (QR) and Quantum Dot (QD).

For the reduction of size of that semi conductor, the confined electron or hole in a thin
semiconductor layer exhibits a dramatic change of their behaviour. The concerned
quantum principle can be developed by reducing the dimensionality of electron’s

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environment from 2D quantum well to 1D quantum wire. Since the dimensionality gives
the number of degree of freedom of electron’s momentum, as a fact, in a quantum well or
nano film, the electron is confined across one direction giving its degree of freedom 2
where as in a nano wire or quantum wire, electron is confined across two directions
resulting its degree of freedom 1. Similarly, in quantum dot, electron is confined across
three directions giving 0 degree of freedom. Similarly in 3D nano tube, the degree of
freedom is 3 for no direction of confinement (as occurs in a bulk material).

Thus for degree of freedom of the carrier ‘ ’ and the number of the directions of
confinement ‘ ’, we have

Because of quantum confinement of electron in nano structure, several properties will be

affected and here the change for the variation of density of state (g(E)) with energy E is
shown for several nano structures.

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o

Again since we have already mention the change of energy gap between two energy
an

bands of a semiconductor in nano size as a consequence of Quantum confinement, here

the following figures shows that effect of confinement.
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 Synthesis of Nano Structure Material

1. Synthesis of Nano Materials:

Synthesis is the process of the production of a nano substance by the union of chemical
elements, groups, or simpler compounds or by the degradation or disintegration of a
complex compound. There are various synthesis procedures of nano materials which can
be broadly classified into three categories as follows:

Physical Process: Physical synthesis procedures includes arc discharge method, electron
beam lithography, mechanical grinding, inert gas condensation, ion implantation, ball
milling, spray pyrolysis, vapour phase synthesis etc. These procedures are generally
applicable at temperatures above .

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Chemical Process: These are the simplest and most inexpensive methods for the
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synthesis of nano materials. Another advantage is that these processes are applicable at
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low temperatures and a nano samples can be produced in a large scale. Sol gel process is
at

the most popular chemical process for nano material synthesis. Moreover Co-precipitation
method, micro emulsion method, electro chemical method, pyrolysis, irradiation, salvo
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thermal, sonochemical etc. are some other chemical processes for nano material
o

synthesis.
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Biological Process: This type of synthesis process uses micro organisms, plant extracts
or DNA, virus, membrane etc. as templates for synthesis of nano materials. Advantage of
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biological process over chemical process is that the later one is more environments
friendly.

2. Top Down and Bottom Up Approach:

In top-down approach, nanoscale objects are made by processing or by breaking
(disintegrating) larger objects in size. Integrated circuit fabrication is an example for top
down nanotechnology. The starting materials in these fabrications are relatively large
structures such as silicon crystals. Lithography is one of the top down technology which
has enabled making tiny chips and there are many types of them such as photo, electron
beam and ion beam lithography.

This top down procedure involves the reduction of size from a larger assembly of
Nanostructure or a bulk material. Basic principle of this approach is to break larger grain
sizes of the bulk material into smaller one by the use of physical processes like crushing,

10
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milling or grinding. Top down approach includes one of the most popular methods for
synthesis solid state reaction.

However there are some limitations of this approach. Uniformly shaped materials cannot
be prepared through this route. The biggest problem of this method is the imperfection of
the surface structure of the prepared sample. Such imperfection always has a significant
impact on physical properties of nano materials. Moreover, the conventional top-down
technique can cause significant Crystallographic damage to the as prepared samples
patterns.

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Here we should now mention that in this top down technology for nano particle synthesis,
the basic technologies are

a) Mechanical Grinding b) Metal Vapour c) Thermal Breakdown d) Chemical Breakdown e)

Spontaneous Chemisorptions

Since the process of chemical purification is not required here, the disadvantages of this
top down technologies are

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a) Here the size of the nano particle as developed through this technology lies within the
range from 10 to 100 nm

b) For same size of the particle, the shape and the geometry of it may vary from one
particle to another particle.

c) Here in this synthesis, the deposition parameters cannot be controlled accurately

d) Through the development of nano particles in this way, imperfections, stresses, defects,
along with the impurities appears also in this synthesis.

On the other hand

Bottom-up approach in nanotechnology is making larger nanostructures from smaller
building blocks such as atoms and molecules. Self assembly in which desired
nanostructures are self assembled without any external manipulation. When the object
size is getting smaller in nanofabrication, bottom-up approach is an increasingly important

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complement to top-down techniques.
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This route or way of this process refers to build up the nanostructure from the bottom
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which may be atom by atom or molecule by molecule or cluster by cluster. It is more
frequently used for preparing most of the nano sized materials with the ability to
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generate a uniform size, shape and distribution.

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It effectively covers chemical synthesis and precisely controls the reaction to inhibit
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further particle growth.

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Bottom-up approach nanotechnology can be found from nature, where biological systems
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have exploited chemical forces to create structures for cells needed for life. Scientists and
engineers perform research to initiate this quality of nature to produce small clusters of
specific atoms, which can then self assemble into more complex structures.
Manufacturing of carbon nano tubes (CNT) using metal catalyzed polymerization method
is a good example for bottom-up approach nanotechnology.

Molecular machines and manufacturing is a concept of bottom-up nanotechnology

introduced by Eric Drexler in his book Engines of Creation in 1987. It has given early views
of how can nanoscales mechanical systems are used to build complex molecular
structures.

Similar to top down process, here also in this bottom up technology, the several
technologies which are included are

a) Sol – gel b) Chemical reduction of salts c) Electrochemistry d) Template – directed e)

Precipitation f) Micro emulsion

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Here also for no requirement of chemical purification, the several disadvantages of such
bottom up technologies are

a) Large scale production is difficult in this way

b) After synthesis in this way, chemical purification is required

The differences between Top down and Bottom up process are

i) Top down procedure involves the reduction of size from a larger assembly of
Nanostructure or a bulk material, but Bottom-up approach in nanotechnology is making
larger a nostructures from smaller building blocks such as atoms and molecules.

ii) In top down process, same size of the particle, the shape and the geometry of it may
vary from one particle to another particle whereas in bottom up process, It is more
frequently used for preparing most of the nano sized materials with the ability to
generate a uniform size, shape and distribution.

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iii) Bottom-up approach nanotechnology can be found from nature, where biological
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systems have exploited chemical forces to create structures for cells needed for life, but
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top down process is completely artificial which is mostly based on several Physical
processes.
at

3. Ball Milling:
M

Ball milling is a very popular physical method for synthesis of nano materials. It is an
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example of top down approach. Ball milling is a mechanical technique widely used to
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grind powders into fine particles and blend materials. Being an environmentally-friendly,
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cost-effective technique, it has found wide application in industry all over the world.

A ball mill is basically grinder

equipment used to reduce the particle
size of active and excipient materials. It
is also known as pebble mill or
tumbling mill. The quality of dispersion
is affected by the factors such as the
milling time, rotational speed, size of
balls and balls/dispersion amount
ratio. Under certain processing
conditions, the particles can be ground
to as small as 100 nm. This technique
has several advantages which include
cost-effectiveness, reliability, ease of

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operation, reproducible results due to energy and speed control, applicability in wet and
dry conditions on a wide range of materials.

A ball milling machine consists of a hallow cylinder having equal length and diameter and
it can rotate along its longitudinal axis. The cylinder is partially filled up with
metallic/ceramics/rubber balls. These balls act as the grinding media. The balls could be of
different diameter and occupy almost 30-50 percent of the mill volume. The large balls
tend to break down the coarse feed materials and the smaller balls help to form the fine
product by reducing void spaces between the balls. The inner surface of the cylinder is
coated with rubber or manganese steel.

For the principle of operation of ball mill, we should note that here ball mills grind bulk
material (called free material) by impact and attrition (friction). In a continuously
operating ball mill, feed material fed through the central hole via a cone in left and
then exposed to the grinding media. The material grinding occurs during the rotation of
the cylinder. With the rotation of the cylinder the grinding balls are lifted up on the rising

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side of the cylindrical shell and then drop down on to the feed, from near the top of the
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shell. In such a way the impact of falling grinding balls causes the abrasion of the particles
between them. After that ground materials are discharged through the central hole via a
er
cone at right in the discharge cap.
at

Here we should note that there are various modes of milling operations depending on the
M

motion of grinding balls. In a mono layer filling mill by grinding media, the balls rotate
around their axis parallel to the drum axis of rotation. In multi layer filling mill by grinding
o
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media, depending on the speed of rotation, several modes of rotation are possible which
are
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i) Cascade Mode Motion: Here the rotation occurs without flying of the balls

ii) Mixed Mode Motion: Motion occurs partly through rolling and partly through flying

iii) Water Fall Mode Motion: Grinding balls rotation only occurs through flying

For efficient operation of such ball milling machine, it is necessary to keep right balance
between the ball size and the size of the feed materials. Although several types of grinding
balls are used in this ball mill, but at the time of selection of the grinding balls, their
weight, size, density, hardness ... etc should be taken carefully. Out of all these
parameters of a grinding ball used in the mill, the very significant parameter is tits weight
which should be sufficient to grind even the largest piece of feed crushed materials.

In this ball milling machine, the grinding of minerals are basically carried out. There are
several types of grinding media used in grinding. According to the geometrical shape of
the grinding media, there are a) balls of different diameter b) short cylinders, steel circles
c) steel bars and d) truncated cones.

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The material used for the production of the grinding media can be divided into three main
groups which are

a) Steel Grinding Media: Here carbon steel is used as a raw material for the production
which is made doped with various chemical elements to impart grinding medias
properties in respect of hardness and strength.

b) Cast Iron Grinding Media: Here the grinding media is Cast iron as gray and white.

c) Ceramic Grinding Media: Such grinding media is used in small sized mill of about 50
litters in chemical and food industries.

According to the production methods, such grinding media are used in two forms –
Grinding Balls and Cylpebs.

Grinding Balls are usually made by steel and cast iron. By several manufacturing methods
like ‘helical rolling’, ‘moulding’, ‘stamping’.. etc such Grinding balls are constructed.

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But Cylpebs are such type of grinding media which are manufactured by casting and
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rolling method. In most of the cases, Cylpebs are produced from ‘gray’ and ‘white’ iron by
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casting method.
at

The advantages of such Ball Milling Technique are

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a) It produces very fine powder with particle size less than 10 microns
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b) It is suitable for milling toxic materials in a complete enclosed form

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c) It has wide application in nano material synthesis

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But the disadvantages are

a) It takes relatively long time for milling

b) Contamination of the product may occur from the grinding balls as well as from the
casing

c) It is difficult to clean the machine after use.

4. Gas Phase Condensation:

As the name suggests gas phase condensation uses evaporation of a metallic source in an
inert gas atmosphere to form nano particles. In its basic from a metallic source which has
to be made into nano structured is used as a heating element inside a chamber. The
chamber has to be previously evacuated to about (1 mm of Hg pressure = 1
torr) and backfilled with inert gas to a low pressure. The adjustment of pressure inside the

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vacuum chamber is a tricky job. The pressure has to be high enough to promote particle
formation, but low enough to prevent their agglomeration.

On resistive heating, the metal vapour migrates from the hot source into the cooler inert
gas by a combination of convective flow and diffusion. The evaporated metal atom
collides with the gas atoms within the chamber and looses kinetic energy and finally the
metal atoms get condensed. Ultimately, the particles are collected for subsequent
consolidation, usually by deposition on a cold surface.

After evaporation of the metal vapour, the liquid particles collide and coalesce in a
controlled environment such that they can grow as per specification. As the liquid
particles are further cooled under control, they become solid and prevent any further
growth.

In most of the cases of inert gas condensation technique, the substrate is cooled with
liquid nitrogen to enhance the deposition efficiency. Particles collected in this manner are

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highly concentrated on the deposition substrate. While the particles deposited on the
substrate have complex aggregate morphology, the structure tends to be classified in
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terms of the size of the crystallites that make up these larger structures.
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At this stage the nano particles are very much reactive. To prevent agglomeration with
any other materials the nano particles are coated with coping agent. Then scraping and
compaction processes take place within the clean environment to ensure powder surface
cleanliness (i.e., to reduce oxide formation) and to minimize problems associated with
trapped gas.

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In this process the parameters which can control the quality of shape and size of the nano
materials are vapour concentration, temperature and pressure, physical properties
(melting point) of the metal. Under same conditions metal with a high melting point
produces smaller particles. Collection of fine sized nano powder is another difficult job
because the nano particles tend to suspend in the gas in constant Brownian motion and
therefore not settled by the action of gravity. Special filters are then used and centrifugal
sedimentation is used to collect powder particles.

The advantages of this gas phase condensation method are

a) Although this process is very old but still it provides a good control over the shape and
size of the final product (nano material)

b) It is continuous process and by this method, thin film and nano powder can be
produced.

.
c) It is an ideal process for synthesis of metal nano particles.

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d) It ensures highest purity relative to liquid phase or solid phase synthesis process.
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e) It can be used for large scale production.
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But the disadvantages are

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a) The process is indeed very slow

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b) Problems in running the process may occur for the aggregation of particles
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c) Adjustment of pressure inside the vacuum chamber is difficult

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d) Special arrangement is needed to collect the nano powder.

5. Vacuum Deposition:
Vacuum deposition which is also known as Vacuum evaporation is a general term of a
typical surface treatment technology. The technology is used to deposit thin layers of
nano materials onto a substrate (also called target surface). As the term suggests, vacuum
deposition technologies must include the process that makes deposition of source (raw)
materials in vapour state through condensation or chemical reaction or conversion in a
vacuum environment.

When the vapour phase of source material is made deposited on target surface through a
physical process like condensation then the process is called physical vapour deposition
(PVD) and when it is made deposited on the substrate through chemical reaction made by
vapour atoms or molecules with the substrate then the process is known as chemical
vapour deposition (CVD). A schematic diagram of CVD is shown in figure.

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 .
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After vaporization, atoms or molecules from the source material reach the target surface
known as the substrate in a vacuum environment without colliding with residual gas
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molecules between the source and the substrate in the deposition chamber.
M

In order to avoid collisions, the mean free path of the molecules aiming the substrate
o

should be very large which requires a vacuum better that 10 Torr inside the deposition
an

chamber. At this pressure, there is still a large amount of concurrent impingement on the
substrate by potentially undesirable residual gases that can contaminate the film
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deposited on the substrate. In such cases, a high (10 Torr) or ultrahigh (less than 1 Torr)
vacuum environment is normally used to produce a film with the desired purity,
depending on the deposition rate, reactivates of the residual gases and depositing species,
and the tolerable impurity level in the deposit.

The advantages of this process of Vacuum Deposition for nano material synthesis are

a) It provides a low pressure plasma environment.

b) Here control of gas and vapour composition can be made

c) Here the mass flow can be controlled within the processing chamber.

i) Physical Vapour Deposition (PVD):

Here for Physical vapour deposition (PVD) it is a very popular vacuum deposition
technique where a thin film of a source material is deposited over the entire substrate
rather than in certain areas. The thickness of the deposited film can range from angstroms

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to millimetres. This particular technology is very versatile in nature and it can develop
nearly homogeneous thin film of almost every type of inorganic materials such as metal,
alloys, compounds and organic materials as well.

Over the past few years the application of PVD technologies has been increased
tremendously in different important sectors of science and technology namely
engineering, chemical, and nuclear, microelectronics and related industries. Since modern
technologies demand multiple and conflicting set of properties materials which a single
material cannot fulfil. So the only solution is therefore a composite material i.e. a core
material along with a coating each having requisite properties to fulfil the requirements.

The primary objective of this type of deposition process is to transfer atoms from a source
material to the substrate in a controllable manner. In this process, whatever be the source
material inorganic or organic, it must remain in solid or liquid state such that it can
vaporize from a condensed phase and then back to a thin film condensed phase.

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Several methods are used to evaporate atoms from the source material and depending on
that PVD variants differ from each other. For example, in thermal evaporation
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vaporization of source material is done through resistive heating, whereas in sputtering
er
the same is done via bombarding the source material with a plasma (accelerated gaseous
at

ions) or in electron beam evaporation the bombardment is done by electrons, in pulsed

laser deposition (PLD) method a high intensity laser ablates material from the source into
M

a vapour state.
o

The several types of PVD processes are thermal evaporation, e beam evaporation, pulsed
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laser deposition, arc vapour deposition, ion plating etc. A few of them will be discussed
here.
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a) Thermal Evaporation:
Thermal evaporation is the simplest and first practical PVD technique for the synthesis of
nano materials. It is normally used for the synthesis of a variety of oxide and non oxide
thin films. The solid source material is evaporated through resistance heating and then
thin layer of atoms are deposited on a substrate via condensation.

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 .
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at
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The substrate on which the thin film is to be deposited is positioned facing the source. The
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pressure inside the vacuum chamber should be such that the mean free path of the
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evaporated atoms has the mean free path larger than the distance between the source
and the substrate. A crystal monitor placed near the substrate records the quantity and
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rate of deposition. Normally the deposition rate in his particular PVD variant is few Atoms
per seconds. Though this process is applicable for thin film preparation in photo voltaic,
anti reflection coating in silicon based solar cells but requirement of high temperature
and ultra high vacuum are the prime limitations of this
process.

Here the advantages of this process of Thermal evaporation are

a) It is a simplest process and economically profitable

b) In this process of vacuum evaporation, solid material of any shape can be taken as
source material.
c) Rate of deposition is high in this process
b) Electron Beam Evaporation:
Electron beam (E-beam) evaporation is a form of Physical vapour deposition technique. In
this technique, the target material to be used as a coating is bombarded with an electron

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beam from a charged tungsten filament to evaporate and convert it to a gaseous state for
deposition on the material to be coated.

The whole process takes place in a high vacuum chamber inside which atoms or molecules
are in a vapour phase. Then these atoms or molecules precipitate a form a thin film
coating or the substrate. Together with sputtering, E-Beam evaporation is the most
common types or physical vapour deposition (PVD). Of these two processes, the E-Beam
deposition technique has several clear advantages for many types of applications.

c) Pulsed Laser Deposition:

Pulsed laser deposition (PLD) is a physical vapour deposition technique where a high
power pulsed laser beam is focused to strike a target of the desired composition. Material
is then vaporized and deposited as a thin film on a substrate facing the target. This
process can occur in ultra high vacuum or in the presence of a background gas, such as
oxygen when depositing films of oxides.

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Pulsed laser deposition (PLD) is a physical vapour deposition process that has been used
for producing high quality films of material over the past few decades. It is a prime
method for producing metal oxide based (MOX) gas sensing layers. The technique attracts
scientific importance when a research group deposited a fine quality thin films of yttrium
based cupric oxide (YBCO)-a high temperature superconductor around 1987.

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Principle of operation: The technique uses high power laser pulses
(typically ) to melt, evaporate and ionize material from the surface of a
target material. Entire process occurs inside a high vacuum chamber which may contain an
inert gas such as argon or neon. Sometimes a background gas such as oxygen may also be
present inside the chamber which provides a reactive atmosphere inside it. The vaporized
or ablated material, containing neutrals, ions, electrons etc., is known as a laser-produced
plasma plume and expands rapidly away from the target surface. The ablated material is
then collected on an appropriately placed substrate upon which it condenses and the thin
film grows.

In practice, the situation is not so simple, with a large number of variables affecting the
properties of the film, such as laser fluency, background gas substrate temperature,
roughness of the substrate surface, ionization density of the ablated material etc. These
variables manipulate the film properties to some extent. However, optimization can
require a considerable amount of time and effort. Indeed, much of the early research into

.
PLD concentrated on the empirical optimization of deposition conditions for individual

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materials and applications, without attempting to understand the processes occurring as
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the material is transported from target to substrate. Generally femto second lasers
er
lasers are used to deposit thin film having little nano meter thickness. A
schematic diagram of pulse laser deposition machine is shown in figure.
at
M

Thus in Pulsed laser deposition, the following steps are taken for the formation of the thin
film with thickness in nano range
o
an

i) The energy of the laser source is made absorbed by the surface of the target.

ii) By the help of laser therapy on the target material, plasma sheet (thin) is made.
.N

iii) The thin plasma sheet is then transported from the target to the surrounding of the
substrate

iv) Substrate is then cooled by flowing water.

v) The residual material is then deposited on the surface of the substrate.

vi) Nucleation i.e. the initial construction and then growth of the film is made on the
surface of the substrate.

ii) Chemical Vapour Deposition (CVD)

Chemical vapour deposition is generally a bottom up approach, used to deposit a thin film
of a solid target material from its vapour phase. This process is extremely popular for
producing thin films of semiconductors, composites, Nano machines, optical fibres,
catalyst, etc. Micro fabrication process generally use CVD to deposit thin films of various

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types of materials such as compounds of silicon (oxide, carbide, nitride etc) in different
forms of carbon (fibre, nano fibre, nano tubes, diamond, graphene etc), tungsten, etc.

A schematic diagram of CVD apparatus is shown in figure. A typical CVD apparatus

consists of a gas supply system, reactor chamber, substrate loading mechanism, energy
source, vacuum system, exhaust system and process control equipment.

Basic principle of CVD is somehow similar to PVD. In CVD the material is coated on a
substrate material. It is basically a process of diffusive convective transport. The target
material is sent to a reaction chamber in the form of vapour at a certain temperature.
Normally CVD processing temperatures are quite high; it typically lies in the range of 850
to .

Inside the reaction chamber, the gaseous target material is transported to the substrate
and the gas reacts with the substrate and gets deposited on to it. The temperature and
pressure inside the apparatus should be controlled significantly and pre-treatment of the

.
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substrate is also required.
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Finally, the apparatus should have a way to remove the excess gaseous waste out. The
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coating material should be volatile as well as stable in order to be converted to the
gaseous phase and then coat onto the substrate. Generally coating material compounds
at

will provide a single element to the deposited material, with others being volatilized
M

during the CVD process.

o

In some cases, coating material may provide more than one element. Such materials
an

actually simplify the delivery system as they reduce the number of reactants to produce a
given compound. CVD coating material can be grouped into a number of categories such
.N

as hybrids, halides, metal carbonyls, metal alkyls and metal alkoxides etc.

The advantages of this CVD are

a) This process of nano synthesis is suitable for thin film deposition over the large area

b) Super quality thin film of nano material can be made by this process and it is extremely
useful in atomic layer deposition process.

c) CVD is widely used in semiconductor industry. As for example, GaAs thin film is made
deposited in integrated circuit or in photo voltaic cell by this method of CVD. This CVD is
also used in Polymerisation for super thin film deposition.

If we compare CVD with PVD, we should mention that

i) PVD is physical vapour deposition whereas CVD is chemical vapour deposition

ii) PVD is performed in solid form whereas CVD is performed in gaseous form

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iii) In PVD, atoms are in moving state and are deposited on the substrate whereas in CVD
gaseous molecules reacts with the substrate

iv) In PVD, deposition occurs at relatively low temperature at about 250oC to 450oC
whereas in CVD, the required temperature for deposition is about 450oC to 1050oC.

a) Sol – Gel:

Chemical methods i.e. Chemical vapour deposition methods are widely used to synthesize
nano materials. Such methods include Sol – Gel process, colloidal, electro – deposition,
Langmuir – Blodgett (LB) films, Inverse micelles.... etc. In particular CVD processes, is a
nano synthesis process in which nano material is obtained as colloidal solution. This
solution is then filtered and dried to obtain powder of the nano particles. Also in some
CVD methods, thin films are obtained by some other processes like electro-deposition,
etching.... etc.

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The CVD method of synthesis has several advantages which are listed below:

1. The most of the techniques used in this method are simple.

2. The method is inexpensive and less instrumentation is required compared to other

physical methods as directed by PVD.

3. During synthesis, doping of atoms (ions) is possible in this method.

4. Large amounts of the nano substances can be received.

5. Products can be made in various kinds of shapes and sizes.

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6. Initially substances are received in the form of liquid but then be converted into dry
powder or thin films quite easily.

7. Self assembly or painting is possible in this method.

Let us now discuss ‘Sol – Gel’ method which is a widely used process for nano synthesis
through CVD process. The schematic diagram of ‘Sol – Gel’ method is shown in figure. The
experimental set up is very simple. Two things are initially required for this process. One is
the solvent and the other is the solute. The process involves conversion of monomers into
a colloidal solution known as the ‘Sol’. The Sol can also be deposited on to preferred
substrates as thin films using two techniques: (i) Spin Coating and (ii) Dip Coating.

The ‘Sol’ gradually evolves towards the formation of a Gel - like biphasic system
containing both a liquid phase and solid phase whose morphologies range from discrete
particles to continuous polymer networks. This Gel is used to form materials of different
types such as nano particles, xerogel, glass or ceramics.... etc. depending upon the further

.
processing steps involved. Nano particles and xerogels are then obtained by simple

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evaporation of solvent. The xerogel can also be formed as ceramics by heat treatment and
ia
glassy nature of the ceramics can be induced by melting techniques.
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Normally, for production of the nano particles, after the formation of Gel, it must be
at

heated up to the stage where the entire sample is burned. Generally then a black floppy
M

and dried mass is formed. This dried mass is then grinded and pelletized and finally
sintered at the required temperature to obtain the desired compound.
o
an

The advantages of this ‘Sol – Gel’ method are

.N

a) In this method, not only ‘thin film’ but also several form of nano material can be made
in several cost effective way which are nano glass, nano ceramics... etc.

b) It requires comparatively low temperature for synthesis.

c) All the products from this method has qualitative surface to volume ratio which is
essential for size effect (Classical and Quantum Confinement both) of nano materials

d) Qualitative nano dust particles can be obtained from this type of chemical synthesis
method.

But still the disadvantages of this method are

a) Source material of high purity is required in this method.

b) Since it is a multi step process, it requires regular monitoring.

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c) In this method, particularly at the time drying of Gel, volume shrinkage and cracking
may occur.

b) Electro Deposition:

Electrodeposition which is also known as electroplating is an electro chemical process that

allows the preparation of solid deposits on the surface of conductive materials. Certainly
It belongs to the category of bottom up approach of synthesizing nonmaterial’s in CVD
process. Since thin films are being extensively used in micro electronics, this fabrication
technique is receiving greater attention to produce thin films of some material to the
surface of another material (target surface) to change its external properties such as to
increase corrosion protection, increase abrasion resistance, improve decorative quality, or
simply to deposit a layer which is part of a more complicated device. This method is a
commercially highly relevant process, providing the basis for many industrial applications
such as electro-winning, refining, and metal plating. For example, nickel metal is

.
electroplated on automotive products so as to inhibit against corrosion, and copper metal

ls
is electro-deposited on to circuit boards to provide low resistance pathways between
ia
electronic components.
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Electrodeposits are formed by the action
at

of an electric current passing in an

electrochemical cell. We know that an
M

electrochemical cell is a device that

o

consists of two conductive or semi-

an

conducting electrodes immersed in an

electrolyte. The electrodes used in
.N

electrodeposition are called the working

electrode (cathode) that consists is the
object where electrodeposition is planned
and the counter-electrode (anode) necessary to complete the electrical circuit.

Electrolytes for electrodeposition are usually aqueous solutions containing positive and
negative ions, prepared by dissolving metal salts. The electric current that flows between
the two conductive electrodes, in presence of an external voltage, is because of the
motion of charged species via migration and diffusion, towards the surfaces of the
polarized electrodes. At the surface of the electrodes, the conduction mechanism changes
from ionic to electronic and this is an intermediate process mediated by the occurrence of
electrochemical reactions that promote the reduction or the oxidation of the ionic
species.

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The advantages of this process of Electrodeposition are

a) It is relatively cheap and fast process

b) It is a low energy consumption process

c) This process can be performed even at room temperature and it is an important matter
in nano synthesis

d) The material waste in this process is low

e) It is a versatile process

f) The nano film as fabricated by this electrodeposition process is extremely strong and
also uniform in thickness

g) It has wide application in several branches like nano technology, Polymerisation,

.
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Biomedical applications, several electronic and optoelectronic applications.

c) Spray Pyrolysis:
ia
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Spray pyrolysis is a process in which a thin film is deposited by spraying a solution on a
at

heated surface, where the constituents react to form a chemical compound. This
M

technique involves three major process stages: precursor solution composition, aerosol
generation and transport and then synthesis. Each one of these stages is tuned according
o

to the final chemical and physical characteristics of the material targeted. The choice of
an

materials/processes at each stage and the corresponding adjustments affect the rest of
the stages to some extent. At the first stage, the chemical composition of the precursor
.N

solution involves a compound(s) that will render after the pyrolysis stage the chemical
composition required.

The selection of the solvent limits the maximum concentration of the precursor
compound in the solution and determines the best choice for the aerosol
generation/transport process and temperature and rate of synthesis. At the second stage,
the proper range of synthesis temperatures is determined and the aerosol droplet size
distribution, determined by the aerosol generation mechanism, sets the morphological
characteristics of the final material produced. At the last stage, the final chemical reaction
takes place on a gas phase or on a hot substrate determines whether the material
synthesized is a powder or a film coating.

According the types of reactions, the chemical spray deposition process are divided into
three groups:

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In the first group, the droplets of the solution reside on the heated surface and the solvent
evaporates. The components may further react in the dry state.

The second group represents a process in which the solvent evaporates before the drops
reach the heated surface and the dry solid impinges on the surface by decomposition.

In the third group, there are processes where the solvent vaporizes as the droplets
approach the substrate with the consequent heterogeneous reaction of the solution
components.

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The most important parameters to be controlled in all of these processes are the
substrate temperature, flow rate of the carrier gas, distance between the nozzle and the
substrate, and the amount and concentration of the solution. Among these variables, the
substrate temperature is considered to be the most important factor in producing thin
film from spray pyrolysis processing. This is because the droplets drying, decomposition,
crystallization, and grain growth depend strongly on this parameter.

This method of ‘Spray Pyrolysis’ is applied to deposit dense film and porous film. It can
also be used in deposition of multi layer films and it is also used in glass industry / Car
industry and also in production of solar cell.

The advantages of this process are

a) It is extremely easy technique for preparing thin film of any composition

b) This method is relatively cost effective

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c) This does not require highly pure chemicals (source material)

d) In this method, vacuum is not necessary for thin film deposition.

d) Hydrothermal Synthesis:

Here the figure shows schematically the procedures adopted in the hydrothermal
synthesis technique. The setup includes a tubular reactor consisting of two parts, each
approximately 3m in length with inner diameter approximately 1.75mm. There are also
two piston pumps, syringe pump, back pressure valve, electric furnace with fluidized sand
bed, cooler, flow mixer, manometers and pressure gauges. All syntheses of metal oxides
are carried out virtually by the same procedure.

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The initial parent solution for synthesis is prepared by dissolution in water of equimolar or
.N

different molar amounts of nitrate, sulphate or acetate of the first metal, with other
salt of the second metal, . The parent solution is then introduced by a syringe pump
into mixer 9 in a 1: 10 ratio to supercritical water, which is introduced into the same mixer
by a piston pump in a continuous mode.

Transformations are performed at temperatures and pressures close to critical parameters

of the mixture containing more than 95% percent of water, temperature above and
pressure exceeding 230 atmosphere. These are the main parameters to be set for the
synthesis for typical nanoparticles using this method.

This process can be performed following any of the three methods:

(i) Temperature difference technique; (ii) Temperature reduction technique and (iii)
Metastable phase technique.

However, the method (i) is widely used and the super saturation in this method is
achieved by reducing the temperature in the area of crystal growth.

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In method (ii), super saturation is achieved by a gradual reduction in temperature of the
solution in the autoclave.

The disadvantage of this method (iii) is the difficulty in controlling the growth process and
introducing the seed crystal.

e) Preparation through Colloidal Methods:

The Colloidal method involves in formation of nano sized particles within a continuous
fluid solvent medium. Ultra fine particles (called aerosol or emulsion particles) (size
ranging from ) are suspended in the dispersing medium to form a colloidal
solution. Due to the attractive inter-molecular forces (also known as Van dar Waals
interaction), the colloidal suspension tends to aggregate and large particles are generated.
In order to prevent particles from aggregation, the dispersing agents are introduced to the
colloidal systems. The energy barrier to agglomeration is highly dependent on the balance
of attractive (Van dar Waals forces) and repulsive forces between the particles. The

.
colloidal solution displays properties as a Brownian motion and it is the energy, which can

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be expressed as product of . ia
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For better understanding, let us consider a few examples of different types of colloids. If
we consider aerosol type of colloid with liquid as dispersed substance and added in gas as
at

dispersing medium, we finally get

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‘Fog’. Similarly for solid aerosol as

dispersed medium when merged
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or made suspended in gas as

an

dispersing medium, we get

‘Smoke’. Again for liquid emulsion
.N

as dispersed medium, when added

with another liquid as dispersing
medium, we get ‘milk’. All these
are the examples of Colloidal
substance.

In this Colloidal method, the

particles with ultrafine sizes such
as quantum dots (ultrafine aerosols) are made by semiconductor and in a certain
approach, the size of quantum dots can be controlled between 1 and about 40 nm,
depending on the change of temperature and heating time of dispersing conducting
medium. As a result, the electrical injection of carriers can be prevented due to the
presence of quantum dots as insulating glass matrix in dispersing medium. The injection
of organic compounds allows for formation of II – VI semiconductor quantum dots. The
crystalline metal and metal oxide nonmaterial’s can be easily formed from as aqueous

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solution and the size can be tuned within 110 nm according to the addition of different
dispersing agents, such as traditional Indian medicinal natural compounds.

f) Molecular Beam Epitaxial (MBE) Growth of Quantum Dots:

i) An Initiation of Quantum Dots:

Quantum dots (QDs) are tiny semiconductor particles a few nano meters in size, having
optical and electronic properties that differ from that of larger particles (Macro) due to
quantum mechanics. When the quantum dots are illuminated by UV light, an electron in
the quantum dot can be excited to a state of higher energy. In the case of a
semiconducting quantum dot, this process corresponds to the transition of an electron

.
from the valence band to the conduction band. The excited electron can drop back into

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the valence band releasing its energy by the emission of light. This process of light
ia
emission is termed as the photoluminescence. The colour of that light depends on the
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energy difference between the conduction band and the valence band.
at

Quantum dots have properties intermediate between bulk semiconductors and discrete
M

atoms or molecules in mesospace. Their optoelectronic properties change as a function of

both size and shape. Larger quantum dots 56 nm diameter emit light of longer
o

wavelengths, with colours such as orange or red. Smaller quantum dots (23 nm) emit
an

shorter wave-lengths, yielding colours like blue and green. The specific colours, however,
vary depending on the exact composition of the quantum dots.
.N

ii) MBE Method in Nano Synthesis:

Molecular Beam Epitaxial (MBE) is an advanced ultra-high-vacuum facility to make

compound semiconductor materials with great precision and purity. These materials are
layered one on top of the other to form semiconductor devices, such as transistors and
lasers, and novel materials for research and development.

MBE is an epitaxial method for thin-film deposition of single crystals. This process was
developed by J.R. Arthur and Alfred Y. Cho in the late 1970s at Bell Telephone
Laboratories. It is widely used in the manufacture of semiconductor devices, including
transistors, and it is considered one of the fundamental tools for the development of
nanotechnologies. MBE is used to fabricate diodes and metal oxide semiconductor field-
effect transistors (MOSFETs) at microwave frequencies and to manufacture the lasers
used to read optical discs such as compact discs (CDs) and digital versatile discs (DVDs).

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 Molecular beam epitaxial
(MBE) is an atomic layer
by atomic layer crystal
growth technique based
on reaction of molecular
or atomic beams with a
heated crystalline
substrate, performed in
an ultra-high vacuum
(UHV) environment. The
term molecular beam
epitaxial was used for the
first time in 1970. The

.
term molecular beam

ls
ia describes a unidirectional
kinematic flow of atoms or molecules with no collisions among them, as opposed to a
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viscous, fluid-like flow. Epitaxial refers to ordered growth of one crystalline layer on
another crystalline layer, with the same (or related) crystal arrangement. Therefore a
at

critical issue in epitaxial crystal growth is the surface conditions of the starting crystal (the
M

substrate) a subsequent layer as they are being grown. Molecular beam epitaxial is unique
in two respects: it is performed in UHV, and it is based on the reaction of atomic and/or
o

molecular beams with a crystalline surface, relying on kinetic processes such as

an

adsorption, desorption, dissociation, migration, reaction and incorporation. These

features allow real-time, in situ monitoring and control during the substrate preparation
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and film growth, to ensure the best conditions for stoichiometry and epitaxial.

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 Optical Properties

Actually nano particles shows several optical properties which are unusual and can’t be
observed in macro or bulk materials. By controlling the shape, size, composition and also
surface parameters carefully, several optical properties can be created in nano materials
which can also be applied in several fields. Thus the study of several optical properties of
the nano materials is very significant in overall studying of Nano materials.

Because of the extremely small size, nano

particles exhibits enhanced optical emission
along with several non linear optical properties

.
mainly for quantum confinement effect of it. As

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for example, if a bulk gold material be
ia
transferred to the nano sized by any of top
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down synthesis, it absorb red light and reflect
at

blue light and looks like blue colored or purple

M

at size 80nm. Again at size of 30 nm, it reflects

o

red light and looks like red colored. But if it has

an

comparatively big size greater than 100 nm

.N

then the electron cloud inside it will get scope to distribute uniformly such that the
incident photon will not be able to penetrate that electron cloud and then that nano
material will be looked shiny.

Thus we see that the colour of nano particle will be different for the variation of its size.
Here the actual fact is that for very small size of the nano material, the electrons inside it
cannot move freely as they do within bulk material. Such restriction in movement of
electron basically occur for quantum confinement effect of nano sized material and for
that size effect, the interaction of electron cloud inside nano particle will be different with
the incoming photon at several nano sized scale and several optical properties will appear.

Again we can take another example for such variation of optical properties in nano sized
material. If we take ZnO bulk material, it blocks UV light for passing through it but it can

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scatter all wavelengths of white light from it. Thus it looks white. But the nano sized ZnO
will block both UV and visible light and it can’t scatter visible light. As a result, the nano
sized ZnO looks transparent.

Actually the variety of optical properties of nano structure at low dimension can be
predicted from the energy dependence of density of state and also from the status of
excitation of the system at reduce dimension.

1. Coulomb Interaction in Nanostructure:

As we have already mention that within nano sized material there are restrictions of the
movement of the carriers (electrons and holes), this restriction for confinement gives the
quantization of the energy sates or energy levels. Mathematically one can show that such

.
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quantization of the energy states in nano material gives the energy difference of two

discrete energy level as where

ia
is the effective mass of the carrier and d is
er
the interval of length in restriction. Coulomb interaction in nano material can be managed
at

with the correction of such Coulomb interaction in bulk material and the correction is
M

made for such restriction of motion of the carrier within nano structure.
o

Since we have already informed that the dimension of nano sized material will affect the
an

degree of freedom of the carrier inside it, the restriction of

.N

the carrier within this stru8cture will also become affected

by this degree of freedom. Again we should recall that the
effective dimension of nano material is D= 3 – I where I is
the number of direction of restriction or limitation in
movement of the carrier for space confinement, in fact,
we have in general the energy value at n’th energy state in

2D Coulomb problem is given by for hydrogenous nano material where

is reduced mass and the factor comes for ‘quantum defect’ at lowest orbital in n’th

state.

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With such restriction in carrier movement for confinement, the additional characteristics
which are also required to take into account for the analysis of the nano optical behavior
are

a) For metallic nano structure, the free electrons participate in resonant vibrations at a
frequency depending on the shape and size and the composition of the nano materials.
When the frequency of the incident light photon matches with this frequency of vibration,
the photon will be strongly absorbed by the nano material and the material looks certain
colored. Obviously, by tuning the size and shape of the given nano system, the peak
wavelength at resonance can be changed and as a result, colour variation will occur.

b) If the nano material has ordered structure with the proper gathering of nano particles
inside it, such that the structural element becomes similar in size to the wavelength of

.
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light then this structure selectively reflect certain portion of the spectrum resulting nano
ia
optical films with some optical responsibilities
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c) For quantum dots (specially semiconductor quantum dot which is the collection of 100
at

to several thousand atoms with bulk bonding geometry, may illuminates and responses
M

like illuminated bulk body with respect to incident photons on it. But here the modified
o

band structure and reduced band gap for confinement will give a few exceptional optical
an

characteristics.
.N

2. Concept of Dielectric Constant for Nanostructures:

Since micro or nano particles can be synthesized from the macro or bulk material, we can
consider the macro system as the sum of micro or nano contributions. Thus
mathematically we can define a macroscopic quantity in terms of a microscopic
quantity as

where is a weighting function or weighting factor which is used to suppress the

statistical fluctuation in the microscopic function .

As for example, consider a bulk system of charge distribution having volume density of
charge usually varying from one source point to another source point. This
charge density is a micro parameter and here the net electrostatic potential contribution
for the whole bulk system of charge at any outer field point will be

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 when and

Now from Maxwell’s equation which include space derivative of the micro quantities, if
we take their averages, it is necessary to have an average quantity

It is easy to note that for constancy of the product at each segment of the
macro or bulk structure, we have

.
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But also we have So we get
ia
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As a result, we can now write the expression of as
at
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o
an

Therefore we see that the average is equal to and we can easily transpose Maxwell’s
equations by changing all microscopic quantities to their macroscopic counterparts.
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Everything which we have uptill now discussed is for macroscopic system and one can
thought that is this macroscopic approach breaks down when the system size is reduced?

In fact for nanostructure, it has been

observed that a local dielectric
constant depending on the position
in nanostructure exists and it differs
from that of the bulk material only a
very close to the structure.

Besides, the average dielectric

constant (where average is taken
over the volume of the
nanostructure) is seen to vary with
the size of the structure.

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In case of homogeneous bulk material with bulk dielectric constant , Coulomb potential
energy between two charged particles in Bulk material is given by

and when the material is inhomogeneous, the potential will be different from .

Also in such a case, the electrostatic energy of a typical changed particle depends on the
position r. In fact, the charge polarizes the dielectrics inducing polarization charge at the
interfaces as well as surface. Thus, the interaction energy known as self-energy depends
on the position of the particle with respect to interface and surface.

Because of the nanometre length scale, the Coulomb interaction between the charged
particle and a dielectric quantum well is largely modified. For example, it has been
indicated by Keldysh that if the semiconductor quantum well (i.e. semiconductor nano

.
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film) is made sandwiched between insulators or semiconductors with a small dielectric
constant the long range Coulomb interaction is significantly enhanced in compared to that
ia
in the bulk or macro material.
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Again it is observed that if a uniform electric field is applied to a nano dielectric sphere,
at

the screened electric field inside the sphere is uniform and given by
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where is the effective relative permittivity or dielectric constant inside nano material
o

and here this unusual result basically occurs due to the strong surface effect for
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polarisation of the nano structure as done by applied field.

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Thus, for a physically meaningful description of a dielectric constant in a nanostructure,

one must take into account the fact that a dielectric constant is required to be
calculated at each position r in the nanostructure by imposing that the macroscopic
relation between the screened field E and applied field is maintained.

Then the average dielectric constant for a nano structure is defined as the average of
this local dielectric constant over the volume of the nanostructure as

3. Charging of Nanostructure:
Consider a quantum dot of radius R which is an ideal nano structure of 0 dimension having
dielectric constant and it is surrounded by the bulk medium of dielectric constant .
The potential energy of a charge q located at which is induced by charge q’ at
in outside region is given by

Where

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 and the fluctuation can statistically be obtained as

Here is the angle between the two vectors .

On the other hand, it can also be shown that if the charge q is located at the center of the
dot, the electrostatic potential in the dot is given by

The second term in the bracket indicates the polarization charge at the surface of the
quantum dot. In the limit of , this constant term however emerges as the main

.
contribution of the potential in the large part of the dot and we get

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Here the main thing is that the electrostatic nature of the nano material differs from that
at

of the bulk medium for the strong polarisation effect on the surface of the structure and
M

here the surface contribution of the polarized charge should be taken into account for its
small shape whereas it can be ignored at any location inside a bulk material for its large
o

shape. Thus effectively the charging of this nano material can be taken in different way
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equivalently as that the electrostatic contribution can be correctly worked out.

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4. Quasi – Particles and Excitons:

The idea of quasiparticles originated in Landau’s theory of Fermi liquids, which was
originally invented for studying liquid helium-3. In physics, quasiparticles and collective
excitations (which are closely related) are emergent phenomena that occur when a
microscopically complicated system behaves as if it is weakly interacting particles in free
space.

For example, as an electron travels through a

semiconductor, its motion is disturbed in a complex way
by its interactions with all of the other electrons and
nuclei; however, it approximately behaves like an
electron with a different mass (effective mass) travelling
unperturbed through free space. This electron with a
different mass is called electron quasiparticles.

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In another example, the aggregate motion of electrons in the conduction band of a
semiconductor or in a metal is the same as if the material instead contained positively
charged quasiparticles called electron holes. Other quasiparticles or collective excitations
include phonons (particles derived from the vibrations of atoms in a solid), plasmons
(particles derived from plasma oscillations), and many others.

Thus a quasiparticle is usually thought of as being like a modified particle; it is built

around a real particle at its core, but the behaviour of the particle is affected by the
environment.

A standard example is the electron quasiparticles: an electron in a crystal behaves as if it

had an effective mass which differs from its real mass. On the other hand, a collective
excitation is usually imagined to be a reflection of the aggregate behaviour of the system,
with no single real particle at its core.

These particles are typically called quasiparticles if they are related to fermions, and called

.
ls
‘’collective excitations’’ if they are related to bosons, although the precise distinction is
not universally agreed upon. Thus, electrons and electron holes are typically called
ia
quasiparticles, while phonons and plasmons are typically called ‘’collective excitons’’.
er
Therefore the quasiparticle consists of the original real, individual particle, plus a cloud of
at

disturbed neighbours.
M

It behaves very much like an individual particle, except that it has an effective mass and a
lifetime. But the collective excitations do not center on individual particles, but instead
o

involve collective, wavelike motion of all the particles in the system simultaneously. For
an

example, a phonon is a classic example of collective excitation associated with the

vibration of atoms in a rigid crystal structure. It is a quantum of a sound wave.
.N

In the same note, a magnon is a collective excitation associated with the electrons’ spin
structure in a crystal lattice. It is a quantum of a spin wave. A Plasmon is a collective
excitation, which is the quantum of plasma oscillations (wherein all the electrons
simultaneously oscillate with respect to all the ions). However, a polaron is a quasiparticle
which cones about when an electron interacts with the polarization of its surrounding
ions.

5. Basic Concept of Direct and Indirect Band Gap Semiconductor:

We know that the band formation of a bulk semiconductor is parabolic when considered
in energy – momentum space. The conduction and valance bands are in opposite sense
and their vertices may or may not lie on the same energy axis at certain momentum value.
This gives a typical classification of a bulk semiconductor which is Direct and Indirect band
gap semiconductors.

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For direct band gap semiconductor, these vertices of two energy bands lies on the same
energy axis and thus they are suitable for making opto – electronic devices because of
photon emission through direct electron – hole recombination without any change of
momentum. As for example, GaAs is a direct band gap semiconductor which is widely
used for fabrication of LED.

On the other hand tetra valent semiconductor Ge, Si... are indirect band gap
semiconductor where valance band and conduction band vertices has a lateral difference
of momentum and in that case, electron hole recombination takes place via a trap with
release of some amount of thermal energy for certain momentum transfer.

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6. Excitons in Direct Band and Indirect Band Semiconductor Nano Crystals:

The fine structure in the lowest excitonic states of quantum dots or nano crystals mainly
depends on the following terms of the Hamiltonian:

1. Confinement interaction 2. Spin-orbit interaction 3. Coulomb interaction and

4. Exchange Interaction

Out of these, in the case of nano crystals, the matrix element for spin-orbit interaction
turns out to be constant. However, the electron – hole exchange interaction increases
with decrease in size of the nano crystal.

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In fact, when the electron-hole exchange interaction is negligible with respect to spin-
orbit interaction, then the effective mass approximation (EMA) can be used to calculate
the splitting energy levels of spherical nano crystals.

.
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In this approximation the magnitude of the splitting related to the electron-hole exchange
ia
of a typical nano crystal in the following way given by
er
where is the exciton Bohr radius, is a characteristic constant related to nature of the
at

semiconductor.
M

This scaling is the consequence of EMA. A closer look into the respective wave functions
o

of bulk and nanophase is the key factor for such scaling relation.
an

A close look to the band structure of semiconductors allows predicting which regions in k-
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space are favourable for the formation of excitons. Because the exciton is composed of a
bound electron-hole pair, the velocities of both particles should be the same. Therefore,
their respective conduction and valence bands should be parallel. This is evidently the
case in the vicinity of the point .

If the intensity of the light that creates excitons is high enough, their density increases so
much that they start to interact among themselves and with the free carriers. In this high-
density regime, biexcitons consisting of two excitons can be created.

Biexcitons have been detected in bulk semiconductors as well as in quantum wells and
dots. Biexcitons consist of two electrons and two holes and, similar to the procedure
followed to study excitons in terms of hydrogenic atoms, these can be compared to
hydrogen molecules.

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7. Quantitative Treatment of Quasi – Particles and Excitons:
Exciton can be treated by the optical excitation across the gap inducing an electron-hole
pair. In a qualitative physical picture, the excitation energy will be equal to the quasi-
particle gap corrected by the average value of the electron-hole pair Hamiltonian as

consists of two terms (i) the kinetic energy term T due to the mixing of electron-hole
wave function to the excited quasi particle states. Secondly (ii) a potential energy term
due to the screened Coulomb interaction between two quasiparticles. The excited energy
can be also written in the form

where is the sum of independent particle energy value .

.
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Here is the self-energy correction. Most of these calculations are done effectively in
ia
the framework of density functional theory (DFT) with suitable approximations such as
er
local density approximation (LDA), generalized gradient approximation (GGA), LDA + GW
etc.
at

As is well-known that LDA gives an underestimation of the energy, most often GW has
M

taken a leading role in computing the energy of the quasiparticle in the excited state. GW
approximation is based on the expansion of the exchange of the quasiparticle in the
o
an

excited state. GW approximation is based on the expansion of the exchange-correlation

self-energy in terms of the dynamically screened electron-electron interaction. The name
.N

GW implies the suitable correction viz Green’s function (G) and the self-energy operator
modified by the retarded interaction . In fact, the self-energy operator can
be written as

is basically the product of G and W. Most often situation due to strong cancellation
between two large quantities it is found that

This eventually suggests the reason why the single crystal particle calculation can yield
quite correct result for . In the LDA scheme, it is found that so that
can be written as . Most of the results however, match with this
single particle calculation for estimation of the excitonic gap.

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8. Radiative Processes:
The expression radiative processes comprises of all the various physical processes by
which a medium releases energy in the form of electromagnetic radiation. At the
microscopic level, this involves the emission of a photon by an elementary particle, as the
result of specific interactions with other particles at particular conditions of temperature,
acceleration and/or excitation.

Several radiative processes producing

continuum emission can be identified:
on one side, black-body and
Bremsstrahlung radiation which are the
source of thermal emission, and on the
other side, cyclotron, gyro synchrotron
and synchrotron emission which are

.
considered as non-thermal processes.

ls
ia
All electromagnetic radiation arises from transition between levels with difference in
electric or magnetic moment. The levels could be discrete or in continuum. And the
er
transition takes place between each pair of levels involving emission and absorption. The
at

processes involve non-vanishing matrix elements with dipole or higher multipole.

M

Radiative properties are fundamental physical properties that describe the interaction of
electromagnetic waves ranging from ultraviolet (UV) to deep infrared (IR) spectral regions
o

with matter.
an

They can be broadly classified into optical radiative properties and thermal radiative
.N

properties. Understanding the radiative properties of materials is critical for the proper
selection and interpretation of temperature measurement techniques in various industrial
processes. Radiative property measurements enable us to understand the physics of solids
and other states of matter.

9. General Formalization of Absorption, Emission and luminescence:

Consider a discharge tube made by glass which is filled by some gas and there are two
metal plates at both ends. If a large enough voltage difference is applied between these
two metal plates, the gas atoms inside the tube will absorb enough energy to make some
of their electrons come off i.e. the gas atoms becomes ionized. These electrons start
moving within the gas through successive collisions with the other atoms making the
electrons of those other atoms excited to their higher energy states and as a result the
electrons in those atoms immediately fall back down and thus electromagnetic radiation
(light) will be emitted. These light or radiation emitted at different wave-lengths will give
the emission spectrum. Only certain spectral lines of particular wavelengths (i.e. colours)

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will be visible. These lines appear due to emission of photons of a specific energy, emitted
by electrons making transitions between specific energy levels of the atom.

When an electron in an atom falls from a higher energy level to a lower energy level, it
emits a photon carrying with energy equal to the energy difference between the two
energy levels i.e.

The frequency of a photon

related to this energy states

transition will be and this

specific photon frequency (or

wavelength) gives us a specific

.
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colour of spectral line.
ia
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Here the fact is that the atoms do not only emit photons; they can also absorb photons. If
a photon hits an atom and the energy of this photon is the same as the energy gap
at

between two electron energy levels in the atom then the electron in the lower energy
M

level can absorb the photon and jump up to the

o

higher energy level. If the photon energy does

an

not correspond to the difference between two

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energy levels, then the photon will not be

absorbed and in that case, it will be scattered
from the atom.

Using this effect, if we have a source of photons

of various energies we can obtain the
absorption spectra for different materials. As
for example, since white light contains different
wavelengths of visible light, when it is allowed
to fall on a medium of specific atoms, in the
absorption spectrum of that white light after passing through that medium, there will be
gaps or absence of a few specific emission spectra. This absence of specific emission
spectra is the appearance of specific absorption spectra and the energy gap responsible

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for that occurrence absorption spectra correspond to energies (wavelengths) for which
there is a corresponding difference in energy levels for the particular element.

The absorbed photons thus give black lines because the photons of these wavelengths
have been absorbed and do not show up. Because of this, the absorption spectrum is the
exact inverse of the emission spectrum. It is the exact opposite of the emission spectrum.

Both emission and absorption techniques can be used to get the same information about
the energy levels of an atom. The dark lines correspond to the frequencies of light that
have been absorbed by the gas. As the photons of light are absorbed by electrons, the
electrons move into higher energy levels. This is the opposite process of emission. The
dark lines, absorption lines correspond to the frequencies of the emission spectrum of the

.
same element. The amount of energy absorbed by the electron to move into a higher level

ls
is the same as the amount of energy released when returning to the original energy level.
ia
In figure, we schematically highlight the features of absorption and emission spectra.
er
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The difference between absorption and emission spectra are that absorption lines are
where light has been absorbed by the atom thus we see a dip in the spectrum whereas
emission spectra have spikes in the spectra due to atoms releasing photons at those
wavelengths.

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Note that in absorption and emission, the electronic transitions between the energy levels
directly take place through the interaction of the electrons with electromagnetic fields in
the system. Most of the effects however can be treated in semi-classical fashion.

Here in this process of emission or absorption within a nano crystal, the only
experimentally observed quantity or experimentally measurable quantity is the
probability of transition of electron which is proportional to intensity of the EM field
inside the nano crystal.

But the fact is that the field inside the nano crystal is not equal to the field in the
surrounding medium of different dielectric constant. The back ground field is usually
smaller than the field inside the nano crystal. This field within the nano medium is
sometimes called local field (which is very similar to the local field at any atomic site when

.
isolated by the micro spherical region in a bulk polarised medium) and this basically

ls
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occurs due to dielectric confinement in nano medium like Quantum Dot.
er
On the other hand, Luminescence is another optical effect closely related to spectroscopy,
at

which is required for the study of the general laws of absorption and emission of radiation
by matter. The phenomenon of certain kinds of substance (called luminous organisms
M

such as bacteria in the sea and/or in decaying organic matter) emitting light on absorbing
various energies without heat generation is called luminescence. Luminescence is
o
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obtained under variety of excitation sources. The wavelength of emitted light is

characteristic of the luminescent substance and not of the incident radiation.
.N

10. Optical Properties of Nanostructures:

The optical properties of low-dimensional structures are very different from those of the
bulk material mainly as a consequence of modified band gap and stronger excitonic
effects. This is especially true in the
case of QDs because of confinement
in all three dimensions. In particular
the optical properties related to
interband transitions in quantum
wells are quite different to those
corresponding to bulk systems,
because of the peculiarities of the
two-dimensional (2D) optical DOS

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and the fact that excitonic absorption is much stronger in 2D systems.

Interband transitions take place from an initial state in the valence band to a final state in
the conduction band. Thus the absorption will appear at energy gap higher than the band
energy gap for the 3D case, because the energy difference between the bands in 3D nano
structure is larger than the energy band gap of the semiconductor. The transition rates or
transition probabilities are computed via Fermi golden rule, from first order time-
dependent perturbation theory

where is the energy density at final state to which transition occurs and the
perturbation term is associated with the interaction between photon and can be
expressed as

.
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11. Optical Properties of Heterostructures:
at
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Now we would like to discuss the optical absorption of systems with reduced
dimensionality based on direct gap semiconductor. In particular we would like to compare
o

the absorption spectra of the bulk structure to quantum wells and quantum dots. The
an

discussion will follow in the line of effective mass approximation considering the one-
particle and excitonic transitions.
.N

Here we know that the wave function presentation of energy band is

with is the periodic part of the Bloch function for the band and is the
envelope function solution of a Schrödinger like equation given by

But we have for parabolic band . Therefore we have

the optical matrix element

Here is the volume of the elementary cell of the semiconductor. The first term in above
equation is non-zero but the second term is zero for interband transitions. While for

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intraband transitions, the reverse is true i.e. the first term is zero while the second one is
non-zero.

For interband transition in bulk semiconductor, the optical matrix element between two
states with different wave vectors, according to Bloch theorem is zero. This indicates that
the transition is vertical with the BZ. In other words, it occurs at fixed . Therefore the
absorption coefficient further reduces to

Since and are respectively the bottom of the conduction band and top of the
valence band, we have the band gap .

Assuming further the independence of we obtain finally

.
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ia with
er
Considering the DOS in 3D, we eventually identify that the absorption coefficient is
at
M
o

We have not assumed any interaction between the quasiparticles. Naturally this
an

absorption process is responsible for the formation of an electron-hole pair. However two
quasiparticles can attract each other via screened Coulomb potential giving rise to
.N

localized states.

Thus the absorption spectrum instead of starting at the energy gap can show lines at
where is the static dielectric constant of the semiconductor.

12. Stokes Shift:

The Stokes Shift is the spectral shift to lower energy between the incident light and the
scattered or emitted light after interaction with a sample.

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In nano material, Stokes shift is primarily the result of two phenomena: vibrational
relaxation or dissipation and solvent reorganization. A fluorophore is a dipole, surrounded
by solvent molecules. When a fluorophore enters an excited state, its dipole moment
changes, but surrounding solvent molecules cannot adjust so quickly.

Stoke's shift can occur in atomic spectroscopy when an electron is excited to a high energy
electronic level emits a photon and relaxes to a lower excited electronic level, the emitted
radiation (solid line) has lower energy, and thus longer wavelength.

A larger Stokes shift eliminates spectral overlap between absorption and emission and
allows detection of fluorescence while reducing interference. This also eliminates
quenching of fluorescence and gives a stronger signal when used for biological imaging.

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 Electron Transport

1. Introduction to Electron Transport in Nanostructure:

Conventionally electrical conduction in a bulk conductor mainly occurs through the drift
motion of a single carrier – electron under certain applied potential gradient. Similarly in a
bulk semiconductor, both drift motion and flow of carrier through diffusion for
concentration gradient are usually taken for electron and holes during electrical
conduction in semiconducting material. In that case somehow quantum tunnelling of the
carrier through barrier potential can be taken as per requirement.

But in a nano material, it is required to connect such effect of drifting or tunnelling of the
carrier with quantum confinement for size effect. Since such confinement effect ensures

.
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the reduced dimension of nano structure, this connection will be also affected to the
behaviour of the carrier in several reduced dimension.
ia
er
As for example, in 2D nano film, only movement of carrier takes place in a plane and then
it is called ‘Parallel transport’ and this will affect the electrical transport in 2D nano
at

structure. Also in this case the electrical conduction in presence of external magnetic field
M

will give Quantum Hall Effect (QHE)

o

On the other hand, in 3D nano tube, mesoscopic transport or quantum transport is taken
an

which is basically the quantization of electrical conduction in unit of . On the other

hand, in a very small nano stricture such as quantum dot (0 Dimension) or nano dot, the
.N

effect of Coulomb Blockade occurs in such electrical transport.

Thus by connecting confinement effect in electrical transport within nano structure,

several exceptional results will appear which are basically absent in the properties of
electrical conduction in bulk material.

2. Carrier Transport in Nanostructures:

We need to know the manifestation of quantum mechanics on the electrical transport

properties of conductor. The question is that will the relation
remain valid for nanoscale also?

The expected effects of electrons in nanostructures are the following:

a) Quantum Confinement b) Tunnelling effect c) Charge discreteness and Strong electron-

electron Coulomb interaction d) Strong Electric field Effects d) Ballistic Transport effect

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Several length scales play important key role in the transport processes. The average
distance travelled by the electrons without being elastically scattered is known as elastic
mean free .

If is the Fermi velocity of electron, then this length scale in terms of elastic
relaxation time Similarly, the average distance the electrons travelled before their
phase is randomized (change) is known as phase coherent length . Again in terms of
dephasing time or phase relaxation time , this coherent length

The Fermi wavelength is nothing but the de Broglie wavelength of Fermi electrons. In
an arbitrary spatial d dimension, the Fermi wave vector is related to the number of
density electrons in the following way

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This enables us to compute the Fermi wavelength in an arbitrary spatial dimension d as
ia
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at

Thus from above expression one can easily obtain the various Fermi wavelengths in
different dimensions as
M
o
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For conduction in the nanostructure, the following conditions are to be satisfied. The
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nanostructures dimension L does satisfy the following limit

All these are quantisation of electrical transport in nano structure (i.e. nano scale
transport) which is particularly the quantization of electrical resistance in nano structure
and this can be visualized from the famous Drude Conductivity as follows.

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Let us consider the random collision processes between electrons. The electron taken
random at time t will have a collision

before time with probability .

The electron will eventually survive at

time from time to without
suffering a collision with

probability .

Thus according to joint probability of

independent processes, the collision
probability at will satisfy the

.
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equation
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The normalized probability solution of the above differential equation is

o

Therefore the current density can be computed from the velocity as

an
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Following the general conductivity relation this electrical conductivity in

nano structure now can be written in the following way

If , then for 2d system , it is easily seen that and is quantized.

In general, the resistance of such a nanostructure can be written as

Because of this exponential dependence with system size L, the resistance additive rule is
not satisfied for nanoscale systems.

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3. Coulomb Blockade Effect:

Quantum dots consist of atoms with an equivalent number of electrons. In

semiconductors, all electrons are tightly bound to the nuclei except for a small fraction of
conduction electrons. This small fraction can be varied from a single free electron to a
several thousand free electrons by attaching a gate to the quantum dot and applying a
voltage.

Due to the three dimensional confinement of the electrons and the resulting quantized
energy spectrum, quantum dots are often regarded as artificial atoms. Quantum dots can
also be operated as transistors via a field-effect gate. These devices are named as Single
Electron Transistors (SETs) and are reminiscent of the classical MOSFET; but instead of the
usual inversion channel, a quantum dot acting as a conducting island, referred to as a
Coulomb island, is embedded between the source and drain electrodes.

The current flows from lead to lead through the quantum dot via a process called

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tunnelling. In this type of situation, the quantum dot is acting as a conducting island,
ia
referred to as a quantum or Coulomb island. In order to model the quantum dot and its
exterior leads, the classical concept of capacitance is used, resulting on a mixed classical-
er
quantum model.
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Firstly a simple model of two conductors separated by an insulating material will be

considered. The space between the conductors will exhibit a capacitance C where

where Q is the net charge of the conductors, and V is the d.c. voltage between the two
conductors. The electrostatic energy stored between them is given by:

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where n is the number of electrons between the conductors (we assume that a single
electron is trapped) and e is the electron charge. This energy is known as the Coulomb
charging energy or simply charging energy and it is the energy required to add charge to
one of the conductors. For both conductors, the charging energy becomes:

This energy surpasses further electron transfer between the leads, unless it is overcome
by either thermal excitations or by an external bias voltage. This suppression of electron
transport is termed Coulomb blockade to tunnelling, or simply Coulomb blockade.

For a simple capacitor formed by two parallel conducting plates of area A and plate
separation d, the capacitance of the configuration is given by: where is the static
dielectric constant.

.
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Therefore, for plates with nanoscale dimensions, the small values of capacitance will lead
ia
to a considerable change in the Coulomb charging energy. While in macro-sized circuits,
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because the area of the capacitor plates is very large, no Coulomb Blockade effects can be
observed.
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For a disk type capacitor of diameter d, the capacitance is given by

For a spherical capacitor of diameter d the capacitance is given by

o
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If the radius of such a spherical capacitor is expressed in nanometre, then the capacitance
is expressed in Farad units as
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4. Thermionic Emission: Richardson’s law

Thermionic emission must not be confused with thermionic emission (of black body for
example) where photons are emitted from heated body. In the case of thermionic
emission, we observe emitted electrons from a metal due to its high temperature. Mobile
electrons in metals, also called valence electrons, are responsible for electric current
conduction. If we increase the temperature of the metal, electrons that to move faster
and some may have enough energy to escape (evaporate) from the metal. The higher the
temperature, the higher will be the current of escaping electrons. This temperature
induced electron flow is called thermionic emission.

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 .
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If we use the hot metal from which electrons evaporate as a cathode on a high potential
M

difference to the anode and then we get electric field between cathode and anode and
emission of electrons can be measured as a anode current.
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Potential barrier at the metal surface tends to prevent free electrons from escaping at low
temperatures. When the metal is heated to sufficiently high temperature, some of free
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electrons get enough energy to carry them over potential barrier. With suitable electric
field these electrons can be then drawn away from metal and measured. Electrons
emitted by the filament are drawn to the anode, and then the anode current is controlled
primarily by the filament temperature and is practically independent of the potential.
Under these conditions anode current is said to be saturated, and is purely a function of
the temperature. Richardson’s law tells us what is the current density of
thermally escaped electrons in the direction perpendicular to heated metal. The famous
Richardson’s equation reads as

where is Richardson’s constant with a value and if U is the

confining potential barrier, then the work function is the minimum amount
of energy needed for an electron to leave the metal and depends on a metal. With
increase of temperature , the number of thermions (thermally excited

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electrons) emitted increases rapidly. The equation is rather dominated by the exponential
factor (which is a very small number since a typical work function is larger than thermal
energies).

Of course, large thermionic currents require high T. For at room temperature

while at 3000K, it is . Increasing T does not ensure
observable electron emission, since material can evaporate, melt or decompose. In this
sense, tungsten (thorium coated iridium) can be used reasonable for this purpose.

There are many other phenomena happening on small accompanying thermionic emission
when real experiment is done. Let’s only mention some of them. The work function in fact
slightly depends on
temperature due to thermal
expansion of the atom
lattice. Richardson’s law
does not take this into

.
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consideration. Vacuum in
ia the tube where experiment
is performed is of course
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not a real vacuum but at a reasonably low pressure. Bulbs that are used in experiment are
at

usually filled with argon gas under negative pressure. Gas atoms may impede electrons at
lower voltages on the path to the anode, but when the field is stronger enough atoms get
M

excited and may themselves cause some anode current. Surface of the filament is
o

contaminated with other atoms besides tungsten and the filament itself has some
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impurity.

This inherently affects the emission probability and work function. At higher voltages,
.N

strong electric field reduces the barrier of electron emission so the work function
decreases. Due to so called Schottky emission, however, electrons can tunnel through the
barrier even if they lack the energy required classically to overcome potential barrier.
Microscopic peaks on the surface of the filament enhance the electric field near the peak
slightly beyond that calculated for a smooth surface.

Photoelectron emission spectroscopy (PES) is the general term for spectroscopic

techniques based on the outer photoelectric effect. The surface of a solid metal is radiated
with ultraviolet light and the kinetic energy of the emitted electrons is analysed. As UV
light has energy lower than 100eV it is able to extract mainly valence electrons.
The resulting spectrums reflects the electronic structure of the sample providing
information on the density of states, the occupation of states and the work function.

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5. Tunnelling Conductivity:
Tunnelling occurs through the insulating gaps between two conducting regimes. In this
mechanism, electrons try to tunnel between conducting regions at points of their closest
approach. However, these tunnel junctions being
extremely smaller in size gives rise to large
thermally activated voltage fluctuations across
the junctions. By tailoring the potential barrier,
the voltage fluctuation can affect significantly
the tunnelling probability and hence the
conductivity. It is interesting to note that the
normal tunnelling conductivity is temperature
independent while this fluctuation induced
tunnelling depends on the temperature in a
characteristic way. The typical systems where this particular type of conduction can occur

.
include conductor-insulator composites, disordered semiconductors and doped organic

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semiconductors. ia
Conductivity due to Fluctuation Induced Tunnelling:
er
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The fluctuation induced tunnelling (FIT) conductivity and high field tunnelling current
density reduces to a simple form
M

where denotes the temperature below which the conduction is dominated by the
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charge carrier tunnelling through the barrier. Note that always appears into the above
equations as an additive constant to T. Therefore, it can be visualized as the temperature
.N

at which the fluctuation effects become important. can effectively give the
estimation of the height of the barrier and the width of the junction. Quantitatively,
the expressions for are and

with . In the above expression A denotes the area of the

capacitance. If the gap width depends on the density as , then it is easy to
visualize that

Moreover, it is evident that the ratio is proportional to and hence proportional to

. These formulas are important in studying the conductivity for many nanocomposite
systems. While limit, becomes temperature independent

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The reason of this temperature independence lies with the elastic tunnelling. If the
temperature is increased from , the absolute magnitude of the exponent
in decreases from their respective values. This indicates that the tunnel barrier as
observed by the electrons is decreased in height by the fluctuating voltages. Moreover,
when , the most rapid change in barrier height takes place. From the experimental
point of view, it is easy to write the resistivity expression from the conductivity as

In case of electronic transport through a thin amorphous layer (thickness less than the
localization length), then a new kind of conduction known as direct tunnelling process
may appear as the dominant one. With the increase of the barrier thickness, it is noticed
that the conductance depends on the temperature and the bias voltage as a power law
which are drastically different from the usual Wntzel-Krammer-Brillouin (WKB) tunnelling
model.

.
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6. Hopping Conductivity: ia
Variable range hopping, in short form as VRH is an important model till date to discuss the
er
electrical conduction at low temperature in amorphous systems. It is necessary to
at

understand this simple model to interpret the low temperature conductivity data of the
M

samples.

Mott’s law of Variable Range Hopping Conduction

o
an

The atoms in amorphous material are distributed at random and the electrons associated
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with them have distribution of energies. An atom might have an empty state whose
energy is slightly higher than that of the occupied state of a chosen given atom. Typically
the activation energy required for electrons to hop to an empty state is very small and
hence the hopping conduction takes place.

Moreover, hopping is always associated with some activation energy because the
localized states have quantized energy levels. The hopping distance varies because of the
random arrangement of the atoms having suitable energy scales and hence the name is
given as variable range hopping (VRH). This hopping process differs from the usual
electrical conduction in normal metal. Here in the hopping process, phonons assist the
transport while in typical band theory; the transport is impeded by the destruction in
periodicity caused by the lattice vibration. The hopping of charge carriers through
different distances is shown in figure in various cases.

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58 61
We consider two localized states – one filled and at or slightly below the Fermi energy
and the other empty above ; their energy and spatial separations are W and R
respectively. The hopping transition rate p is given by

The first factor is the quantum mechanical tunnelling probability and is just the overlap of
the two localized states (one below the Fermi energy and the other above )
exponentially decaying with the same characteristic localization length . The
exponential nature of the wave function is the characteristic feature of the ground state
Eigen function of hydrogen like atom and is isotropic in nature. R is the typical hopping

distance between the localized states is the energy separation between

.
the final and initial state.

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The second factor arises because of the
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fact that the different localized states
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must have different energy. This

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difference in energy is supported

by the phonon scattering and governed
o
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by the Boltzmann weight at temperature

T. Note that essentially depends
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on separation between the localized states. At high enough temperature or high electric
field, the variable range hopping distance R becomes equal to the nearest neighbour
distance. The attempt frequency depends on the strength of the electron-phonon
coupling and the phonon density of states but almost independent of R and W.

An electron will always try to have lowest W, the energy difference between the localized
states as well as the lowest hopping distance R. However, these two conditions cannot be
satisfied simultaneously. In fact, the electrons have a tendency to hop to more distant
neighbours where the energy difference W is smaller. This automatically gives rise to an
optimum value of the hopping distance R obtained by maximizing the transition
probability. This maximization is simply done by the optimization of the exponent given
by , where depends on R.

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59 61
Depending on the specific for of the localized wave function, there may be an additional
pre-factor in the above equation. However it is seen that the exponential is the most
common form of the localized wave function used in the literature. In order to highlight
the differences between tunnelling and variable range hopping, a schematic diagram of

.
these two events is shown in figure.

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7. Defects and Impurities:
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Defects in materials are inevitable. They will always form due to the fact that all processes
are almost always far from equilibrium and take place at finite temperatures .
o
an

According to thermodynamics, the change in Gibbs free energy of a chemical reaction in a

closed system at a given temperature T is given by
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Where is the change in enthalpy while denotes the change in entropy of the
reaction. The reaction will proceed spontaneously as long as until becomes a
unique global minimum. In fact, is the condition for thermal equilibrium at a given
temperature T.

The creation of single unassociated point defects in an elemental crystalline solid

eventually increases the internal energy and hence, the enthalpy of the defect formation
is positive. On the other hand, the configuration entropy of the system will also
increase. Finally, the equilibrium defect concentration will be determined by the condition
when the Gibbs free energy of the system reaches its minimum. Thus, thermodynamically,
the point defect will always be present in a crystal at above 0K.

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60 61
It is important to have knowledge about the types of imperfections that exist and the
roles they play in affecting the behaviour of materials. Defects/impurities are ubiquitous
in nature. They are indeed very important because they have strong influence on
properties not only by themselves but also through interaction with other various defect
types. Impurities are essential for giving semiconductors the properties that render them
useful for electronic as well as optoelectronic devices. The intrinsic carrier concentrations
in most semiconductors however are quite low.

Adding small amounts of impurities allows control of the conductivity of the

semiconductor: shallow donors, such as phosphorous in silicon, produce n-type
conductivity (carried by electrons), and shallow acceptors, such as boron in silicon,
produce p-type conductivity (carried by holes). These doped layers and the junctions

.
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between them control carrier confinement, carrier flow, and ultimately the device
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characteristics. Commonly used semiconductors such as Si and GaAs can be doped both p-
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type. Constraints on doping still limit device performance.
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8. Deep Level Defects and Impurities:

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Deep-level traps or deep-level defects are generally undesirable type of electronic defect
in semiconductors. They are deep in the sense that
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the energy required to remove an electron or hole

from the trap to the valence or conduction band is
much larger than the characteristic thermal
energy , where is the Boltzmann constant and T
is temperature. Most often, the word Deep signifies
the energy of the order of 150 meV from the
conduction band or valence band edges.
Semiconductor properties are strongly influenced by
defects with which produce deep levels in the band
gap.

The binding energies E of the shallow impurities or shallow levels of donor and acceptor
impurities are typically (away from one of the band edges).

So ( is the host band gap). So these impurities are often labelled shallow
impurities or shallow levels. The effective mass approximation (EMA) has been very

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61 61
successful at predicting the defect energy levels E. Moreover, shallow levels can be
introduced non-uniformly into the material so that p-n junctions are possible.

9. Surface Defects:
Surface defects are associated with boundaries that are separate regions of the materials
and have different crystal structure. These are essentially two-dimensional in character
and appear due to change in orientations of the planes and stacking sequence of planes.
They are caused during solidification or mechanical or thermal treatment of the materials.
These are areas of distortions which lie about a surface having a thickness of a few atomic
diameters (in other words the thickness is negligible compared to other dimensions of the
surface).

.
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From the thermodynamics point of view, surface defects are not stable rather they are
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metastable in nature and can be removed under suitable conditions. These defects tailor
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the mechanical properties, electrical resistance and corrosion resistance.
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Surface defects can broadly classify

into three categories:
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1. Free surface/External surface

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2. Gain Boundaries/Inter-crystalline
boundaries

3. Internal defect/Stacking faults

All of these defects however have two important characterizations. Firstly, since they are
surfaces in a crystal hence they must have particular atomic structure depending on
orientation. Secondly, they have a positive energy. The energy per unit area is equal to
the surface tension of the interface.

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62 61
 Characterization [Ch.5]

1. X – Ray Diffraction: Diffraction of X-rays by Crystals: Bragg’s Law:

We all know that when a wave passes through a very narrow hole having dimension
comparable to the wave length of that wave, the direction of propagation of that wave
will bent from the original direction
and then the wave is said to be
diffracted. Similar to that fact if we
consider diffraction of X ray which is
basically electromagnetic wave
having very high frequency and very
short wavelength, its wavelength
can considered to be compared with

.
the inter atomic spacing in a crystal

ls
lattice. Thus X ray may be diffracted ia
from a crystal lattice in real sense
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and that was first imagined by Bragg at his time of crystallographic generation.
at

To study such X ray diffraction through crystal lattice, Bragg first makes a few assumptions
which are
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a) When X ray passes through the crystal lattice. It will be scattered fully elastically from
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each atomic site at any lattice point.

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b) Scattered X ray from atomic site can be taken in a particular sense as a reflected wave
when reflected from the corresponding lattice plane supposed to be passing through the
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given atomic site.

c) All the so called reflected waves from a set of parallel lattice planes interfere
constructively to produce a strong diffracted beam.
In this Bragg’s approach, as shown in figure, we consider an atom A in a lattice structure
and also consider another atom B where two parallel lattice planes are taken with inter
planar spacing (normal separation) 𝐝 through these two atoms A and B as shown. If we
now take scattering of two parallel incoming X ray beams at the same incident angle 𝛉
with the lattice plane, their scattering can now be considered as the reflection from the
same lattice plane at angle of reflection 𝛉 as suggested by Bragg.
Thus the path difference of these two scattered waves (reflected as considered) will now
become ∆= 𝐂𝐁 + 𝐁𝐃 = 𝐝𝐒𝐢𝐧𝛉 + 𝐝𝐒𝐢𝐧𝛉 = 𝟐𝐝𝐒𝐢𝐧𝛉.
As a result, for constructive interference as made by these two parallel scattered waves to
give strong diffracted X ray beam, we have the phase difference

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 𝟐𝛑
𝛗= (𝟐𝐝𝐒𝐢𝐧𝛉) = 𝟐𝐧𝛑 ⇒ 𝟐𝐝𝐒𝐢𝐧𝛉 = 𝐧𝛌 .
𝛌

This is well known Bragg’s equation for X ray diffraction from crystal lattice.

2. Optical Microscopy:

Microscopy is that tools of analysis through which we can see or we can take the image of
microscopic objects and even macro molecules. There exist a wide variety of such
microscopic tools for analyzing the bulk (volume) and surface properties of nano structure
and also for studying the bio molecules in biological process. It includes all possible forms
of microscopic instruments, microscopic processes, and microscopic methods for
magnifying those micro objects by using electromagnetic radiations. Among of such
several microscopy, the most relevant are light or optical microscopy, electron
microscopy, .... etc.

For optical microscopy, it uses glass lens for bending and focussing light to the object. For

.
these purpose, the technique with refraction, reflection or diffraction of light or radiation

ls
as guided by several fundamental rules of optics are used. And all these are used together
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in a most useful optical instrument, called “Compound Microscope” where the principle
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are given below.
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In this case the instrument is constructed by taking the combination of two coaxial lenses
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when one of this two lenses in front

of which the object is placed
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objective lens where as the other

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lens behind of which eye should be

placed is called eye piece lens. As
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shown in figure, when the objective

is placed in front of objective beyond
of its focal length then the real
image of it will be formed by the
objective lens on the other side of it.

This real image will then behave like

a virtual object with respect to the
eye piece lens and in that case if by
proper adjustment, the real image as
formed by objective lens be placed
within the focal length of the eye
piece then naturally the final image as made by the eye piece lens will be virtual,
magnified and inverted with respect to the object. For respective object and image
position u and v relative to the objective lens, since the eye piece acts as a simple

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microscope, the angular magnification of this compound microscope with lens separation
L will be 𝐌 = 𝐌𝐨𝐛𝐣𝐞𝐜𝐭𝐢𝐯𝐞 × 𝐌𝐞𝐲𝐞 𝐩𝐢𝐞𝐜𝐞 .

𝐯 𝐯 𝐃
So we have 𝐌 = 𝐮 × 𝐌𝐞𝐲𝐞 𝐩𝐢𝐞𝐜𝐞 = × (𝟏 + 𝐟 ) .
𝐮 𝐞

𝟏 𝟏 𝟏 𝟏 𝟏 𝟏 𝐯 𝐯
Again for the objective we get 𝐯 − =𝐟 ⇒ +𝐮=𝐟 ⇒ = (𝐟 − 𝟏) . Hence finally
−𝐮 𝐨 𝐯 𝐨 𝐮 𝐨
𝐯 𝐃
we get 𝐌 = (𝐟 − 𝟏) × (𝟏 + 𝐟 ) where 𝐟𝐨 and 𝐟𝐞 are the respective focal length of
𝐨 𝐞
objective and eye piece of this compound microscope. Since for this magnifying system we
have for greater magnification 𝐯 → 𝐋 , we finally have the maximum magnifying power
𝐋 𝐃
of a compound microscope as 𝐌 = (𝐟 − 𝟏) × (𝟏 + 𝐟 )
𝐨 𝐞

For this light or optical microscopy, there are several components which are

Bright – Field Microscopy:

.
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In a bright-field microscope, both diffracted (diffracted by the sample) and undefracted
ia
(light that is transmitted through the sample undeviated) lights are collected by the
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objective lens. Therefore, the image of the sample is generated against a bright
background. Hence, this method is termed as the bright-field microscopy. Most biological
at

samples are intrinsically transparent to the light resulting in poor contrast. To increase the
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contrast of the image, the specimens are therefore generally stained with the dyes.
However, intrinsically colored samples such as erythrocytes can directly be observed using
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bright-field microscopy.
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Dark – Field Microscopy:

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In dark-field microscopy, the contrast of the image is increased by eliminating the

undefracted light. The sample is illuminated by the light coming from a ring at an oblique
angle. If there is no sample in the path of the light ray, no light is collected by the
objective lens. Presence of sample results in the diffraction of light. The objective lens
collects the diffracted light generating a bright image against a dark background.

Phase Contrast Microscopy:

A phase contrast microscope provides very high contrast as compared to the bright-field
and dark-field microscopy methods. The image in a phase contrast microscope is
generated from both diffracted and undefracted lights. Like dark-field microscopy, the
sample is illuminated by the light coming from a ring which is called a condenser annulus.
The diffracted and the undefracted lights are separated in space allowing selective
manipulation of their phases and intensities. The diffracted as well as the undefracted
light is collected by the objective lens. A phase plate is placed at the back side of the

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 𝛌
objective lens that increases the phase of the undefracted light by 𝟒 and decreases that of
𝛌 𝛌
diffracted light by 𝟒. A total phase difference of 𝟐 is therefore obtained between the
diffracted and the undiffracted light beams before they are focused on the image plane.
As the intensity of the undiffracted light is very high, it is selectively reduced to ~𝟑𝟎% of
the initial intensity by a semi-transparent metallic film on the phase plate. Two waves that
𝛌
have 𝟐 phase difference interfere destructively thereby diminishing the light intensity. Any
phase change caused by the sample is therefore converted into an amplitude signal by a
phase contrast microscope thereby increasing the contrast.

3. Advantages and Disadvantages of an Optical Microscope:

Advantages:
These are some advantages of an optical microscope:

.
1. Images are obtained directly with no need of sample pretreatment.

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2. This is the only microscopy which can take real color images.
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3. It is fast, and adaptable to all kinds of sample systems from gas to liquid, and to solid
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sample systems, in any shapes or geometries.

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4. It is easy to be integrated with digital camera systems for data storage and analysis.
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Disadvantages:
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The main disadvantage of an optical microscope is that its resolution is low, usually down
to only sub-micron or a few hundreds of nanometers. This is mainly due to the light
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diffraction limit.

4. Electron Microscopy (EM):

The nanoparticles are usually too small to be visualized with conventional optical
microscope. We have seen that optical microscopes are generally used for visualization of
materials at micron (𝟏𝟎−𝟔 𝐦) level with reasonable resolution. Further magnification
cannot be achieved through optical microscopes mainly due to aberrations and limitation
in the wavelength of visible light. Hence it is necessary to use appropriate tools which
adequately characterize the detail structure and surface morphology at the molecular or
atomic level. This is important not only for understanding the fundamental properties but
also for exploring the functional and technical performance of nanomaterials in
technological applications.

With the advent of technology and fundamental science several microscopy techniques
have been developed over the past few years to characterize nanomaterials in every

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detail. Such techniques use ELECTRONS to study the surface properties of the specimen
and include scanning electron microscopy (SEM), transmission electron microscopy
(TEM/HRTEM), scanning tunnelling microscopy (STM), atomic force microscopy (AFM),
etc. The basic principles of all such techniques are different but the common thing is that
they all produce a highly magnified image of the surface of the nanosamples under
investigation.

There are two basic models of the electron microscopes: Scanning electron microscopes
(SEM) and transmission electron microscopes (TEM). In a SEM, the secondary electrons
produced by the specimen are detected to generate an image that contains topological
features of the specimen. The image in a TEM, on the other hand, is generated by the
electrons that have transmitted through a thin specimen. The basic working principles of
these two microscopes and their applications in extracting structural information of
nanomaterial are described in detail below.

a) Louis de Broglie hypothesis: Calculation of Wavelength of an Electron:

.
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In electron microscopy, electrons are used to investigate the structure of nanomaterials
ia
and other bio samples. We know that the resolution of an instrument is inversely
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proportional to the wavelength of the source of radiation. Further the wavelength
at

associated with an electron can be controlled by the external voltage through which the
electron is accelerated. Hence, resolution of the device using electron can be increased by
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external voltage. This can be understood from the following discussion.

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Louis de Broglie in 1924 theorized that particles have wave-like characteristics. Three
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years later, electron diffraction experiments carried out independently by Davisson and
Germar and Thomson and Reid demonstrated the wave behaviour of the electrons.
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Within next five years, the idea to use electrons for microscopy was realized when Knoll
and Ruska published the images recorded using electrons.

According to be Broglie hypothesis, a material particle has an associated matter wave. The
momentum P of an electron and the wavelength 𝛌 of the matter wave associated with the
𝐡
electron are related through an equation given by 𝛌 = 𝐩 … … … … (𝟏)

where h is Planck’s constant (𝟔. 𝟔𝟐𝟕 × 𝟏𝟎−𝟐𝟕 𝐞𝐫𝐠 𝐬); m is the mass of the particle
(𝟗. 𝟏 × 𝟏𝟎−𝟐𝟖 𝐠) and 𝐯 =velocity of the electron. This equation (1) suggests that Planck’s
constant h provides a link between the wave nature (𝛌) and the particle nature (𝐩) of a
particle.

For a low-energy (non-relativistic) particle of mass m and kinetic energy 𝐄𝐊 , de Broglie

𝐡 𝐡
wavelength associated with the particle is given by 𝛌 = 𝐩 = … … (𝟐)
√𝟐𝐦𝐄𝐊

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For a high-energy (relativistic) particle of rest mass 𝐦𝟎 and kinetic energy 𝐄𝐊 , de Broglie
𝐡 𝐡𝐜
wavelength associated with the particle is given by 𝛌 = 𝐩 = … … (𝟑)
√𝐄𝐊 (𝐄𝐊 +𝐦𝟎 𝐜 𝟐 )

Here momentum p for a high-energy particle is calculated in the following way:

According to Einstein’s special theory of relativity, the relation between total energy E,
momentum p, kinetic energy 𝐄𝐊 and rest mass 𝐦𝟎 of a relativistic free particle is given by

𝐄𝟐 = 𝐩𝟐 𝐜 𝟐 + 𝐦𝟐𝟎 𝐜 𝟒 = (𝐄𝐊 + 𝐦𝟎 𝐜 𝟐 )𝟐
𝟏
𝐩𝟐 𝐜 𝟐 + 𝐦𝟐𝟎 𝐜 𝟒 = 𝐄𝐊𝟐 + 𝐦𝟐𝟎 𝐜 𝟒 + 𝟐𝐄𝐊 𝐦𝟎 𝐜 𝟐 ⇒ 𝐩𝟐 𝐜 𝟐 = 𝐄𝐊 (𝐄𝐊 + 𝟐𝐦𝟎 𝐜 𝟐 ) ⇒ 𝐩 = 𝐜 √𝐄𝐊 (𝐄𝐊 + 𝟐𝐦𝟎 𝐜 𝟐 )

When an electron passes through a potential difference (accelerating voltage field) 𝐕𝐩 , its
kinetic energy with be equal to the energy of the field, i.e. 𝐞𝐕𝐩 . We know that 𝐄 = 𝐦𝐜 𝟐 .
By restating this for velocities below the speed of light and particles with true mass, the
energy of an electron may be expressed as follows:

.
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𝟏
𝐞𝐕𝐩 = 𝐦𝐯 𝟐 .
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𝟐
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By using some assumptions about the velocity of the particle and its mass, it is possible to
express either wavelength (𝛌) or velocity (𝐯) in terms of the accelerating voltage(𝐕𝐩 ). By
at

further substituting the values of h and m above, the equation for 𝛌 reduces to the
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𝟏.𝟐𝟑𝐧𝐦
following: 𝛌 = .
√𝐕𝐩
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In typical electron microscopes, electrons are produced in a gun and accelerated through a
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high potential difference. Generally an acceleration voltage in the range of one hundred
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thousand (𝟏𝟎𝟎 𝐤𝐕) to a few million volts is used in an electron microscope. In June 1995,
Osaka University, Japan, the world’s highest voltage of 𝟑𝟎𝟎𝟎 𝐤𝐕 was applied. There are
advantages of ultrahigh voltage electron microscope over conventional electron
microscope. The high voltage electrons have more penetrating power and a very high
resolution of down to a tenth of a nanometre can be reached.

When electrons are accelerated through such a very high potential difference, gain huge
amount of energy and the wavelengths associated with the electrons decrease. The wave-
like property of the electrons dominate with smaller and smaller value of wavelength.

b) Macroscopic description: (Average size is very large compared to de

Broglie wavelength)
A body of size d (dimension) moving with momentum p is associated with matter wave of
wavelength 𝛌. The relative magnitudes of size d and wavelength 𝛌 decide whether the
body will exhibit particle property or wave property. If 𝐝 ≫ 𝛌, the particle property
dominates. Such a body is called a macroscopic system and the description is macroscopic.

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The classical picture in this case is adequate and a wave picture is not suitable. Examples
of the particles are a cricket ball, sand, a biological virus, etc.

Consider an example

A virus has a size 𝐝~𝟏𝟎𝐧𝐦 − 𝟑𝟎𝟎𝐧𝐦; mass 𝐦~𝟏𝟎−𝟏𝟓 𝐤𝐠 and average

speed 𝐯~𝟏𝐦𝐦 𝐬 −𝟏 = 𝟏𝟎−𝟑 𝐦𝐬 −𝟏 .

The de Broglie wavelength is given by

𝐡 𝐡 𝟔. 𝟔𝟐𝟔 × 𝟏𝟎−𝟑𝟒 𝐉. 𝐬
𝛌= = = = 𝟔. 𝟔𝟐𝟔 × 𝟏𝟎𝟏𝟔 𝐦 = 𝟔. 𝟔𝟐𝟔 × 𝟏𝟎−𝟕 𝐧𝐦
𝐩 𝐦𝐯 (𝟏𝟎−𝟏𝟓 𝐠) × (𝟏𝟎−𝟑 𝐦𝐬 −𝟏 )

Clearly, in this case we have 𝐝 ≫ 𝛌. Hence the particle-like property of the virus is
dominated. This guarantees that the virus can be looked upon as particle.

5. Scanning Electron Microscopy (SEM)

.
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Scanning electron microscope is an electron microscopy technique that images the sample
ia
surface by scanning it with a high energy beam of electrons. The accelerated beam of
electrons coming from the electron gun strikes the surface of the sample under
er
consideration. Due to interaction with the sample kinetic energy associated with the
at

electron beam is dissipated as a variety of low energy signals.

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These includes secondary electrons, backscattered electrons (BSE), diffracted

backscattered electrons, photons (characteristic X-rays that are used for elemental
o

analysis and continuum X-rays), visible light (cathode-luminescence-CL), and heat

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Secondary electrons and the backscattered electrons are generally used for imaging the
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samples surface, specifically secondary electrons are mainly responsible for showing the
morphology and topography of the sample surface and the back scattered electrons are
responsible for illustrating contrast in composition in multiphase sample. Characteristics
X-rays are the second most common imaging mode for an SEM. The inelastic collisions of
the incident electrons with electrons in discrete orbital’s of atoms in the sample generate
characteristics X-ray of a fixed wavelength.

So these characteristic X-rays are used to identify the elemental composition of the
sample by a technique known as energy dispersive X-ray (EDX). The most immediate
result of observation in the scanning electron microscope is that it displays the texts shape
of the sample. The resolution in SEM is determined by BEAM DIAMETER.

Different types of SEM

The different types of scanning electron microscopes are as follows:

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1. Conventional (high vacuum) SEM 2. Variable Pressure or Low Vacuum SEM 3. Cryo on
an SEM (Cryo-SEM) 4. Environmental SEM 5. Focused ion beam (FIB) 6. Electron-beam (E-
beam) lithography

6. Basic Principles of Scanning Electron Microscopy:

Accelerated electrons in an SEM carry significant amounts of kinetic energy, and this
energy is dissipated as a variety of signals produced by electron-sample interactions when
the incident electrons are decelerated in the solid sample. These signals include secondary
electrons (that produce SEM images), backscattered electrons (BSE), diffracted
backscattered electrons (EBSD that are used to determine crystal structures and
orientations of minerals), photons (characteristic X-rays that are used for elemental
analysis and continuum X-rays), visible light (cathode-luminescence-CL), and heat.
Secondary electrons and backscattered electrons are commonly used for imaging samples:
secondary electrons are most valuable for showing morphology and topography on

.
samples and backscattered electrons are most valuable for illustrating contrasts in

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composition in multiphase samples (i.e. for rapid phase discrimination).
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X-ray generation is produced by inelastic collisions of the incident electrons with electrons
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in discrete orbital (shells) of atoms in the sample. As the excited electrons return to lower
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energy states, they yield X-rays that are of a fixed wavelength (that is related to the
difference in energy levels of electrons in different shells for a given element). Thus,
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characteristic X-rays are produced for each element in a mineral that is excited by the
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electron beam. SEM analysis is considered to be ‘’non-destructive’’; that is X-rays

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generated by electron interactions do not lead to volume loss of the sample, so it is

possible to analyze the same materials repeatedly.
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The basic components of a typical SEM are shown in figure. The electron beam passes
through a pair of scanning coils or pairs of deflector plates in the electron column to the
final lens, which deflect the beam horizontally and vertically so that it scans in raster
fashion over a rectangular area of the sample surface. Electronic devices are used to
detect and amplify the signals and display them as an image on a cathode ray tube in
which the raster scanning is synchronized with that of the microscope. The image
displayed is therefore a distribution map of the intensity of the signal being emitted from
the scanned area of the specimen.

The sample under consideration should be conductive so that the electron beam
subjected to scan the sample surface has a path to ground for conventional imaging.
However for non-conducting samples, specimens are generally coated with a layer of
conductive material by low vacuum sputter coating or high vacuum evaporation to
prevent accumulation of static electronic charge on the specimen during electronic
irradiation. The maximum resolution obtained in an SEM depends on multiple factors, like

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the electron spot size and interaction volume of the electron beam with the sample. While
it cannot provide atomic resolution, some SEMs can achieve resolution below 1nm.
Typically modern full-sized SEMs provide resolution between 1-20 nm whereas desktop
systems can provide a resolution of 20 nm or more.

7. Essential components of all SEMs include the following:

Following components are essential for a scanning electron microscope:

1. Electron Source (‘’Gun’’) 2. Electron Lenses 3. Sample Stage 4. Detectors for all signals of
interest 5. Display/Data output devices 6. Infrastructure Requirements:

(i) Power Supply; (ii) Vacuum System; (iii) Cooling system; (iv) Vibration-free floor and (v)
Room free of ambient magnetic and electric fields.

SEMs always have at least one detector (usually a secondary electron detector), and most

.
have additional detectors. The specific capabilities of a particular instrument are critically

ls
dependent on which detectors it accommodates. The quality of image formed in a SEM is
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really impressive. One such image is shown in figure. The scanning electron microscopic
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image is better than the corresponding optical microscopic image. One such comparison
of image obtained in these two microscopies is shown in figure.
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8. Application of SEM:
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Scanning electron microscopy is a remarkably versatile technique. There are many

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different types of SEMs available, tailored to specific needs. With SEM one can:
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a) Image morphology of samples (e.g. view bulk material, coatings, sectioned material,
foils, even grids prepared for transmission electron microscopy).

b) Image compositional and some bonding differences (through contrast and using
backscattered electrons).

c) Image molecular probes: metals and fluorescent probes.

d) Undertake micro and nanolithography: remove material from samples; cut pieces out
or remove progressive slices from samples (e.g. using a focused ion beam).

e) Heat or cool samples while viewing them (while possible in many instruments it is
generally done only in ESEM or during Cryo-scanning electron microscopy).

f) Wet and dry samples while viewing them (only in an ESEM).

g) View frozen material (in an SEM with a cryostage).

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h) Generate X-rays from samples for microanalysis (EDS; WDS).

i) Study optoelectronic behaviour of semiconductors using cathodo-luminescence.

j) View/map grain orientation/crystallographic orientation and study related information

like heterogeneity and micro strain in flat samples (Electron backscattered diffraction).

k) Electron diffraction using electron backscattered diffraction. The geometry may be

different to a transmission electron microscope but the physics of Bragg diffraction is the
same.

9. Limitations of SEM:

The basic limitations of this SEM are

a) Image morphology of samples (e.g. view bulk material, coatings, sectioned material,
foils, even grids prepared for transmission electron microscopy).

.
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b) SEM cannot take colour images. The colour is often added artificially in colored SEM
images. Note: Some SEMs can collect true colour images via a wavelength selective
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cathodo-lumence (CL) detector.
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c) SEM cannot image through water. Note: An ESEM using a wet Scanning Transmission
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Electron Microscope (STEM) detector can be used to image through thin water films.
o

d) The SEM cannot reliable image charged molecules that are mobile in a matrix. For
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example, some species (e.g. 𝐍𝐚 +) are volatile under the electron beam because the
negative electron beam exerts a force on charged material.
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e) SEM is not good for quantifying surface roughness at small scale. Atomic Force
Microscope (Scanning Probe Microscopy) is more useful for this task.

f) Measurements involving height (Z-axis) cannot be taken directly in an SEM. This

requires two images that have been titled relative to one another to create a 3D image,
and specialized processing software.

g) Generally, SEMs are not used for experiments involving liquids, chemical reactions, and
air-gas systems although some specialized machines and sample chambers do allow for
these experiments.

h) The resolution of the SEM is not high enough to image individual atoms (use a
transmission electron microscope).

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10. Transmission Electron Microscopy (TEM)
The first electron microscope was developed by Knoll and Ruska in 1930s. It was a
transmission electron microscope. They focused the electrons on a thin specimen and
detected the transmitted electrons through the specimen and reported about the
structural information of the specimen. Hence, transmission electron microscopy is a
microscopic technique where a beam of electrons is transmitted through an ultra thin
specimen and interacts with the bulk of the sample in course of passing through it. TEM
can provide imaging, diffraction and spectroscopic information of the sample under
consideration with an atomic or subatomic spatial resolution.

11. Basic principle of transmission electron microscopy

Various components of a TEM is shown in figure and its vertical image is shown in figure.
A brief description for each component is presented below.

.
Electron Gun

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The electron source consists of a cathode and an anode. The cathode is a tungsten
er
filament which emits electrons when being heated. A negative cap confines the electrons
into a loosely focused beam. The beam is then accelerated towards the specimen by the
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positive anode. Electrons at the rim of the beam will fall onto the anode while the others
M

at the center will pass through the small hole of the anode. The electron source works like
a cathode ray tube.
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Electromagnetic Lens System

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After leaving the electron source, the electron beam is tightly focused using
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electromagnetic lens and metal apertures. The system only allows electrons within a small
energy range to pass through, so the electrons in the electron beam will have a well-
defined energy.

1. Magnetic Lens: Circular electro-magnets capable of generating a precise circular

magnetic field. The field acts like an optical lens to focus the electrons.

2. Aperture: A thin disk with a small (2-100 micrometers) circular through-hole. It is used
to restrict the electron beam and filter out unwanted electrons before hitting the
specimen.

Sample preparation for TEM

The very first requirement of TEM is that the specimens to be analyzed must be very thin.
As for SEM, the specimens in TEM also need to be fixed and dried. In TEM, preparation of
specimens is a fairly tedious process. The samples are usually fixed using a combination of
glutaraldehyde and paraformaldehyde. A secondary staining is done with 𝐎𝐒 𝐎𝟒 (Osmium

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tetroxide). 𝐎𝐒 𝐎𝟒 fixes the unsaturated lipids and being a heavy metal acts as an electron
stain too. The samples are then dehydrated exactly as done for SEM analysis. The dried
samples are then sectioned to obtain ultrathin (< 𝟏𝟎𝟎𝐧𝐦 𝐭𝐡𝐢𝐜𝐤𝐧𝐞𝐬𝐬) sections. Epoxy
and acrylic resins are also used for embedding the samples for sectioning. The sections are
then stained with a heavy metal stain as uranyl acetate and phosphotungstic acid. The
stained sample is then deposited on a carbon coated grid and analyzed by TEM. The
sample holder is a platform equipped with a mechanical arm for holding the specimen and
controlling its position.

Imaging system
The imaging system consists of another electromagnetic lens system and a screen. The
electromagnetic lens system contains two lens systems, one for refocusing the electrons
after they pass through the specimen, and the other for enlarging the image and
projecting it onto the screen. The screen has a phosphorescent plate which glows when
being hit by electrons. Image forms in a way similar to photography.

.
Working Principle:
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TEM works like a slide projector. A projector shines a beam of light which transmits
through the slide. The patterns painted on the slide only allow certain parts of the light
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beam to pass through. Thus the transmitted beam replicates the patterns on the slide,
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forming an enlarged image of the slide when falling on the screen.

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TEMs work the same way except that they shine a beam of electrons (like the light in a
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slide projector) through the specimen (like the slide). However, in TEM, the transmission
of electron beam is highly dependent on the properties of material being examined. Such
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properties include density, composition, etc. For example, porous material will allow more
electrons to pass through while dense material will allow less. As a result, a specimen with
a non-uniform density can be examined by this technique. Whatever part is transmitted is
projected onto a phosphor screen for the user to see.

Resolution
The resolution is typically described as the distance between the first order peak and the
first order through. Resolution is empirically described as the ability to discriminate
between two points. If an object is just below the level of resolution, the peaks generated
by the two points will make the object appear to be a single point. The resolution of TEM
is much better than a light microscope. Images of cotton stem using a light microscope
(left) and a TEM (right) which clearly demonstrates the difference in resolution between
the two. The encircled region of the image (left) in light microscope is shown in the
diagram (right) which shows the clarity and magnification of the image.

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Abbe’s equation
Resolution in a perfect optical system can be described mathematically by Abbe’s
𝟎.𝟔𝟏𝟐×𝛌
equation. This equation is given by 𝐝= 𝐧 𝐬𝐢𝐧𝛉

Where 𝐝 =resolution; 𝛌 =wavelength of imaging radiation; 𝐧 =index of refraction of

medium between point source and lens, relative to free space; 𝛉 =half the angle of the
cone of light from specimen plane accepted by the objective (half aperture angle in
radians) and 𝐧 𝐬𝐢𝐧𝛉 is often expressed as numerical aperture (NA).

This is the diffraction-limited resolution of an optical system. If all aberrations and

distortions are eliminated from the optical system, this will be the limit to resolution. If
aberrations and distortions are present, they will determine the practical limit to
resolution.

Equation for resolution in TEM

.
ls
𝟎.𝟔𝟏𝟐×𝛌
This value for 𝛌 can then be substituted into Abbe’s equation =
ia . Since angle 𝛉 is
𝐧 𝐬𝐢𝐧𝛉
usually very small, for example 𝟏𝟎−𝟐 radians (a likely figure for TEM), the value of 𝛉
er
approaches that of 𝐬𝐢𝐧𝛉, so we replace it. Since 𝐧 (refractive index) is essentially 1, we
at

eliminate it, and we multiply 0.612 by 12.3 to obtain 0.753. Therefore, the equation
𝟎.𝟔𝟏𝟐×𝛌 𝟎.𝟕𝟓𝟑
𝐝= reduces to: 𝐝 =
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𝐧 𝐬𝐢𝐧𝛉 𝛉√𝐕𝐩
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where 𝐝 =resolution in nm; 𝛉 =half aperture angle and 𝐕𝐩 =accelerating velocity.

an

Now solving for 100,000 volts, the result is 0.24 nm or𝟐. 𝟒Å. This improves with higher
accelerating voltage and gets worse with lower voltages. (Using Einsteinium calculations,
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the resolution is: 𝟎. 𝟐𝟐 𝐧𝐦 𝐨𝐫 𝟐. 𝟐Å) Each lens and aperture has its own set of aberrations
and distortions. If aberrations and distortions are present, they will determine the
practical limit to resolution.

Advantages of TEM
A Transmission Electron Microscope is an impressive instrument with a number of
advantages such as:

1. TEMs offer the most powerful magnification, potentially over one million times or
more.

2. TEMs have a wide-range of applications and can be utilized in a variety of different

scientific, educational and industrial fields

3. TEMs provide information on element and compound structure

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4. Images are high-quality and detailed

5. TEMs are able to yield information of surface features, shape, size and structure

6. They are easy to operate with proper training

Disadvantages of TEM
1. TEMs are large and very expensive.

2. Sample preparation is often much more elaborate. It is often necessary to coat the
specimen with a very thin layer of metal (such as gold). The metal is able to reflect the
electrons.

3. The sample must be completely dry. This makes it impossible to observe living
specimens.

.
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4. Potential artefacts from sample preparation. ia
5. It is not possible to observe moving specimens (they are dead).
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6. Operation and analysis requires special training

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7. Samples are limited to those that are electron transparent, able to tolerate the vacuum
chamber and small enough to fit in the chamber
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8. TEMs require special housing and maintenance.

9. It is not possible to observe color. Electrons do not possess a color. The image is only
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black / white. Sometimes the image is colored artificially to give a better visual
impression.

10. Maintenance costs are high.

11. The energy of the electron beam is very high. The sample is therefore exposed to high
radiation, and therefore not able to live.

12. Basic Principle of Operation of AFM:

The atomic force microscopy is based on the physical scanning of nanosamples, at sub
micron level, using a sharp tip of atomic scale. Figure shows schematically the diagram of
an AFM. A typical AFM set up consists of a sharp tip mounted on a micro scales cantilever,
a laser, a position sensitive detector, a piezoelectric tube (PZT) scanner and other control
electronics. The curved cantilever is made off either silicon or silicon nitride. The sharp tip
located near the end of the cantilever beam raster scans over the surface of the sample
under investigation using a piezoelectric scanner. When the tip is brought near the surface

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of the sample, forces between the tip and surface molecule of the sample lead to a
deflection of the cantilever.

The interaction force acting between the tip and the sample’s surface may be mechanical
contact force, electrostatic forces, Van Dar Waals forces, capillary forces and magnetic
forces. The deflection of the cantilever is measured through a laser beam reflected from
the top of the cantilever into an array of position sensitive photo-diodes. In order to avoid
the collision between the tip and the sample, a feedback mechanism is often employed
such that, the distance between the tip and the sample is so adjusted that the interaction
force between the tip and sample remains constant. The sample under investigation is
mounted on a PZT crystal which can move the sample in z direction for maintaining a
constant force and in the x and y directions for scanning the sample. The resulting map of
the area 𝐬 = 𝐟(𝐱, 𝐲) represents the topography of the sample.

Scanner in AFM

.
ls
The movement of the tip or sample in the x, y and z-directions is controlled by a
piezoelectric tube scanner, similar to those used in STM. For typical AFM scanners, the
ia
maximum ranges are 𝟖𝟎𝛍𝐦 × 𝟖𝟎𝛍𝐦 in the x-y plane and nearly 𝟓𝛍𝐦 for the z-direction.
er
The scanner moves across the first line of the scan, and back. It then steps in the
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perpendicular direction to the second scan line, moves across it and back, then to the
third line, and so forth. The path differs from a traditional raster pattern in that the
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alternating lines of data are not taken in opposite directions.

o

Probes in AFM
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The probe is a very important component of an AFM because different probes can
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measure different properties of the sample. In addition, the probe determines the force
applied to the sample.
Regarding AFM, the
most common probes
are the cantilevers that
are highly suited to
measure the topography
of a sample. Different
coatings on the
cantilevers measure
different properties of
the sample. The tip and
the cantilever as an
integrated component
can be fabricated from
silicon or silicon nitride

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using photolithographic techniques. From a single silicon wafer it is possible to make more
than 1000 probes. Regarding the physical properties, the cantilever ranges from
𝟏𝟎𝟎 𝐭𝐨 𝟐𝟎𝟎 𝛍𝐦 in length, 𝟏𝟎 𝐭𝐨 𝟒𝟎 𝛍𝐦 in width, and 𝟎. 𝟑 𝐭𝐨 𝟐 𝛍𝐦 in thickness.

Properties of Cantilever
The spring constant of a cantilever has a critical importance in atomic force microscopy. It
is lower than the spring constant between atoms in a solid, which is of the order of
𝟏𝟎 𝐍𝐦−𝟏 . The spring constant of the cantilever depends on its shape, its dimension and
the material from which it’s made of. Shorter and thicker cantilevers tend to be stiffer and
consequently have higher resonant frequencies. Commercial available cantilevers range
the value of spring constant over four orders of magnitude, from thousands of a Newton
per meter to tens of Newton’s per meter. Resonant frequencies range from a few
Kilohertz to hundreds of Kilohertz allowing high-speed response for non-contact
operation.

.
ls
Different Classes of AFM
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Depending on the nature of force interacting between the tip and the sample surface AFM
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can be classified as follows
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Chemical or Frictional Force Microscopy: Here the cantilever senses the frictional
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force between the atoms of the probe and the atoms on the surface of the sample.

Electrostatic Force Microscopy: In this case cantilever senses the electric field acting
o
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between the probe tip and the sample surface.

Magnetic Force Microscopy: Here a magnetic probe tip is used and the cantilever
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senses the magnetic field between the tip and the sample surface to image the magnetic
structure of the samples surface.

13. Scanning Tunnelling Microscopy (STM)

The invention of STM in 1981 by Gerd Bining and Heinrich Rohrer (at IBM Zrich) opened a
new field of research in surface science. Gerd Bining and Heinrich Rohrer won the Nobel
Prize in Physics for their remarkable achievement in 1986. A scanning tunnelling
microscope (STM) is an instrument for providing surface images with atomic level
resolution. For an STM, good resolution is considered to be 0.1 nm lateral resolution and
0.01 nm (10 pm) depth resolution.

With this resolution, individual atoms within materials are routinely imaged and
manipulated. The STM can be used not only in ultra-high vacuum but also in air, water,
and various other liquid or gas ambient, and at temperatures ranging from near zero
Kelvin to over 1000 C.

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Basic principle of Scanning Tunnelling Microscopy
The components of an STM include a scanning tip, Piezo-electric controlled height and x, y
scanner, coarse sample-to-tip control, vibration isolation system, and computer. A
schematic diagram of a scanning tunnelling microscope is shown in figure. The resolution
of an image is limited by the radius of curvature of the scanning tip of the STM. The
scanning tip is often made of tungsten or platinum-iridium, sometimes gold is also used.
Tungsten tips are usually made by electrochemical etching, and platinum-iridium tips by
mechanical shearing.

.
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at
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o
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STM is based on several principles but the main concept behind the working principle of
STM is the concept of quantum tunnelling. When a conducting tip is brought near to a
metallic or semi-conducting surface under investigation, an electric bias applied between
the two allows electrons to tunnel through the vacuum between them. Once tunnelling is
established, the tip’s bias and position with respect to the sample can be varied (with the
details of this variation depending on the experiment) and data are obtained from the
resulting changes in current. This tunnelling current is a function of tip position, applied
voltage, and the local density of states (LDOS) of the sample. Information is acquired by
monitoring the current as the tip’s position across the surface, and is usually displayed in
image form.

STM is a very challenging technique, as it requires extremely clean and stable surfaces,
sharp tips, and sophisticated electronics, but nonetheless many hobbyists have built their
own. Due to extreme sensitivity of tunnel current to height, proper vibration insulation or
an extremely rigid STM body is imperative for obtaining usable results. The transmission

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coefficient and the tunnel current vary exponentially with the probe to surface atom
separation d and respectively given by the expressions as follows: 𝐓 = 𝐀 𝐓 𝐞−𝟒𝐤𝐝 and
𝐈𝐓 = 𝐂𝐓 𝐞−𝐤𝐝

Here 𝐀 𝐓 𝐚𝐧𝐝 𝐂𝐓 are two constants which take into account the effect of other factors. The
tunnelling current 𝐈𝐓 depends so strongly on the separation d such that it is even
dominated by the contribution flowing between the last atom of the tip and the nearest
atom in the surface. If the separation between the tip and the sample changes by 10% (of
the order of 1), the tunnelling current also changes by an order of magnitude. This
exponential dependence gives STMs their remarkable sensitivity.

STM also requires an excellent vibration control. In the first STM by Binning and Rohrer,
magnetic levitation was used to keep the STM free from vibrations; now mechanical
spring or gas spring systems are often used. Additionally, mechanisms for reducing eddy
currents are sometimes implemented. Maintaining the tip position with respect to the
sample, scanning the sample and acquiring the data is fully computer controlled. All

.
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images produced by STM are in gray scale, with colour optionally added in post-processing
in order to visually emphasize important features.
ia
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Application of Scanning Tunnelling Microscopy
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Scanning tunnelling microscopy is a powerful characterization probe used in

M

nanotechnology and nanoscience for providing information on the topography and defect
structure of a surface in the atomic scale. It is successfully used to investigate discrete
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atomic states of colloidal quantum dots and other such systems. It can also image and
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manipulate individual atoms in a sample. Moreover it can be used as a spectrometer from

measuring electronic energies. The instrument has also been used to move single
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nanotube or metal atoms and molecules on smooth surfaces with high precision.

Difference between a Scanning Tunnelling Microscope and an Atomic Force

Microscope:
1. AFM captures precise images by moving a nanometre sized tip across the surface of the
image. The STM captures images using quantum tunnelling.

2. The probe makes a direct contact with the surface or calculates the incipient chemical
bonding in AFM. The STM images indirectly by calculating the quantum degree tunnelling
between the probe and sample.

3. The tip in AFM touches the surface gently touches the surface whereas in STM, the tip is
kept at a short distance from the surface.

4. AFM resolution is better than the STM. This is why AFM is widely used in
nanotechnology.

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5. When Scanning Tunnelling Microscope is normally applicable to conductors, the Atomic
Force Microscope is applicable to both conductors and insulators.

6. The AFM suits well with liquid and gas environments whereas STM operates only in
high vacuum.

7. Of the two microscopes, the Scanning Tunnelling Microscope was the first to be
developed.

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 Applications [Ch.6]
1. Application of Nanoparticles in Medicine:
Nanoparticles are widely used in medical sciences. We first discuss the use of polymeric
micelle nanoparticles to deliver drugs to tumours. The use of polymer coated iron oxide
nanoparticles to break up clusters of bacteria, possibly allowing more effective treatment
of chronic bacterial infections. The surface change of protein filled nanoparticles has been
shown to affect the ability of the nanoparticles to stimulate immune responses.

These nanoparticles may be used in inhalable vaccines. The cerium oxide nanoparticles act
as an antioxidant to remove oxygen free radicals that are present in a patient’s blood
stream following a traumatic injury. The nanoparticles absorb the oxygen free radicals and
then release the oxygen in a less dangerous state, freeing up the nanoparticles to absorb
more free radicals. Researchers are developing ways to use carbon nanoparticles called
nano diamonds in medical applications.

.
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For example, nano diamonds with protein molecules attached can be used to increase
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bone growth around dental or joint implants. Researchers are testing the use of
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chemotherapy drugs attached to nano diamonds to treat brain tumours. Other
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researchers are testing the use of chemotherapy drugs attached to nano diamonds to
treat leukemia.
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There are indeed several advantages using nanoparticles in drug delivery.

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* Particle size and surface characteristics of nanoparticles can be easily manipulated to

achieve both passive and active drug targeting after parenteral administration.
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* They control and sustain release of the drug during the transportation and at the site of
localization, altering organ distribution of the drug and subsequent clearance of the drug
so as to achieve increase in drug therapeutic efficacy and reduction in side effects.

* Site-specific targeting can be achieved by attaching targeting ligands to surface of

particles or use of magnetic guidance.

* The system can be used for various routes of administration including oral, nasal,
parenteral, intra-ocular etc.

*Nanoparticles can better deliver drugs to tiny areas within the body.

* Engineering on the nanoscale enables researchers to exercise exquisite and previously

unthinkable control over the physical attributes of polymers and other biomaterials.

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* Nanoparticles overcome the resistance offered by the physiological barriers in the body
because efficient delivery of drug to various parts of the body is directly affected by
particle size.

*Nanoparticles aid in efficient drug delivery to improve aqueous solubility of poorly

soluble drugs that enhance bioavailability for timed release of drug molecules, and precise
drug targeting.

* The surface properties of nanoparticles can be modified for targeted drug delivery for
e.g. small molecules, proteins, peptides, and nucleic acids loaded nanoparticles are not
recognized by immune system and efficiently targeted to particular tissue types.

* Targeted nano-drug carriers reduce drug toxicity and provide more efficient drug
distribution.

* Nanocarriers holds promise to deliver biotechnology drugs over various anatomic

extremities of body such as blood brain barrier.

.
2. Applications of Quantum Dots:
ls
ia
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Quantum dots (QDs) are often referred to very tiny man-made semiconductor particles,
whose size are normally no more than 10 nanometers. Their extreme small size renders
at

their optical and electronic properties different from those of bulk materials. A majority of
M

QDs have the ability to emit light of specific wavelengths if excited by light or electricity.
According to existing literature, the electronic characteristics of QDs are determined by
o

their size and shape, which means we can control their emission wavelengths by tuning
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their size. Typically, smaller QDs (e.g., radius of 2-3 nm) emit shorter wavelengths
generating colours such as violet, blue or green. While bigger QDs (e.g., radius of 5-6 nm)
.N

emit longer wavelengths generating colours like yellow, orange or red. Their highly
tunable optical properties based on their size are fascinating, leading to a variety of
research and commercial applications including bio imaging, solar cells, LEDs, diode lasers,
and transistors.

Potential applications of quantum dots include single-electron transistors, solar cells,

LEDs, lasers, single-photon sources, second-harmonic generation, quantum computing,
and medical imaging. Their captured small size allows for some QDs to be suspended in
solution, which may lead to use in inkjet printing and spin-coating.

Quantum dot-based light-emitting diodes (QD-LEDs) represent a form of light-emitting

technology and are regarded like a next generation of display technology after the organic
light-emitting diodes (OLEDs) display. QD-LEDs are different from liquid crystal displays
(LCDs), OLEDs, and plasma displays due to the fact that QD-LEDs present an ideal blend of
high brightness, efficiency with long lifetime, flexibility, and low-processing cost of organic
LEDs. So, QD-LEDs show theoretical performance limits which surpass all other display

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technologies. In figure, we describe the various processes involved in hybrid LED and an
energy band gap scheme of QD-LED.

Researchers have demonstrated that grapheme quantum dots doped with nitrogen can be
used as a catalyst to make hydrocarbons from carbon dioxide. Scientists have developed a
solar cell that uses a copper indium serenade sulphide quantum dots. Unlike quantum
dots containing lead or cadmium the copper based quantum dot is non-toxic as well as
low cost.

People also exploring the use of quantum dots to treat antibiotic resistant infections.
Magnetic quantum dots in Spintronic semiconductor devices have been used as memory
chips. Spintronic devices are expected to be significantly higher density and lower power
consumption because they measure the spin of electronics to determine 1 or 0, rather
than measuring groups of electronics as done in normal/current semiconductor devices.

Researchers are also developing humidity and pressure sensors using grapheme quantum

.
dots. These sensors are originally intended for spaceflight applications because they can

ls
function at a very low pressure. Quantum Dots can be used for producing images of
ia
cancer tumours. Currently this is used in animals to evaluate the performance of cancer
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treatments. Quantum dots are being used to produce miniature lasers for use in
communications devices. The advantage of these lasers is the high speed data transfer
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with low power consumption.

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Quantum dots can be used in TV or computer displays. Displays using quantum dots
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should be thinner, lower power consumption than current displays as well as able to be
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flexible.

3. Applications of QDs in Bio Imaging:

.N

Various kinds of organic dyes have been used in bio imaging for decades. However, most
of the organic dyes suffer from low quantum yield and photo stability. However, with the
advancement of nanotechnology, QDs have been considered to be superior to traditional
organic dyes in many respects. For example, it has been found that QDs are 20 times
brighter and 100 times more stable more than traditional fluorescent materials. With the
help of well-established inorganic synthetic techniques, it is now possible to produce QDs
with high brightness.

For bio imaging applications, the fluorescent probes have to remain well-dispersed and
stable in the aqueous medium with a wide range of pH and ionic strengths. Various
approaches have been developed to make the QDs water-dispersible. Great efforts have
been devoted to employing QDs for in vitro and in vivo imaging, which are important to
the diagnoses of many diseases, and understanding of embryogenesis, and lymphocyte
immunology.

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4. Applications of Nanowires:
A Nanowire is a nanostructure, with the diameter of the order of a
nanometer(𝟏𝟎−𝟗 𝐦𝐞𝐭𝐞𝐫𝐬). It can also be defined in terms of aspect ratio being greater
than 1000. Alternatively, nanowires can be defined as structures that have a thickness or
diameter constrained to tens of nanometers or less and an unconstrained length. At these
scales, quantum mechanical effects are important which coined the term ‘’QUANTUM
WIRES’’. Many different types of Nanowires exist, including superconducting (e.g. YBCO),
metallic (e.g. Ni, Pt, Au), semiconducting (e.g. silicon Nanowires (SiNWs), InP, (GaN) and
insulating (e.g. 𝐒𝐢𝐎𝟐 , 𝐓𝐢𝐎𝟐 ). In figure, the typical SEM image of growth of silicon by
catalytic VLSCVD method is depicted.

Nanowires can be used for transistors. Transistors are used widely as fundamental
building element in today’s’ electronic circuits. As predicted by Moore’s law, the
dimension of transistors is shrinking smaller and smaller into nanoscale. One of the key
challenges of building future nanoscale transistors is ensuring good gate control over the

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channel. Due to the high aspect ratio, if the gate dielectric is wrapped around the
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Nanowires channel, we can get good control of channel electrostatic potential, thereby
turning the transistor on and off efficiently. In figure, a schematic picture of 𝐙𝐧𝐎
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nanowire having aspect ratio 300-500 is represented.
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Due to the unique one-dimensional structure with remarkable optical properties, the
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Nanowires also open new opportunities for realizing high efficiency photovoltaic devices.
Compared with its bulk counterparts, the nanowire solar cells are less sensitive to
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impurities due to bulk recombination, and thus silicon wafers with lower purity can be
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used to achieve acceptable efficiency, leading to a reduction on material consumption.

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Besides, Nanowires are also being studied for use as photon ballistic waveguides as
interconnects in quantum dot/quantum well photon logic arrays. Photons travel inside
the tube, electrons travel on the outside shell. When two Nanowires acting as photon
waveguides cross each other the juncture acts as a quantum dot.

Conducting Nanowires offer the possibility of connecting molecular-scale entities in a

molecular computer. Dispersions of conducting Nanowires in different polymers are being
investigated for use as transparent electrodes for flexible flat-screen displays.

Because of their high Young’s module, their use in mechanically enhancing composites is
being investigated. Because Nanowires appear in bundles, they may be used as
tribological additives to improve friction characteristics and reliability of electronic
transducers and actuators.

Because of their high aspect ratio, Nanowires are also uniquely suited to dielectrophretic
manipulation, which offers a low-cost, bottom-up approach to integrating suspended

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dielectric metal oxide Nanowires in electronic devices such as UV, water vapour, and
ethanol sensors.

To create active electronic elements, the first key step is to chemically dope a
semiconductor Nanowires. This has already been done to individual Nanowires to create
p-type and n-type semiconductors. The next step is to find a way to create a pn junction,
one of the simplest electronic devices. This is achieved in two ways. The first is was to
physically cross a p-type wire over an n-type wire. The second method involved chemically
doping a single wire with different dopant along the length. This method created a p-n
junction with only one wire. After p-n junctions are built with Nanowires, the next logical
step is to build logic gates. By connecting several p-n junctions together, researchers have
been able to create the basis of all logic circuits: the AND, OR, and NOT gates have all
been built from semiconductor Nanowires crossings.

It is possible that semiconductor Nanowires crossings will be important to the future of

digital computing. Though there are other uses for Nanowires beyond these, the only ones

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that actually take advantage of physics in the nanometer regime are electronic.
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5. Applications of semiconductor Nanowires in sensing of Proteins and
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Chemicals:
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In FET devices, the modulation of conductance (flow of electrons/holes) in the

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semiconductor, between the input (source) and the output (drain) terminals, is controlled
by electrostatic potential variation (gate-electrode) of the charge carriers in the device
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conduction channel. In an analogous, the methodology of a Bio/Chem-FET is based on the

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detection of the local change in charge density, or so-called field effect that characterizes
the recognition event between a target molecule and the surface receptor.
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This change in the surface potential influences the Chem-FET device exactly as a gate
voltage does, leading to a detectable and measurable change in the device conduction.
When these devices are fabricated using semiconductor Nanowires as the transistor
element the binding of a chemical or biological species to the surface of the sensor can
lead to the depletion or accumulation of charge carriers in the bulk of the nanometer
diameter Nanowires i.e. (small cross section available for conduction channels).
Moreover, the wire which serves as a tunable conducting channel is in close contact with
the sensing environment of the target and thus leads to a short response time along with
orders of magnitude increase in the sensitivity of the device.

While several inorganic semiconducting materials such as Si, Ge and metal oxides (e.g.
𝐈𝐧𝟐 𝐎𝟑 , 𝐒𝐧𝐎𝟐 , 𝐙𝐧𝐎, etc.) have been used for the preparation of nanowires, Si is usually the
material of choice when fabricating nanowire FET-based chemo/biosensors.

Several examples of the use of silicon Nanowires (SiNW) sensing devices include the ultra
sensitive, real-time sensing of biomarker proteins for cancer, detection of single virus

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particles, and the detection of nitro-aromatic explosive materials such as 2,4,6 Tri-nitro
toluene (TNT) in sensitive superior to these of canines. Silicon Nanowires could also be
used in their twisted form, as electromechanical devices, to measure intermolecular
forces with great precision.

Because of the high aspect ratio, the wires have an extremely high ratio of surface area to
volume. That makes them very good as detectors, because all that surface area can be
treated to bind with specific chemical or biological molecules. The electrical signal
generated by that binding can then easily be transmitted along the wire.

6. Single Electron Transfer devices:

Single-electron devices (SEDs) were first advocated in the late 1980s. SEDs have been
studied from the viewpoints of various applications, e.g., digital and analog integrated
circuits for ultralow power consumption, sensors, and metrological tools. The operating
principle of the basic SED is based on the Coulomb blockade, which prohibits single

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electrons from passing through a tunnel junction into a tiny conductive island. The first
SED was made of metal. Since that pioneering work, various materials, such as compound
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semiconductors, Si, and carbon nanotube, have been explored. Among these, Si has great
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advantages: it offers SEDs with highly stable characteristics and fabrication processes that
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are compatible with those for Si integrated circuits.

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More fascinating is the possibility that Si-based SEDs with a single-electron transfer
function could offer a promising way to make the ultimate circuits that use one electron
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to represent one bit of information because of the simple structure and operation of Si
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SEDs compared with those made of other materials. Room-temperature single-electron

transfer, however, has been a tremendous challenge because of the extreme difficulty of
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making conductive islands small enough (<10nm) for the Coulomb blockade to overcome
the thermal energy. In addition, for implementation in real applications, the small signal
originating from single electrons must be detected with high precision to enable us to
access the processed/calculated data (i.e., single electrons).

With the discovery of state-of-the-art nanotechnology, the size of the electronic devices
has been reduced enormously and it has become possible to control the motion of electric
charges at the level of a single electron (SE). Such SE devices are being studied since a few
decades ago in a variety of fields including future low-power large scale integration (LSI),
high-sensitivity sensors, and solid-state quantum computing. Among the categories of SE
devices, the SET has been the most widely investigated because it is a field-effect
transistor that is likely to be suitable for a wide range of applications.

7. Applications of Single Electron Transfer devices:

In this section, various applications of single electron devices in basic physics and
technology are described in details.

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1. Supersensitive electrometers: The single-electron transistors are highly sensitive and
these have enabled them as electrometers in unique physical experiments. For example,
they have made possible unambiguous observations of the parity effects in
superconductors. Absolute measurements of extremely low dc currents (~𝟏𝟎−𝟐𝟎 𝐀) have
been demonstrated using SETs. A modified version of the SET has been used for the first
proof of the existence of fractional-charge excitations in the fractional quantum Hall effect
(FQHE).

2. Single electron spectroscopy: One of the most important applications of single-electron

electrometric is the possibility of measuring the electron addition energies in quantum
dots and other nanoscale objects. This measurement helps to locate the energy level
distribution.

3. DC current standards: One of the possible applications of single-electron tunnelling is

fundamental standards of dc current for such a standard a phase lock SET oscillations or
Bloch oscillations in a simple oscillator with an external RF source of a well characterized

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frequency f. The phase locking would provide the transfer of a certain number m of
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electrons per period of external RF signal and thus generates dc current which is
fundamentally related to frequency as𝐈 = 𝐦𝐞𝐟. This arrangement have limitation of
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coherent oscillation that are overcome by the use of such a stable RF source to drive
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devices such as single-electron turnstiles and pumps which do not exhibit coherent
oscillations in the autonomous mode.
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8. Advantages of Single Electron Transistors:

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Following are the advantages of single electron transistors (SETs) :

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1. Low energy consumption 2. High sensitivity 3. Compact size 4. High operating speed 5.
Simplified circuit 6. Feature of reproducibility 7. Simple principle of operation 8. Straight
forward co-integration with traditional CMOS circuits.

9. Disadvantages of Single Electron Transistors:

Following are the disadvantage of single electron transistors:

1. Integration of SETs in a large scale: To operate SETs at room temperature, large

quantities of mono dispersed nanoparticles less than 10nm in diameter must be
synthesized. But, it is very hard to fabricate large quantities of SETs by traditional optical
lithography and semiconducting process.

2. It is difficult to link SETs with the outside environment.

3. Practically difficult to fabricate Single electron transistors (SETs)

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10. Carbon Nanotube based Transistors:
Since their discovery in 1991, carbon nanotube have attracted much attention and
research funding, due to the strength of their cylindrical structure, which is constructed of
a hexagonal array of carbon atoms. Structure as well as the unique electrical, magnetic,
and optical characteristics has generated a huge potential of industrial and scientific
applications. The fields of carbon nanotube applications include: photo-electric elements,
electric elements, biomedical science, energy materials, and artificial diamonds.

Carbon nanotube can be used in applications that include Field Emission Devices, memory
devices (high-density memory arrays, memory logic switching arrays), Nano-MEMs, AFM
imaging probes, distributed diagnostics sensors, and strain sensors. Other key applications
include: thermal control materials, super strength and light weight reinforcement and
nanocomposites, EMI shielding materials, catalytic support, gas storage materials, high
surface area electrodes, and light weight conductor cable and wires.

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11. Applications of CNT based Transistors:
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The unique nature of carbon combines with the molecular perfection of single-walled
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CNT’s to endow them with extraordinary material properties as indicated above. In such
case, each atom donates a delocalized 𝛑-electron. Instead of remaining with its donor
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atom, this electron freely moves about the whole structure resulting in the first known
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molecule with metallic-type electrical conductivity. Such carbon nanotubes are widely
used in various fields of technology. Some of the applications of this nanotube are
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mentioned below.
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1. Field emission: CNTs are the best known field emitters of any material. This is due to
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their high electrical conductivity and the unbelievable sharpness of their tip. As the tips
radius of curvature becomes smaller, the electric field becomes more concentrated and
results in increased field emission. This is similar to the case of lighting rods – which are
also made sharp. In addition, the sharpness of the tip also indicates that they emit at
specifically low voltage. This is a key fact for building low-power electrical devices. CNTs
can carry an amazingly high current density, as high as 𝟏𝟎𝟗 𝐀/𝐜𝐦𝟐 . Additionally, the
current is extremely stable. This feature is used in field-emission flat-panel displays. It
should be mentioned here that a single electron gun is used in conventional cathode ray
tube (CRT) display whereas CNT-based displays use a separate electron gun (or even many
of them) for each individual pixel in the display. Low turn-on and operating voltages, high
current density and steady, long-lived behaviour makes CNTs very attractive field emitters
in this application. General types of low-voltage cold-cathode lighting sources, electron
microscope sources, and lighting arrestors are other applications utilizing the field-
emission characteristics of CNTs.

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2. Energy storage: The intrinsic properties of CNTs make them the preferred material for
use as electrodes in capacitors and batteries. It is to be noted that these two technologies
are of fast-growing significance. CNTs possess good electrical conductivity, an extremely
high specific surface area (~𝟏𝟎𝟎𝟎 𝐦𝟐 /𝐠) and most importantly, their linear geometry
makes their surface easily accessible to the electrolyte. It has been demonstrated that
CNTs have the highest reversible capacity of any carbon material for use in lithium-ion
batteries. CNTs serve as excellent materials for super capacitor electrodes applications
and are currently being marketed for this application.

In addition, CNTs find applications in various fuel cell components. Because of their high
thermal conductivity and surface area, they are valuable as electrode catalyst supports in
PEM fuel cells. Owing to their high electrical conductivity, they may also be used in gas
diffusion layers. The high strength and toughness-to-weight characteristics of CNTs prove
useful as parts of composite components in fuel cells that are used in transport
applications, where durability is paramount.

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12. Heterostructures Lasers:
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Semiconductor lasers based on gallium arsenide and related materials are widely used in
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applications such as optical communication system, sensing, compact disc players,
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distance measurement, etc. The performance of these lasers can be improved using a
buried heterostructures offering lateral carrier and optical confinement. In particular, if
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the confinement (burying) layer is implemented by epitaxial re growth of an appropriate

aluminium-free semi-insulating material, several additional advantages like passivation of
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etched surfaces, reduced tendency to oxidation, low capacitance and integration

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feasibility are realized in practice.

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In heterostructures laser devices, a layer of low band gap material is sandwiched between
two high band gap layers. One commonly-used pair of materials is gallium arsenide (GaAs)
with aluminium gallium arsenide(𝐀𝐥𝐱 𝐆𝐚𝟏 − 𝐱𝐀𝐬). Each of the junctions between different
bandgap materials is called a heterostructure, hence the name ‘’double heterostructure
laser’’ or DH laser. The middle layer is termed as the active region and has a thickness of a
few hundred angstroms. The schematic cross-sectional view of a heterostructures laser
diode is shown in Figure. The advantage of a DH laser is that free electrons and holes exist
simultaneously in the active region. This means that many more of the electron-hole pairs
can contribute to amplification. In addition, light is reflected within the heterojunction;
hence, the light is confined to the region where the amplification takes place. The double
heterostructures are used to fabricate light emitting devices.

The creation of DH lasers led not only to new light-emitting device concepts and new
physics but also to important technological peculiarities which are indicated below:

1. Fundamental need for structures with well-matched lattice parameters;

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2. The use of multicomponent solid solutions to match the lattice parameters;

3. Fundamental need for epitaxial growth technologies.

Because of electron confinement in double heterostructures, DH lasers have essentially

become the direct precursors to quantum-well structures. Further it should be stated that
the active layer has an element that has the effect of splitting the electron levels as a
result of quantum-size effects. This increases the optical activity in conjunction with the
narrow band gap.

Nanowire lasers are used for ultrafast transmission of information in light pulses.
Nanowire lasers are nanoscale lasers with potential as optical interconnects and optical
data communication on chip. Nanowire lasers are built from III-V semiconductor
heterostructures, the high refractive index allows for low optical loss in the nanowire
core. Nanowire lasers are sub wavelength lasers of only a few hundred nanometers.
Nanowire lasers are Fabry-Perot resonator cavities defined by the end facets of the wire

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with high-reflectivity; recent developments have demonstrated repetition rates greater

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than 200GHz offering possibilities for optical chip level communications.
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13. Magnetic Quantum Well:
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A quantum well is nothing but a potential well having desired discrete energy levels. With
the discovery of delicate scientific instruments, it has become possible to control magnetic
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materials on the nanometer scale. The fine structures of these magnetic materials exhibit
a wide range of fascinating phenomena, such as low dimensional magnetism induced
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magnetization in noble metals, electron interference patterns, oscillatory magnetic

coupling and giant magneto resistance. Magnetic multilayer’s have been fabricated with
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nanometer spacing and are among the first metallic quantum structures to be
incorporated into electronic devices, such as reading heads for hard discs. Compared to
conventional devices, quantum well devices are much faster and operate much more
economically.

In this nanometer scale well, it is possible to tailor the electronic and magnetic properties.
A typical example of an engineered solid is the magneto resistive reading head for data
stored on a magnetic hard disc. The giant magneto resistance (GMR) reading head consists
of Co, Cu and Permalloy (Ni-Fe) and change their electrical resistance under the exposition
to a magnetic field of a stored bit. By these wells, one can find some features in a related
phenomenon such as oscillatory magnetic coupling where an oscillation in the magnetic
orientation of two layers with film thickness takes place. In fact, by inverse
photoemission, one can investigate the discrete energy levels in magnetic quantum well.

It has been observed that there are periodic changes in the DOS when the thickness of Cu
film is changed a couple of atomic layers. These structures can be viewed as the smallest
man made interferometers at the atomic limit. This helps one to map out the wave

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function of electrons. It turns out that DOS maxima are correlated with oscillations of the
magnetic coupling in multilayer. The magneto resistance oscillates with the same period.
This study thus provides a direction for understanding these magnetic phenomena as the
effects of quantized electron levels in nanostructures.

Beside GMR effect in reading heads, there are other magnetic effects that can be
incorporated into electronic devices. Magneto resistance induced by spin-polarized
tunnelling is also the central theme of magnetic random access memory (MRAM) and is
now used in magnetic reading heads. As a result, a new field called magneto electronics
has been developed where spin currents are used instead of charge currents. Electrical as
well as magnetic measurements provide the practical information about these electrons
integrated over all momenta. The angle resolved photoelectron spectroscopy (ARPES) can
be used to resolve the momenta of these electrons. Spin currents can be controlled by
spin doping where magnetic atoms are introduced as dopant for selecting one type of spin
carrier. The Fe/Ni ratio of 20/80 corresponds to Permalloy and is regarded as a dominant

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material in magneto electronics.

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14. Micro Electromechanical systems (MEMS) and their applications:
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MEMS (micro-electromechanical system) are a miniature machine that has both
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mechanical and electronic components. The physical dimension of MEMS can range
between 𝟐𝟎𝛍𝐦 to 1mm, a dimension many times smaller than the width of a human hair.
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They usually consist of a central processing unit and several components which can
interact with the surroundings through sensors. Because of the large surface area to
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volume ratio of MEMS, forces produced by ambient electromagnetism and fluid dynamics
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are more important in design considerations compared to the conventional macroscopic

devices. In fact, MEMS became practical since they could be fabricated using modified
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semiconductor device fabrication technology such as molding and plating, wet etching,
dry etching and electro discharge machining etc.

MEMS are a process technology used to create tiny integrated devices or systems that
combine mechanical and electrical components. They are fabricated using integrated
circuit (IC) batch processing techniques and can range in size from a few micrometers to
millimetres. These devices (or systems) have the ability to sense, control and actuate on
the micro scale, and generate effects on the macro scale. In the most general form, MEMS
consist of mechanical microstructures, micro sensors, micro actuators and
microelectronics, all integrated onto the same silicon chip. It is natural that when
processing several thousand components at the same time, the operating costs can be
reasonably reduced. These components further allow for high precision processing of
applications with a high aspect ratio.

A transducer is a device that transforms one form of signal or energy into another form.
The term transducer can therefore be used to include both sensors and actuators and is

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the most generic and widely used term in MEMS. A sensor is a device that measures
information from a surrounding environment and provides an electrical output signal in
response to the parameter it measured. On the other hand, an actuator is a device that
converts an electrical signal into an action. It can create a force to manipulate itself, other
mechanical devices, or the surrounding environment to perform some useful function.

Some common commercial applications of MEMS include:

1. Inkjet printers, which use piezoelectric or thermal bubble ejection to deposit ink on
paper.

2. Accelerometers in modern cars for a large number of purposes including airbag

deployment and electronic stability control.

3. Inertial Measurement Units (IMUs): MEMS Accelerometers and MEMS gyroscopes in

remote controlled, or autonomous, helicopters, planes and multirotors (also known as
drones), used for automatically sensing and balancing flying characteristics of roll, pitch

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and yaw.
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4. MEMS magnetic field sensor (magnetometer) may also be incorporated in such devices
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to provide directional heading.
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5. MEMS are also used in Inertial navigation systems (INSs) of modern cars, airplanes,
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submarines and other vehicles to detect yaw, pitch, and roll; for example, the autopilot of
an airplane.
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6. Accelerometers in consumer electronics devices such as game controllers (Nintendo

Wii), personal media players/cell phones (virtually all smart phones, various HTC PDA
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models) and a number of Digital Cameras. Also it is used in PCs to park the hard disk head
when free-fall is detected, to prevent damage and data loss.

7. MEMS microphones in portable devices, e.g., mobile phones, head sets and laptops.
The market for smart microphones includes smart phones, wearable devices, smart home
and automotive applications.

8. MEMs are also used in precision temperature-compensated resonators in real-time

clocks.

9. MEMs also find applications in silicon pressure sensors e.g., car tire pressure sensors,
and disposable blood pressure sensors.

10. They are also used in displays e.g., the digital micro-mirror device (DMD) chip in a
projector based on DLP technology, which has a surface with several hundred thousand
micro-mirrors or single micro-scanning-mirrors also called micro-scanners

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11. They are also used in optical switching technology, which is used for switching
technology and alignment for data communications.

12. Bio-MEMS find their applications in medical and health related technologies from Lab-
On-Chip to Micro-Total-Analysis (biosensor, chemosensory), or embedded in medical
devices e.g. stents.

13. MEMS is also routinely used in interferometry modulator display (IMOD) applications
in consumer electronics (primarily displays for mobile devices), used to create
interferometry modulation, and reflective display technology as found in mica sol
displays.

14. MEMS is used in fluid acceleration such as for micro-cooling.

15. Recently, MEMS is used in micro-scale energy harvesting including piezoelectric,

electrostatic and electromagnetic micro harvesters.

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13. Nanoelectromechanical systems (NEMS) and their applications:
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Nanoelectromechanical systems (NEMS) are a class of devices integrating electrical and
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mechanical functionality on the nanoscale. In a simple note, they are devices that
inherently convert electrical energy to mechanical and vice versa. NEMS are nothing but
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the integrated transistor-like nanoelectronics with mechanical actuators, pumps, or

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motors, and may thereby form physical, biological, and chemical sensors. These systems
possess potentially large quantum mechanical effects such as zero point motion, and a
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high surface-to-volume ratio useful for surface-based sensing mechanism. NEMS can
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either be produced by bottom-up approach (e.g. chemical self-assembly methods, CVD

methods, hot plate technique) or by top-down methods (e.g. metallic thin films, etched
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semiconductor layers etc.)

NEMS have critical structure elements at or below 100nm. This distinguishes them from
MEMS where the critical structure elements are on the 𝛍𝐦 length scale. Besides,
compared to MEMS, NEMS combine smaller mass with higher surface area to volume ratio
and are therefore most effective for applications regarding high frequency resonators and
ultra-sensitive sensors.

A key application of NEMS is atomic force microscope tips. The increased sensitivity
achieved by NEMS leads to smaller and more efficient sensors to detect stresses,
vibrations, forces at the atomic level, and chemical signals. AFM tips and other detection
at the Nano scale rely heavily on NEMS. NEMS also find applications in high precision
surgical equipment used in robotic surgery. NEMS also promise to revolutionize
measurements related to extremely small displacements, extremely weak forces
particularly at the molecular level. Thus, it paves the path leading to fundamental
research in basic sciences. NEMS applications are envisaged in sensing, displays, portable

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power generator, energy harvesting, drug delivery and imaging, 𝐩𝐇 sensors, protein
concentration detectors and relays and switches with nanotubes. Nanomachine because
of small mass and size are attracting the researchers for potential applications and
fundamental measurements. Besides, it has high rating of fundamental power.

Many of the commonly used materials for NEMS technology have been carbon based,
specifically diamond, carbon nanotube and grapheme. This is mainly because of the useful
properties of carbon based materials which directly meet the needs of NEMS. The
mechanical properties of carbon (such as large Young’s modulus) are fundamental to the
stability of NEMS while the metallic and semiconductor conductivities of carbon based
materials allow them to function as transistors. Carbon-based materials have served as
prime materials for NEMS use, because of their exceptional mechanical and electrical
properties.

NEMS sensors have been used for mass spectrometry applications: NEMS devices due to
the small size are extremely sensitive to changes in its properties. This property has

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recently been utilized to demonstrate mass spectrometry on bio molecules using
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extremely sensitive NEMS devices. As part of the sensors area, NEMS devices made of
carbon nanotube are being used as extremely sensitive mass sensors to measure mass of
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individual protein molecules. Research emphasis in this area includes the fabrication of
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suspended single walled carbon nanotube and development of an ultra-high vacuum

system for performing mass spectrometry.
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NEMS and MEMS have played important key roles in many areas such as transportation,
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communications, environmental monitoring, defence system, health care and varieties of

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consumer products. These systems inherently possess smaller dimensions, less weight and
power dissipation and improved speed along with precision. NEMS is expected to serve as
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an enabling technology merging engineering with life sciences in ways which are not
currently feasible micro scale tools and technologies.

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