Nanoscience

BIRTH OF NanoTechnology

Plenty of rooms at the bottom

“… it seems that the laws of physics

present no barrier to reducing the size of computers until bits are the
size of atoms, and quantum behavior holds way.”
- Richard P. Feynman (1985)

2
 Moore’s law
The number of components in integrated circuits will be doubled
Every 18 months.

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 Nano Science
Nano Science can be defined as the study of phenomena and
manipulation of materials at Atomic, Molecular and
Macromolecular scales where properties differ significantly
from those at a larger scale.

Nano Science is the study and understanding of properties of

Nano Particles.

Nano Technology
Nanotechnology can be defined as the design,
characterization, production and application of structures
devices and systems by controlling shape and size at a Nano
meter Scale.
 Nano Material
1. Nano Materials could be defined as the materials with at least
one of its dimensions in the range of a Nano meter.
2. Thus the material need not be so small that it cannot be seen, it
can be a large surface or a long wire whose thickness is in the
scale of Nanometers.
3. Materials that are Nano scale in one dimension are layers, such
as a Thin films or Surface coatings.
4. Materials that are Nano Scale in two dimensions include Nano
wires and Nano tubes.
5. Materials that are Nano scale in three dimensions are particles
for example precipitates, colloids and quantum dots (Small
particles of Semiconductor Materials)
 Why properties of Nano Materials are different ?
The properties of Nano Materials are very much
different from those at a larger scale.
Materials in nanometers dimension are significantly
different from that bulk materials. This is due to
[Link] surface area to volume ratio.
2. Large fraction of atoms at the surface.
3. High surface energy
[Link] confinement effect.
5. Reduced imperfections.
These factors can change or enhance properties such as
reactivity, strength and electrical characteristics.
 Increase in a Surface Area to Volume ratio

Nano Materials have a relatively larger Surface area when

compared to the same volume or mass of the material
produced in a larger form.

Let us consider a Sphere of radius “r”.

Its Surface Area =4πr2.
Its volume= 4/3πr3
Surface Area to Volume Ratio= 3/r.
Thus when the radius of the Sphere decreases , its Surface
to Volume ratio increases.
 1m

surface area  6 1m2  6m2

 Let us consider one Cubic Volume shown in figure its the
Surface Area is 6m2 .
 When it is divided into eight pieces its Surface Area
becomes 12m2, similarly When the same volume is divided
into 27 pieces its Surface Area becomes 18m2.
 Thus we find that when the given volume is divided into
smaller pieces the Surface Area increases.
 Hence as particle size decreases a greater proportion of
atoms are found at the surface compared to those inside.
 Nano particles have a much greater surface area per given
volume compared with larger particles. It makes materials
more Chemically reactive.
1
m
2

1 2
surface area  6  ( m)  8  12m 2
2
 Quantum Confinement
Electronic energy levels are continuous in the bulk
materials, whereas nano crystals have discrete energy
levels. This is due to the confinement of the
electronic Wave function to the physical dimensions
of the particles. This phenomenon is called
Quantum confinement.

Spatial dimensions of the system are of the order of

de Broglie wavelength of carriers and hence energy
levels and density of states are quantized.
 Underlying concept in quantum confinement is
particle in a box problem, in which the spacing
between the energy levels increases as the length of
the box decreases.

Energy level separation increases as the size of the size

of the nano crystals decreases.

Confinement depends on parameters like dielectric

constant and effective mass.
 Types of Quantum Confinement

Dimension Variation 
Zero dimensional confinement:
particles are free to move in all the three spatial directions.
One dimensional confinement: particles are confined in
one direction and free to move in Other two directions.
This is known as Quantum well systems.
Quantization is inversely proportional to thickness of the wall.
Two dimensional confinement:
particles are confined in two directions and free to move in
one direction. This is known as Quantum Wire systems.
Quantization is inversely proportional to the diameter of the wire.
Three dimensional confinement:
particles are resatricted to move in all three directions.
This is known as Quantum Dot systems.
Quantization is inversely proportional to the diameter of the sphere.
Nanoscale materials are divided into three category

1. Zero dimension – length, breadth and heights are confined at

single point. (for example, Nano/Quantum dots)

2. One dimension – It has only one parameter either length (or)

breadth (or) height ( example: nano/Quantum wires )

3. Two dimensions- it has only length and breadth (for example,

quantum well)

1. Three dimensions -it has all parameter of length, breadth and

height. (for example, Nano Particles).
Density of states: No. of states with energies between E and E+dE
Quantum dot
• It is a zero dimensional system
• The electron movement was restricted in entire three
dimensions
• It is a semiconductor nano-structure that confines the motion of
conduction band electrons, valence band holes or excitons in
all three spatial directions.

Quantum dot

In quantum dot all the three dimensions are reduced to zero

Quantum Wire
• It is a one-dimensional system
• The electron can move in one direction and restricted in two
directions.
• Quantum wires are ultra fine wires or linear arrays of Nano dots,
formed by self-assembly
• They can be made from a wide range of materials such as Semiconductor
Nanowires made of silicon, gallium nitride and indium phosphide.

* Nanowires can be prepared by growth techniques such as

1. Chemical Vapour deposition (CVD)
2. Electroplating

Nanowires have potential applications in

1. In high-density data storage
2. In electronic and opto-electronic Nanodevices
General properties of Nanowire
 Diameter – 10s of nanometers
 Single crystal formation -- common crystallographic orientation along the
nanowire axis
 Minimal defects within wire
 Minimal irregularities within nanowire arrays.

Some example of Nanowire

Quantum well
• It is a two dimensional system
• The electron can move in two directions and restricted in one direction.
• Quantum wells are formed in semiconductors by sandwitching the material
between two laters of a material with a wider band gap

Semiconductor substrate
growth (single
layer)
Properties of Nano materials
 Physical Properties of Nano Particles
• Crystal structure of Nano particles is same as bulk
structure with different lattice parameters.
• The inter atomic spacing decreases with size and
this is due to long range electrostatic forces and the
short range core-core repulsion.
• The Melting point of Nanoparticles decreases with
size.
• The total surface area (or) the number of surface
atom increases with reducing size of the particles
 Mechanical properties
• Due to nano size mechanical properties like
melting point, hardness, wear resistance, fracture
toughness, elastic modulus are modified to large
extent
• Synthesis of Metals with grain size of 50 – 100 nm
gives extremely high strength. Relation between
grain size and yield strength is
• The Melting point of Nanoparticles decreases with
size due to high surface to volume ratio.
• Hardness of the nanomaterials is high due to less
imperfections.
 Optical properties
• Optical band gap of semiconductors and
conductors increases as the size decreases.
Bulk Gold- Yellow; nano sized Gold –Red

• Colour of materials arises due to surface Plasmons

(natural oscillations of electrons within a
nanosphere). If the size is reduced then surface
Plasmon frequency changes and hence change in
colour is observed.
 Electrical properties
• The electronic structure of Nano materials is
different from its bulk material.
• The density of the energy states in the conduction
band changes.
• The Ionization potential at Nano sizes are higher
than that for the bulk materials
• Carrier concentration decreases and mobility of the
carriers increases.
• Bulk Carbon – Conductor; CNT-
Conductor/semiconductor.
 Magnetic Properties
• Some materials exhibit different magnetism at nano scale
when compared to their bulk nature.
Eg. Bulk pd and pt are not magnetic whereas their
nanoparticles are ferromagnetic.

• Bulk Gold is diamagnetic, when capped with suitable

molecules Gold exhibits ferromagnetism.

• Permanent magnetism is observed in the case of thiol

capped Gold nanoparticles.

• Super paramagnetism occurs when the material is

composed of nano crystallites of size 1 – 10 nm.
 Preparation of Nanomaterials

Physical Methods Chemical Methods

Electro- Chemical Chemical vapor

Ball Milling Sputtering/ Deposition reactions Deposition
Evaporation
Applications of Nano Materials
1. Nanotechnology Applications in Medicine

• Because of their small size, nanoscale devices can readily interact with
biomolecules on both the surface of cells and inside of cells.
• By gaining access to so many areas of the body, they have the potential to detect
disease and the deliver treatment.
2. Sunscreens and Cosmetics

• Nanosized titanium dioxide and zinc oxide are currently used in some sunscreens, as
they absorb and reflect ultraviolet (UV) rays.
• Nanosized iron oxide is present in some lipsticks as a pigment.

3. Fuel Cells

The potential use of nano-engineered membranes to intensify catalytic processes could

enable higher-efficiency, small-scale fuel cells.
 4. Displays
• Nanocrystalline zinc selenide, zinc sulphide, cadmium sulphide and lead telluride are
candidates for the next generation of light-emitting phosphors.
• CNTs are being investigated for low voltage field-emission displays; their strength, sharpness,
conductivity and inertness make them potentially very efficient and long-lasting emitters.

5. Batteries
• With the growth in portable electronic equipment (mobile phones, navigation devices,
laptop computers, remote sensors), there is great demand for lightweight, high-energy
density batteries.

• Nanocrystalline materials are candidates for separator plates in batteries because of their
foam-like (aerogel) structure, which can hold considerably more energy than conventional
ones.

• Nickel–metal hydride batteries made of nanocrystalline nickel and metal hydrides are
envisioned to require less frequent recharging and to last longer because of their large
grain boundary (surface) area.
 6. Catalysts
In general, nanoparticles have a high surface area, and hence provide higher catalytic
activity.

7. Medical Implantation

• Unfortunately, in some cases, the biomedical metal alloys may wear out within the lifetime
of the patient. But Nano materials increases the life time of the implant materials.

• Nanocrystalline zirconium oxide (zirconia) is hard, wear resistant, bio-corrosion resistant

and bio-compatible.

• It therefore presents an attractive alternative material for implants.

• Nanocrystalline silicon carbide is a candidate material for artificial heart valves primarily
because of its low weight, high strength and inertness.
8. Magnetic Nano Materials applications

• It has been shown that magnets made of nanocrystalline yttrium–samarium–cobalt

grains possess unusual magnetic properties due to their extremely large grain interface
area (high coercivity can be obtained because magnetization flips cannot easily
propagate past the grain boundaries).

• This could lead to applications in motors, analytical instruments like magnetic

resonance imaging (MRI), used widely in hospitals, and microsensors.

• Nanoscale-fabricated magnetic materials also have applications in data storage.

• Devices such as computer hard disks storage capacity is increased with Magnetic Nano
materials

9. Water purification

•Nano-engineered membranes could potentially lead to more energy-efficient water

purification processes, notably in desalination process.
NANO SCIENCE
 Nanotechnology is ancient history

The stunning Lycurgus cup (AD 400) reveals a brilliant red when light
passes through its sections of glass containing gold-silver alloyed
nanoparticles.
 What is Moore’s Law?

Moore's Law states that the number of transistors that can be placed on an
integrated circuit for the same price will increase exponentially by a factor of
2 every 18 to 24 months. In other words, put simply Moore's Law claims that
CPU processing power will double approximately every two years for the price
of 1,000 dollars
For the better part of the '70s, '80s, '90s,
and into the first decade of the 21st century,
Moore’s law proved to be correct—but only
because it was a self-fulfilling prophecy,
according to a recent article in the science
journal Nature, which argues that the
prophecy is about to come to an end.
Bulk 2D 1D 0D
What are Carbon nanotubes.
•Carbon nanotubes (CNTs) are allotropes
of carbon. These cylindrical carbon
molecules have interesting properties
that make them potentially useful in
many applications in nanotechnology,
electronics, optics and other fields of
materials science, as well as potential
uses in architectural fields. They exhibit
extraordinary strength and unique
electrical properties, and are efficient
conductors of heat. Their final usage,
however, may be limited by their
potential toxicity.
 How CNTs are made
• Arc discharge
– CNTs Can be found in the carbon soot of graphite
electrodes during an arc discharge involving high current.
This process yields CNTs with lengths up to 50 microns.
• Laser Ablation
– In the laser ablation process, a pulsed laser vaporizes a
graphite target in a high-temperature reactor while an inert
gas is inserted into the reactor. Nanotubes develop on the
cooler surfaces of the reactor as the vaporized carbon
condenses.

• Other methods where CNTs are created:

- Chemical Vapor Decomposition
- Natural, incidental, and controlled flame environments
 TYPES OF NANOTUBES

Carbon nanotubes are basically sheets of graphite rolled up into a tube as shown in
this figure. Hence, the hexagonal two dimensional lattice of graphite is mapped on
a one-dimensional cylinder of radius R with various helicities characterized by the
rolling vectors (n,m).

(n,0) zigzag nanotube

(n,n) armchair nanotube

(n,m) chiral nanotube

 Properties
• Strength
• Electrical
• Thermal
• Defects
• One-Dimensional Transport
• Toxicity
 Strength Properties
• Carbon nanotubes have the strongest tensile
strength of any material known.
• It also has the highest modulus of elasticity.
Young's Modulus Tensile Strength Elongation at
Material
(TPa) (GPa) Break (%)
SWNT ~1 (from 1 to 5) 13-53E 16
Armchair
0.94T 126.2T 23.1
SWNT
Zigzag SWNT 0.94T 94.5T 15.6-17.5
Chiral SWNT 0.92
MWNT 0.8-0.9E 150
Stainless Steel ~0.2 ~0.65-1 15-50
Kevlar ~0.15 ~3.5 ~2
KevlarT 0.25 29.6
 Electrical Properties
• If the nanotube structure is armchair
then the electrical properties are
metallic
• If the nanotube structure is chiral
then the electrical properties can be
either semiconducting with a very
small band gap, otherwise the
nanotube is a moderate
semiconductor
• In theory, metallic nanotubes can
carry an electrical current density of
4×109 A/cm2 which is more than 1,000
times greater than metals such as
copper
 Thermal Properties
• All nanotubes are expected to be very good thermal
conductors along the tube, but good insulators laterally to
the tube axis.

• It is predicted that carbon nanotubes will be able to

transmit up to 6000 watts per meter per Kelvin at room
temperature; compare this to copper, a metal well-known
for its good thermal conductivity, which transmits 385
watts per meter per K.

• The temperature stability of carbon nanotubes is estimated

to be up to 2800oC in vacuum and about 750oC in air.
 Defects

• Defects can occur in the form of atomic

vacancies. High levels of such defects can
lower the tensile strength by up to 85%.

• Because of the very small structure of CNTs,

the tensile strength of the tube is
dependent on its weakest segment in a
similar manner to a chain, where the
strength of the weakest link becomes the
maximum strength of the chain.
 One-Dimensional Transport
• Due to their nanoscale dimensions, electron transport in
carbon nanotubes will take place through quantum effects
and will only propagate along the axis of the tube. Because of
this special transport property, carbon nanotubes are
frequently referred to as “one-dimensional.”
 Applications
• Nanotubes hold the promise of creating novel
devices, such as carbon-based single-electron
transistors, that significantly smaller than
conventional transistors.
 Nanotubes’ excellent strength to weight ratio
creates the potential
to build an elevator to
space.
 Quantum Computing
• Nanotubes and other Fullerenes can be filled
with molecules that have either an electronic
or structural property which can be used to
represent the quantum bit (Qubit) of
information, and which can be associated with
other adjacent Qubits.
 Health Hazards
• According to scientists at the National Institute
of Standards and Technology, carbon nanotubes
shorter than about 200 nanometers readily
enter into human lung cells similar to the way
asbestos does, and may pose an increased risk
to health.
• Carbon nanotubes along with the majority of
nanotechnology, are an unexplored matter, and
many of the possible health hazards are still
unknown.
 References
• [Link]
• Chae, H.G.; Kumar, S. (2006). "Rigid Rod Polymeric Fibers". Journal of
Applied Polymer Science 100:791-802: 791. doi:10.1002/app.22680.
• Hong, Seunghun; Sung Myung (2007). "Nanotube Electronics: A flexible
approach to mobility". Nature Nanotechnology 2: 207–208.
doi:10.1038/nnano.2007.89
• Meo, S.B.; Andrews R. (2001). "Carbon Nanotubes: Synthesis, Properties,
and Applications". Crit. Rev. Solid State Mater. Sci. 26(3):145-249: 145.
doi:10.1080/20014091104189.
• Kolosnjaj J, Szwarc H, Moussa F (2007). "Toxicity studies of carbon
nanotubes". Adv Exp Med Biol. 620: 181–204. PMID 18217344
• Ebbesen, T. W.; Ajayan, P. M. (1992). "Large-scale synthesis of carbon
nanotubes". Nature 358: 220–222. doi:10.1038/358220a0
Fullerene
 Fullerene
● An allotrope of carbon.

● The most famous fullerene is C60.

● Discovered by H. W. Kroto and R. Smalley at Rice University ,USA

(1985). Nobel prize in chemistry in 1996.

Buckminister Fuller

● Popularly known as Buckministerfullerene in honour of the

American architect Buckminister Fuller.

● The shape of C60 resembles the dome structure based on hexagons

and pentagons designed by Buckminister Fuller in 1960s.
 Types of fullerenes

Since the discovery of fullerenes in 1985, structural variations on

fullerenes have evolved well beyond the individual clusters themselves.

Examples include:
● Buckyball clusters: The smallest member is C20 (unsaturated
version of dodecahedrane) and the most common is C60.
● Nanotubes: Hollow tubes of very small dimensions, having single or
multiple walls; potential applications in electronics industry.
● Megatubes: Larger in diameter than nanotubes and prepared with walls
of different thickness; potentially used for the transport of a variety of
molecules of different sizes.
● Polymers: Chain, two-dimensional and three-dimensional polymers are
formed under high pressure high temperature conditions.
● Nano-onions: Spherical particles based on multiple carbon layers
surrounding a buckyball core; proposed for lubricants.
● Linked "ball-and-chain" dimers: two buckyballs linked by a carbon
chain.
● Fullerene rings.
 Buckyball clusters
● C60 is also known as buckyball or Buckminsterfullerene as
it is a spherical cluster of carbon atoms arranged in a series of five and six membered
rings to form a soccer ball shape.
 Buckyball clusters
● Other relatively common clusters are C70, C72, C74, C76, C80, C82 and C84
(plenty of others, higher or lower than C60, exist too but less abundant in the
experimentally produced mixture fullerene soot).

C70 C80 C84

 Structure of C60
● A truncated icosahedron structure
♦ Icosahedron: A polygon with 60 vertices and 32 faces. 12
faces are pentagonal and 20 faces are hexagonal.
♦ A carbon atom is present at each vertex.

● Aromatic and has several resonance structures.

● Pentagons are separated by hexagons: The isolated

pentagon rule.

● Valancies of each carbon atom are satisfied by two single

and one double bond (sp2 hybridised carbon ).

● Fullerene cages are about 7-15 Å in diameter, and are one

carbon atom thick.
 Structure of C60
● The bonding pattern of the
C60 fullerene , with yellow
bonds representing double
bonds and red bonds
representing single bonds.
♦ The pentagonal rings
contain only single bonds.
Double bonds have a shorter
bond length and lead to
instability in the pentagonal
ring.
♦ The limitations on double
bond locations lead to poor
delocalization of electrons,
increasing the molecule’s
reactivity.
 Carbon nano-onion

Carbon nano-onion along with a TEM image

showing the layered graphitic shells.
Carbon nanotube
Carbon megatube
 Properties of fullerenes
● Quite stable from chemical and physical points of view
(breaking the balls requires temperatures of about 1000 °C).
● Highest tensile strength of any known 2D structure or
element.
● Highest packing density of all known structures.
● Impenetrable to all elements under normal circumstances,
even to a helium atom with an energy of 5 eV.
● A black powdery material.
● Very tough and thermally stable.
● Exists as a discrete molecule unlike the other two allotropes
of carbon (graphite and diamond).
● Can be compressed to lose 30% of its volume without
destroying its carbon cage.
● Forms deep magenta solution in benzene.
 Applications of fullerenes
● As a lubricant due to its spherical structure -the buckyballs act
as a molecular ball bearings.
● As a superconductor when mixed with alkali metals.
● Used as a soft ferromagnet (TDAE C60 ).
● Used in electronic, microelectronic and non-linear
optical devices.
● Researchers have found that water-soluble derivatives of
fullerenes inhibit the HIV-1 protease (enzyme responsible for the
development of the virus) and are therefore useful in fighting the
HIV virus that leads to AIDS.
● Organic Photovoltaics (OPV).
● Polymer Electronics.
● Catalysts.
● Water purification & bio-hazard protection.
Quantum Tunneling
 What is Quantum Tunneling?
At the quantum level, matter has corpuscular and wave-like
properties
Tunneling can only be explained by the wave nature of matter as
described by quantum mechanics
Classically, when a particle is incident on a barrier of greater
energy than the particle, reflection occurs
When described as a wave, the particle has a probability of existing
within the barrier region, and even on the other side of it
 Examples:Tunneling Diodes
Developed in 1958 by Leona Esaki at Sony
Tunneling diodes are designed with a
heavily doped p-n junction that is only 10
nm wide
At low voltages, the p and n states are
aligned, allowing electrons to tunnel across
the gap
As voltage increases these states become
more misaligned and fewer electrons flow
This negative resistance region allows the
diode to operate at very high frequencies,
well into the Gigahertz range
 Examples: Alpha-Particle Decay
• The phenomenon of tunneling explains the alpha-particle decay of heavy,
radioactive nuclei.
• Inside the nucleus, an alpha particle feels the strong, short-range attractive nuclear
force as well as the repulsive Coulomb force.
• The nuclear force dominates inside the nuclear radius where the potential is
approximately a square well.
• The Coulomb force dominates
outside the nuclear radius.
• The potential barrier at the nuclear
radius is several times greater than
the energy of an alpha particle.
• According to quantum mechanics,
however, the alpha particle can
“tunnel” through the barrier. Hence
this is observed as radioactive decay.

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 How Can This Be?
Solutions to the wave equation
have the general form (I)
In the barrier region, the solution
becomes (II)

The wave function decays

exponentially in the barrier region

If some portion of the

wavefunction still exists on the
other side of the barrier,
transmission has occurred

The width of the barrier is the most

prominent factor in determining
the probability of transmission
The Scanning Tunneling Microscope was invented in 1981 by
Gerd Binnig and Heinrich Rohrer
When a metal tip, usually made of tungsten or platinum-
iridium, is brought within .4-.7nm of the sample, electrons
tunnel across the gap and create a current in the tip
This current is then fed to a computer and used to generate an
image of the atomic surface of the sample

At this distance the coulomb force between

the tip and an atom of the sample is
actually enough to move the atom
This has allowed physicists to create images
and structures on the atomic level
1) Constant current mode
2) Constant height mode