NanoPhysics

and
Nanotechnology
 Nanomaterials
All materials are composed of grains, which in turn
comprise many atoms. The visibility of these grains
depends on their size. The materials possessing grains of
size ranging from 1 to 100 nm, are known as
“Nanomaterials” and the developed technology is called
Nanotechnology. This was first discovered by Feynman in
1959.

Examples: ZnO, TiO2,Cu-Fe alloys etc.,

 What do you mean by Nano Particles
Nano Particles are the particles of size between 1 nm to 100 nm

Nanometer - One billionth (10-9) of a meter

• The size of Hydrogen atom ~0.04 nm
• The size of Proteins ~ 1-20 nm
• Virus is ~100 nm
• Diameter of human hair ~ 10 µm

When the size of the object is reduced to nanoscale: exhibits

different properties than the same material in the bulk form.

Example : Opaque substances turn to transparent; inert elements

become catalysts; solids change in to liquids; insulators become
conductors
 What is Nanotechnology?
➢ Nanoscience : study of properties of the materials at the
nanoscale where properties differ significantly than those at
larger scale
➢ Nanotechnology : Applications of nanoscience

❖ The application of structures, devices, and systems by

controlled manipulation of size and shape of materials at
the nanometer scale
 Why Nanotechnology?
With nanotechnology it is possible to control matter on every
important length scale.

These developments in nanotechnology can effect domains such as:

Materials: new materials which are harder, more durable and resistance,
lighter and less expensive can produced.

Electronics: electronics components will become smaller and smaller,

allowing the deign of more computers.

Energy: a vast increase in the potential of solar energy generation.

Health and Biotechnology: great expectations are held in the areas of

prevention, diagnostics and treatment.
 Classification of Nanomaterials:

Nanomaterials are classified as zero dimmensional, one dimensional,

two dimensional, three dimensional nanostructures.

Energy vs Density of states

Zero dimensional nanomaterials: Materials wherein all dimensions are
measured with in nanoscale (no dimensions, or 0-D, are larger than 100nm).
Ex: Clusters or Bulk form
One dimensional Nanomaterials: - This consists of ultrafine grains layered over
layers or buried layers
Ex: Nano wires and nano tubes.
Two dimensional Nanomaterial: - In these Nanomaterial, grains will be
layered in the form of multi-layers
Ex: Thin films or surface coatings.
Three dimensional Nanomaterials: - This consists of nanometer sized grains.
Ex: Polycrystalsforms and quantum dot.
SIGNIFICANCE OF NANOSCALE:

Quantum, Mechanical and Thermodynamic properties of the materials

become important at nanolevel that cannot be seen at macroscopic level.

Nanoscience : Properties of the material change with the function of

physical dimensions of the materials

Not predominant from macro to micro range; but only when nano size is
reached

Two principle factors cause the properties of nanomaterials to differ

significantly from other materials i.e. increased in surface area to volume ratio
and quantum confinement .

These factors can change or enhance the properties such as reactivity,

strength and electrical characteristics.
INCREASE IN SURFACE AREA TO VOLUME RATIO :

Nanomaterials have a relatively larger surface area when compared

to the larger form of the material of same volume.
Let us consider a sphere of radius ‘r”.
Its surface area = 4ᴨr2
Its volume = 4/3ᴨr3
Surface area to its volume ratio = 4ᴨr2 = 3/r
-----
4/3ᴨr3

Thus, when the radius of the sphere decreases, its surface area to volume
ratio increases.
 Let us consider another example. For a one cubic volume shown in fig.
The surface area is 6m2. When it is divided in to eight pieces its surface area
becomes 12m2.When the same volume is divided in to 27 pieces its surface area
becomes 18m2 . Thus we find that when the given volume is divided in two
smaller pieces, the surface area increases. Hence nanoparticles have a greater
surface area per given volume compared with larger particles.

For example, a nanomaterial of size 10nm has 20% of its atoms on its surface
and at 3nm has 50% of its atoms.
QUANTUM CONFINEMENT: -

The properties of materials can be studied based on their energy levels.

When atoms are isolated, their energy levels are discrete. When very large
number of atoms closely packed to form a solid the energy levels split and form
bands. Nanomaterial is intermediate to the above cases. As a result, the energy
levels change, when the material size is reduced to nanoscale, energy levels of
electrons changes. This effect is called “Quantum confinement”

This affects the optical, electrical and magnetic properties of nano materials.
The bandgap increases as the size of the nanostructure decreases
• Quantum confinement is the spatial confinement of electron and hole
pairs in one or more dimensions
1-D confinement- Quantum well
2-D confinement – Quantum wire
3-D confinement – Quantum dot

• Quantum confinement is more prominent in semiconductors because

they have an energy gap in their electronic band structure

• Metals do not have a band gap, so quantum size effects less prevalent.
Quantum confinement is only observed at dimensions below 2 nm

• The Quantum confinement is observed when size the particle is too small
to be comparable to the de-Broglie wavelength of electron
Properties of Nanomaterials: -
As the size of the nano particle is very less, these materials exhibits
peculiar physical, electronic, magnetic, mechanical and chemical properties.

➢Physical properties :-
• Since the size of the particle is very less, the particles are very close to each
other and hence the inter particle spacing is very less in nano materials.
•Because of its very less size, these nano materials cannot be further divided into
smaller particles and it does not have any dislocation in it. Thus we can say that
they have high strength, hardness and toughness.
•The melting point of nano materials will be very less.
➢Mechanical properties :-
•Mechanical properties such as hardness, toughness, elastic modulus varies from
material to material.
•They exhibit super plastic behavior.

➢Chemical properties:-
•The nano structures in chemistry are collides and these are formed in a
condensed phase having size in the range from 1 to 100nm.
•The chemical reactivity of a cluster depends on the cluster size. This is useful in
the preparation of catalytic agents. Some chemically inert bulk materials become
good chemical catalyst in the nano phase, for example: Platinum and gold.
•In chemical reactions, the rate of increase in mass transport increases as the
particle size decreases.
➢Magnetic properties: - The nanomaterials shows variation in their magnetic
property, when they change from bulk state to nano phase state. Some of the
examples are listed in table (1).

S.No Material Bulk state Nano-phase state

1 Iron, Ni,Cobalt Ferro-magnetic Super Para-magnetic

2 Sodium, Potassium Para-magnetic Ferro magnetic

3 Chromium Anti-ferromagnetic Para-magnetic

➢Optical Properties

• Semiconductor particles are made very small , Quantum effects come into
play which limits the energies of electrons and holes can exist in the
particle.
• Energy in relation to the wavelength : colour ; depends on the size
• Controlling the size : particle can be made to emit or absorb specific
wavelengths

Optical absorption spectrum of gold parcticles 20

➢ Electrical properties: -
• The energy bands in these materials will be very narrow
• The properties like conductivity or resistivity are come under category of
electrical properties. These properties are observed to change at
nanoscale level like optical properties.
• The electrical conductivity of same materials change when they pass from
bulk phase to nanoparticle phase.
For example, bulk silicon is an insulator; it becomes a conductor in
nano phase. Nanomaterial semiconductors such a Ge and Si does not
show semi conducting property
• Conductivity of a bulk or large material does not depend upon dimensions
like diameter or area of cross section
• However it is found that in case of carbon nanotubes conductivity changes
with change in area of cross section
• The carbon nanotubes can act as conductor or semiconductor in
behaviour
Fabrication of Nanomaterials:-
Nano materials can be generally fabricated in two broad ways,
namely
(i) Top-down approach
(ii) Bottom – up approach
Top-down approach: - In which, the bulk solid materials are broken
into nano sized particles.

Ball Milling Plasma Arching Laser Sputtering

(ii)Bottom – up approach: - Building of the material from bottom

(atom by atom, molecule by molecule or cluster by cluster)
Chemical Solution-
Electro Sol-Gel
Vapour Phase
Deposition method
Deposition Reduction
Bottom-up or top-down?
. Figure: Schematic representation of the building up of Nanostructure
 Ball Milling or Mechanical crushing

• High energy mills used for fabrication of nanoparticles include attrition

mill, planetary ball mill, vibrating ball mill, low-energy tumbling mill and
high energy ball mill.

• Principle :
– Small hard balls are allowed to rotate inside a container and then it is
made to fall on a solid base with high force to crush the solid into
nanoparticles

• Construction:
– Hardened steel or Tungsten Carbide balls are put in to the container
with the powder of the particles, Container is then tightly closed.

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• Working :

– Balls are rotated around the central axis: Material is forced to press
against the balls : Milling balls impart energy on collision : produce
small grained nanoparticles.

Schematic of Ball Milling Technique

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• Advantage:

– Operated on a large scale

– Few mg to several kg of nanoparticles can be produced

▪ Applications:

➢ Preparation of elemental and metal oxide nanocrystals such as Co, Cr,

Fe etc

➢ Intermetallic compounds can be prepared

➢ Useful in producing new types of building materials, fireproof

materials, glass ceramics etc

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 Arc discharge method for carbon Nanotubes
• The principle of this technique is to vaporize carbon in the presence of
catalysts (ion, nickel, cobalt….) under reduced atmosphere of inert gas
(helium or argon)

• After triggering of the arc between two electrodes a plasma is formed

consisting of the mixture of carbon vapour, the rare gas (helium or argon)
and vapours of catalysts

• The vaporization is the consequence of the energy transfer from the arc to
the anode made graphite doped with catalysts

• The anode erosion rate is more or less important depending on the power
of the arc and also on the other external conditions.
Schematic Diagram of Arc deposition method
Apparatus:
➢ Apparatus must be connected with vacuum diffusion pump to a helium
supply
➢ The electrodes are two graphene rods usually high purity
➢ Anode is a long rod approximately 6mm diameter and cathode short rod
approximately 9 mm diameter
➢ DC bias 12-15V applied between two carbon electrodes in a helium
atmosphere
➢ Carbon atoms ejected from anode and accumulated in cathode as
nanotubes

Applications:
➢ Synthesis of metal nanoparticles
➢ Synthesis of Nanowires eg: Ag nanowires
➢ Synthesis of nano meta oxides
➢ Production carbon nanotubes
➢ Preparing graphene flakes
 Chemical Vapour Deposition
➢ To produce high purity, high performance solid materials.

➢ Often used in semiconductor industry for the production of thin films

➢ Principle: Synthesis of the materials in which chemical components in

vapour phase transforms to a solid film at some surface (substrate)

➢ Main Theme: Occurrence of the chemical reaction : start at the vapour

phase

➢ Use: Ability to control the components and physical conditions of the gas
phase
• Micro and Nano fabrication processes of various form including
monocrystalline, polycrystalline, amorphous and epitaxial.

• Method useful for producing Synthetic diamonds and nano diamonds.

• Sequential process; Vacuum deposition process

• Initial vapour phase : series of quasi-steady sub processes: formation of a

solid thin film (micro/nano structure)

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CVD on the whole: Precursor gases are to be delivered to the reaction
chamber at ambient temperatures. The gases passes through the chamber
and they come in contact with the substrate, react or decompose by
forming a solid phase and gets deposited on the substrate.
Two main Steps :
1. Transport Process
2. Deposition Process

Set up of CVD 36
Transport Process:
➢ Transport of the gas phase materials to reaction tone
➢ Convection of the gas phase materials due to pressure gradients

Convection in CVD:
Flow of the gaseous fluid as it moves through the reactor after being
injected from the gas supply.

Convection : Two types

A. Forced Convection: Pressure gradient across the chamber
B. Free Convection : Buoyancy of the hot gases

➢ Diffusion of gaseous reactants to the substrate surface

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Deposition Process:
➢ The adsorption of the reactant species on the substrate surface sites by
surface migration followed by surface chemical reaction between the
reactant species
➢ Incorporation of the condensed solid products in to the macro/nano-
structure of the growing film

Steps involved in CVD Process

Processes involved in CVD
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➢ Viscous Friction : Gas molecules experience it when they come close
to the substrate surface. Due to this, the flow velocity slows down,
remaining transport is by means of diffusion.
➢ Transition from Convection to diffusion : the gas molecules are
adsorbed to the gas molecule followed by surface reaction

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Pulsed Laser Deposition:
• Pulsed laser deposition (PLD) is a physical vapour deposition (PVD)
technique where a high-power pulsed laser beam is focused inside
a vacuum chamber to strike a target of the material that is to be
deposited.

• This material is vaporized from the target (in a plasma plume) which
deposits it as a thin film or cluster on a substrate. This process can occur
in ultra high vacuum or in the presence of a background gas, such as
oxygen

• While the basic setup is simple relative to many other deposition

technique

• The physical phenomena of laser-target interaction

Configuration of a PLD deposition chamber
Working:
When the laser pulse is absorbed by the target, energy is first
converted to electronic excitation and then into thermal, chemical and
mechanical energy resulting in evaporation, ablation, plasma formation.
The ejected species expand into the surrounding vacuum in the form of a
plume containing many energetic species including atoms, molecules,
electrons, ions.

The process of PLD can generally be divided into four stages:

➢ Laser ablation of the target material and creation of a plasma
➢ Dynamic of the plasma
➢ Deposition of the ablation material on the substrate
➢ Nucleation and growth of the film on the substrate surface
• The ablation of the target material upon laser irradiation and the creation
of plasma are very complex processes.

• In the second stage the material expands in a plasma parallel to the

normal vector of the target surface towards the substrate due to Coulomb
repulsion and recoil from the target surface.

• The third stage is important to determine the quality of the deposited

films. The high energetic species ablated from the target are bombarding
the substrate surface

• The nucleation process and growth of the thinfilm depend on Laser

parameters, Surface temperature, Substrate surface, Background pressure
 Carbon Nanomaterials
• Fullerences and carbon nanotubes (CNTs) are the two important
nanomaterials.

• The fullerences and carbon nanotubes are a class of allotropes of carbon

which conceptually are graphene sheets rolled into spheres or tubes
respectively.
 Fullerenes
• Fullerenes are very large graphitic systems. Fullerene commonly refers to a
molecule with 60 carbon atoms.

• It was discovered in 1985 by Harry kroto and Richard smalley. They named
it buckminsterfullerene, in recognition of the architect Buckminster Fuller

• C60 Is a hollow, spherical molecule about 1mm in diameter, comprising 60

carbon atoms.

• It is also known as bucky ball and has 32 faces. These ball like molecules
bind with each other in the solid state to form a crystal lattice having a FCC
structure.

• After the discovery of C60 other related molecules (C36, C70, C76 and C84 )
composed of only carbon atoms, but possess different geometric
structures
Geometric structure:
• In C60, 60 carbon atoms are placed. Each carbon site is equal to every
other site. The average nearest neighbour C-C distance in C60 (1.44A0) is
approximately the dame to that in graphite (1.42A0).
• Each carbon atom in C60 is trigonally bonded to other atoms
• There are 20 hexagonal faces and 12 additional pentagonal faces in each
C60 molecule with a molecule diameter of 7.10A0

The C60 molecule

Synthesis:
• Fullerenes are synthesized by arc discharge between graphite electrodes
in around 200 torr of He gas.
• The heat generated at the contact point between the electrodes
evaporates carbon to form soot and fullerenes.
• They condense on the water cooled walls of the reactor.
• The carbon soot contains up to ~ 15% fullerenes: C60 (~13%) and C70 (~2%)
• The fullerenes are next separated from the soot by use of liquid
chromatography.
• Applications:
• C60 has the right size to fit into an enzyme, which would kill the virus such
as AIDS
• Useful in industrial applications such as optical devices, chemical sensors
and chemical separation devices.
• Useful in the production of diamonds and carbides as cutting tools or
hardening agents
• For producing polymers of rugged structure and high reactivity.
 Carbon Nanotubes

• A carbon nanotube is a cylindrical rolled up sheet of graphene, which is a

single layer of graphite atoms arranged in a hexagonal pattern as shown in
figure.
• Each nanotube is a single molecule composed of millions of atoms
• The length of (~100nm) of a carbon nanotube is much greater than its
diameter (~2nm).
• Their hexagonal structure gives them great tensile strength and elastic
properties.
Types of Carbon Nanotubes:
Carbon nanotubes are of two types
(1) Single walled nanotubes (SWNT)
(2) Multi walled nanotubes (MWNT)

Single walled nanotubes (SWNT):

➢ Single walled nanotube consisits of a graphene sheet rolled on leading to a
single cylinder as shown in fig
➢ The ordered arrays of single wall nanotubes called ropes
➢ The SWNTs have diameters from 1nm to 5 nm and are usually well over 1
mm in length
➢ SWNTs can be considered as long wrapped graphene sheets
➢ They can be considered as nearly one dimensional structure
Multi walled nanotubes (MWNT):
• A multi walled carbon nanotube (MWNT) is the arrangement of several
coaxial tubes of graphene sheets forming a tube like structure as shown in
fig
• Each MWNT has form 2 to 50 such tubes
• Separation beween neighbouring tube is nearly 0.34 to 0.36 nm
• MWNTs have inner diameter from 1.50to 15nm and outer diameter from
2.5 to 30 nm
• MWNTs are useally well over 1 mm in length
Synthesis of Carbon Nanotubes:
There are number of methods of making CNTs and fullerenes such as
➢ arc deposition,
➢ Pulsed laser deposition
➢ and Chemical vapour deposition

Properties of CNTs:
➢ Because of sp2 carbon-carbon bonds, carbon nanotubes can bend like a
rubber tube even with a high strength
➢ Thermal conductivity of carbon nanotubes is 10 times that of silver
➢ Some CNT have superior conductivities than that of copper, where as
others act more like semiconductors
➢ SWNT consist of two separate regions with different physical and chemical
properties
Applications:
➢ Energy storage
➢ Hydrogen storage
➢ Electrochemical super capasitors
➢ Field emitting devices
➢ Transistors
➢ Nano probes and sensors
 Graphene:

• Graphene is a one atom thick planar sheet of Sp2 bonded carbon atoms
that are densely packed in a honeycomb crystal larrice.
• The names comes from GRAPHITE
• The carbon-carbon bond length in graphene is ~1.42Ao
• Graphene is the basic structural element of all other graphitic materials
including graphite, CNTs and fullerenes.
Properties of Graphene:

• The expected structure of graphene is hexagonal lattice

• Intinsic graphene is a semi metal or zero gap semiconductor
• It exhibits high electron mobility at room temperature
• It exhibits thermal conductivity at room temperature
• It exhibit high young’s modulus hence it is very strong and rigid

Applications:
• It is used as the channel in FET due to high carrier mobility
• Graphene - based FET used in amplifiers
• They are used in phase shift detectors
• Wide applications in logic gates.
 Applications of Nanotechnology

(i) Mechanical Engineering :-

•Since they are stronger, lighter etc; they are used to make hard metals.
•Nano - MEMS ( Micro-Electro Mechanical Systems ) are used in ICS, optical
switches, pressure sensors, mass sensors etc
•Nanocrystalline ceramics are used in automotive industry as high strength
springs, ball bearings and valve lifters.

(ii) Electrical Electronics and Communication Engineering:-

•Orderly assembled nano materials are used as quantum electronic devices and
photonic crystals.
•Some of the nano materials are used as sensing elements. Especially the
molecular nano materials are used to design the robots, assemblers etc.
•They are used in energy storage devices such as hydrogen storage devices,
magnetic refrigeration and in ionic batteries.
• Dispersed nano materials are used in magnetic recording devices, rocket
propellant, solar cells, fuel cells etc.
• Recently nano robots were designed which are used to remove the
damaged cancer cells and also to modify the neuron network in human
body.

(iii) Computer Science Engineering and IT:-

• Nano materials are used to make CD’s and Semiconductor laser.

• These materials are used to store the information in smaller chips.
• They are used in mobiles, lap-tops etc.
• Further they are used in chemical/ optical computer.
• Nano-dimensional photonic crystals and quantum electronic devices plays
a vital role in the recently developed computers.
(iv) Bio-Medical and Chemical Engineering:

-Consolidated state nano particles are used as catalyst, electrodes in solar

and fuel cells.
•Bio-sensitive nano particles are used in the production of DNA-chips, bio-
sensors etc.
•Nano-structured ceramic materials are used in synthetic bones.
•Few nano materials are also used in adsorbents, self-cleaning glass, fuel
additives, drugs, Ferro fluids, paints etc.
•Nano-metallic colloids are used as film precursor.
Nano shells as Cancer Therapy
Nano shells are injected into cancer area and they recognize cancer cells. Then by
applying near-infrared light, the heat generated by the light-absorbing Nano shells
has successfully killed tumor cells while leaving neighboring cells intact.
Thank you