Unit - 4

Advance Material and Synthesis

Contents

Introduction to nanomaterials, Nano-science and nano-

technology, Two main approaches in nanotechnology,
Bottom up technique, Top down technique, Quantum dot
and graphene, Methods to produce Nanomaterials,
Chemical vapour deposition, Sol-gel process, Molecular
beam epitaxy, Physical and chemical properties of
nanomaterials, Carbon nanotubes: single and multi-walled
nanotubes, Synthesis of Nanotubes: carbon arc method,
Laser evaporation method, Sputtering, applications of
advanced materials.
Advanced materials can be defined in many ways. The broadest definition
is to refer to all materials that represent advances over the traditional
materials that have been used for hundreds or even thousands of years.
From this perspective, advanced materials refer to all new materials and
modifications to existing materials to obtain superior performance in one
or more characteristics that are critical for the application under
consideration. They can also exhibit completely novel properties.

Materials that are utilized in high-technology applications are termed

as advanced materials. These advanced materials are typically traditional
materials whose properties have been enhanced, and also newly
developed, high-performance materials. Furthermore, they may be of all
material types (e.g., metals, ceramics, polymers), and are normally
expensive. Advanced materials include semiconductors, biomaterials,
and smart materials and nanoengineered materials .
Nanoscience
Nanoscience is the study of the fundamental principles of
molecules and structures with dimensions of the order of 1 to
100 nanometers (nm). The structures with size ranging
between 1 nm to 100 nm are known as nanostructures.

Nanotechnology
The branch of knowledge dealing with the applications of
nanostructures and nanodevices is known as nanotechnology.
Generally, nanotechnology deals with structures of the size
100 nanometer (100 x 10-9 metre) or smaller, and it involves
developing materials or devices within that range.
Origin
The concept of nanotechnology was first used by Richard
Feynman in a talk titled “There is plenty of room at the
bottom’’ given by him at an American Physical Society
meeting at Caltech on Dec 29, 1959. In this talk, Feynman
described a process by which the ability to manipulate
individual atoms or molecules might be developed.
Fundamental Concepts

One nanometer is one billionth or 10-9 of a metre. By

comparison typical carbon- carbon bond lengths or spacing
between these atoms in a molecule, are in the range 0.12—
0.15 nm. The DNA double helix has a diameter around 2nm.
On the other hand, the smallest cellular life forms, the bacteria
of the genus of mucoplasma, are around 200nm in length. We
can have an idea of nanoscale with the help of following
comparison.

Size of nanometer Size of a marble


Size of meter Size of the earth
Particles: A particle is defined as small size object that
behaves as a whole unit in terms of its transport and
properties.
Fine Particles: Particles having size between 100nm to 2500
nm are known as fine particles.
Ultrafine-paricles: Particles having size between 1 nm and
100 nm are known as ultrafine particles.
Nanoparticles: Ultra fine particles having size between 1 nm
to 100 nm are called nanopartcles.
Nanoclusters: A group of nanoparticles having at least one
dimension between 1 nm and 10 nm is known as nanocluster.
Nanopowders: Nanopowders are agglomerates of ultra fine
particles, nanoparticles, nanoclusters.
Nanocrystals: Nanosized single crystal is often referred to as
Nanocrystals.
Quantum well: If one dimension of material is reduced to
nano range, while the other two dimensions remain large.
Quantum wire: If the two dimensions of material are
reduced to nano range, while the third one dimension remain
large.
Quantum Dot: If all dimensions are reduced to nano range.

Bulk Well Wire Dot

Nanoparticles are bridge between bulk materials and
atomic/molecular structures. A bulk material should have
constant physical properties regardless of its size but at
nanoscale this often is not the case. The properties at the
nanoscale become size dependent. The properties of the
material change as their size approaches the nanoscale
because the percentage of atoms at the surface of the
material becomes significant. For bulk materials larger than
one micrometer, the percentage of surface atoms becomes
miniscule relative to the total number of atoms of the
material. In case of nanomaterials, the percentage of the
surface atoms becomes very high compared to that of the
atoms embedded in the bulk of the material. Consequently,
the surface of the material becomes dominant in influencing
the properties of the materials with the result that
nanomaterials exhibit interesting and sometimes unexpected
properties.
For instance:
opaque substance can become transparent (copper);
inert materials can attain catalytic properties (platinum,
gold);
stable materials can turn combustible (aluminum);
solids turn in to liquids at room temperature (gold);
insulators become conductors (silicon).
Materials such as gold, which is chemically inert at normal
scale, can serve as potent chemical catalyst at nanoscale.
The materials at nanoscale show quantum size effect where
electronic properties of the solids are altered with great
reduction in particle size.
Copper nanoparticles smaller than 50nm are considered super
hard materials and they do not exhibit the same malleability
and ductility as bulk copper.

Ferroelectric materials smaller than 10nm can switch their

magnetization direction using room temperature thermal
energy, thus making them useless for memory storage.

Suspensions of nanoparticles are possible because the

interaction of particle surface with solvent is strong to
overcome the difference in density which usually results in
the material either floating or sinking in the liquid.
Nanomaterials

The materials reduced to nanoscale are known as

nanomaterials. The nanomaterials fall into following
categories:

Inorganic Nanomaterials

Organic Nanomaterials (Fullerenes)

Inorganic Nanomaterials

Metal Nanoclusters: lead, copper etc.

Magnetic Clusters: iron, manganese, and cobalt
Semi-conducting Nanoclusters: Ge, Si etc.
Inert- Gas Crystals: krypton and xenon
Super fluid Clusters: liquid He4 at temperature 2.2K,
becomes a super fluid and its viscosity drops to zero
Molecular Clusters: (NH3) n, (CO2)44 , (C4H8)30.
Organic Nanomaterials

Fullerenes
Fullerenes are a family of carbon allotropes.
These are molecules composed entirely of carbon in the
form of hollow sphere, ellipsoid, tube or plane.
The spherical fullerenes are known as buckyballs and
cylindrical ones are known as carbon nanotubes or
buckytubes.
Graphene is an example of planar fullerenes which are
similar in structure to graphite.
Basic Principles of Nanoscience and Nanotechnology

We define Nanoscience 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 and nanotechnologies as the
design, characterization, production and application of
structures, devices and systems by controlling shape and size
at the nanometer scale.

There are two main approaches used in nanotechnology for

building Nanomaterials.
Bottom up approach: Nanomaterials are constructed atom-
by-atom or molecule-by-molecule. It can be done by two ways
(i) Self assembly: atoms or molecules arrange themselves into
a structure due to their natural properties like in chemical
synthesis , and (ii) Positional assembly: by using tools to
move each atom or molecule individually. The production by
this approach is laborious and not suitable for industrial
applications.

Top Down approach: Nano objects are constructed from

larger entities without atomic level control. E.g. by etching to
create circuit on the surface of silicon microchips.
Quantum dots are semiconductor particles with typical
diameter of 2–10 nm. They are so named because, due to
their nanoscale size, quantum effects play a significant
part in their light emitting properties. Quantum dots emit
light via this mechanism: under external stimulus, some of
the electrons of the dot material absorb sufficient energy
to escape their atomic orbit. This creates a conductance
region in which the electrons can move through the
material, effectively conducting electricity. As these
electrons drop back into atomic orbit, energy is released
in the form of light, the color of which depends on the
amount of energy released.
Because of the dots’ small size, the amount of energy
released is relatively consistent from electron to electron,
yielding emissions of a single color. The color is entirely
dependent upon the size of the dot, with larger dots (e.g.,
5-6 nm) providing lower energy emissions (i.e., reds and
oranges) and smaller dots (e.g., 2-3 nm) providing higher
energy emissions (i.e., blues and violets). This property is
sometimes referred to as “quantum confinement,”
indicating that constraints at the atomic level are
predominant.
Graphene
Carbon is one of the most abundant yet versatile elements
available on our planet, making it nature’s favorite building
block. While some carbon-based molecules are incredibly
complex, graphene is simply a sheet of repeating carbon
units that is just one atom thick. Due to the nature of
bonding, the carbons in graphene arrange themselves into
a hexagonal pattern with beautiful six-sided symmetry.
Discovery
Graphene itself is not a new molecule, having been known to
exist as graphite – a mass of graphene sheets. However, it
wasn’t till 2004 when the real deal, single-layer graphene, was
isolated and characterized. These single-atom-thick sheets
were found to be surprisingly stable at room temperature,
while also possessing some very interesting properties.
It was a big achievement for the scientists working in the field
as well as for the wider community. For years, it was theorized
that harnessing the potential of graphene’s unique properties
could transform the landscape of technology and electronics.
With its isolation, it would be only a matter of time before this
wonder material took over the world.
Properties
Graphene exhibits high thermal and electrical conductivity, it is
stronger and lighter than any metal alloy in existence, while
having the added benefit of being both transparent and
flexible. To find out why graphene behaves in such a
fascinating matter, we need to study its electrons. After all,
chemistry is governed by the comings and goings of electrons.
In graphene, all the electrons from the carbon atoms are
delocalized – they can move freely over the entire structure. In
addition, these electrons possess no mass due to quantum
effects, making them extremely quick. This leads to the
material being an extremely conductor of heat and electricity.
Due to the nature of its carbon bonding, graphene is also the
strongest material ever discovered, surpassing the tensile
strength of even Kevlar.
Applications
One key area in which graphene has been earmarked for success is
within the semiconductor industry. Billions of silicon transistors are
manufactured every day, finding their way into the electronic devices
we can’t seem to live without. Some forms of graphene, such as
nanoribbons, can be transformed into a semiconducting material
that is many times more efficient than silicon.
Since carbon is such a good building block, it is also possible to react
graphene with other atoms to change its structure and properties.
For example, graphene can react with palladium nanoparticles,
making it sensitive to tiny molecules such as hydrogen. These
‘nanosensors’ can detect analytes that are too small or too low in
concentration for traditional sensors.
Even in biology and medicine, graphene has found potential
applications. Its high surface area makes it an ideal candidate as
a drug delivery system, transporting drugs to targeted areas in our
bodies where they can do their job.
Methods to produce Nanomaterials
Physical & Chemical Properties of Nanomaterials

Physical Properties of Nanomaterials

The major reasons for very different properties of

nanomaterials:
. The potential experienced by atoms inside bulk material is
very different from experienced by atoms on surface. A sphere
as a volume and surface area

Therefore the surface area to volume ratio can be

approximated as 3/r. This gives the idea that as the particle
size becomes smaller and smaller, the number of atoms on
the surface is greater proportion to the total number of
atoms. Hence the particle size decreases and the surface
atoms starts playing more crucial role in the description of
properties of nanomaterials. Due to the small dimensions
nanomaterials have extremely large surface area to volume
ratio.
The nanometer feature sizes of nanomaterials also have
spatial confinement effect on the materials; which bring the
quantum effects. The confinement of nanomaterials has
profound effects on the properties of nanomaterials. The
energy band structure and charge carrier density in the
materials can be modified quite differently from their bulk
counterpart and in turn will modify the electronic and optical
properties of the materials.

When a bulk metal is reduced in size, the continuous levels in

the conduction band are replaced by a set of discrete energy
levels and a gap opens up.
The energy levels of a very small cluster containing about
three atoms can be modeled by a quantum mechanical
treatment of a particle in a box. This is known as quantum size
effect.

The colour of a cluster depends on its size.

There is a significant shift in the optical absorption spectra

towards the blue as the particle size is reduced.

The band gap increases as the particle size decreases.

Nanoparticles of silicon and germanium undergo fragmentation

when subjected to intense laser light.
Multiple ionization of clusters causes them to become unstable
resulting in a very rapid high energy dissociation or explosion.
This phenomenon is called Coulombic explosion.

Carbon nanotubes are metallic or semiconducting depending

on their diameter and structure.

Carbon nanotubes have high thermal conductivity, display

magneto-resistive effect at low temperature.

Carbon nanotubes are resilient and they have high tensile

strength.

When a small electric field is applied parallel to the axis of the

tube, electrons are emitted at a very high rate from the ends
of the tube. This is called field emission.
Chemical properties of nanomaterials

The ability of Nanoclusters to react with other species depends

on cluster size.

Nanotubes serve as catalyst for some chemical reactions.

Nanotubes can be used as chemical sensors.

Carbon Nanotubes
Carbon Nanostructures : Small carbon clusters
Laser evaporation of a carbon substrate in a pulse of He gas can be
used to make carbon clusters. The neutral cluster beam is
photoionised by ultraviolet laser and analyzed by mass
spectrometer. For the number of atoms N less than 30, there are
cluster of every N, although some are more prominent than others.
These clusters have linear structure when N is odd, and they have
closed structure when N is even. Mass spectrum of carbon clusters
have a very prominent peak at N = 60. It is due to C60 cluster of
carbon.
Fullerenes
Fullerenes are a family of carbon allotropes. These are molecules
composed entirely of carbon in the form of hollow sphere, ellipsoid,
tube or plane. The spherical fullerenes are known as buckyballs and
cylindrical ones are known as carbon nanotubes or buckytubes.
Graphene is an example of planar fullerenes which are similar in
structure to graphite.
Structure of C60 and its crystal
The C60 molecule has been named fullerene after its inventor R.
Buckminster Fuller who designed a model that resembles the
structure of C60 . Originally, the molecule was called Buckminster
fullerene, but this name is a bit unwieldy, so it has been shortened
to fullerene. A sketch of the molecule is shown in the figure.
It has 12 pentagonal and 20 hexagonal faces symmetrically arrayed
to form a ball. In fact, a soccer ball has the same geometrical
configuration as fullerene. These ball like molecules bind with each
other to form a crystal lattice having a face centered cubic
structure. In the lattice each C60 molecule is separated from its
nearest neighbour by 1 nm and they are held together by weak
forces called Van der Waals forces. Because C60 is soluble in
benzene, a single crystal of it can be grown by slow evaporation
from benzene solution. Since C60 has spherical structure, it is known
as buckyball.
Larger fullerenes such as C70, C76, C80, and C84 have also been found.
C20 and C26 carbon molecules have also been synthesized. Buckyball
B 80 has also been synthesized.
Carbon Nanotube
Carbon nanotubes are cylindrical fullerenes. These tubes of carbon
are usually only a few nanometers wide, but they can range from
less than a micrometer to several millimeters in length. They often
have closed ends, but can be open ended as well. There are also
cases in which it reduces in diameter before closing off
Types of Nanotubes

Single walled Tube: These tubes have a single wall only. Most single
walled nanotubes have a diameter close to 1 nanometer with a
tube length that can be many million times longer than the
diameter. The structure of a single walled tube can be
conceptualized by wrapping a one atom thick layer of graphite in to
a seamless cylinder.
Multi walled Nanotube: Multi walled nanotube consist of multiple
layers (coaxial tubes) of graphite. The interlayer distance in multi
walled nanotube is approximately 330 A0 . The morphology and
properties of double walled nanotube are similar to those of single
walled nanotube but their resistance to chemicals is significantly
improved.
Nanotorus
Nanotorus is a theoretically described carbon nanotube. Nanotorus
are predicted to have many unique properties such as very large
magnetic moments.
Carbon Nanobuds
Carbon nanobuds are materials which combine carbon nanotubes
and fullerenes. In this new material, fullerenes are covalently
bonded to the outerside walls of the nanotube. Consequently,
carbon nanobuds exhibit properties of nanotubes and fullerenes
both
Synthesis of

Laser Evaporation Method

Figure illustrates the apparatus for making carbon nanotubes by
laser evaporation.
A quartz tube containing argon gas and graphite target is
heated to12000 c. Contained in the tube, but somewhat outside
the furnace, is a water-cooled copper collector. The graphite
target contains small amounts of cobalt and nickel that act as
catalytic nucleation sites for the formation of the tubes. An
intense pulsed laser beam is incident on the target, evaporating
carbon from the graphite. The argon then sweeps the carbon
atoms from high temperature zone to the colder copper
collector on which they condense into nanotubes.

Tubes of 10-20 nm in diameter and 100 µm long can be made

by this method.
Carbon Arc Method
Carbon Arc Method

A potential of 20-25 V is applied across carbon electrodes of 5-

20 µm diameter and separated by 1 mm at 500 torr pressure of
flowing helium. Carbon atoms are ejected from the positive
electrode and they form nanotubes at the negative electrode.
As the tubes form, the length of the positive electrode
decreases, and a carbon deposit forms on the negative
electrode. To produce single walled nanotubes, a small amount
of cobalt, nickel or iron is incorporated as catalyst in the central
region of the positive electrode. If no catalyst is used, the
tubes are multi-walled types, which are nanotubes within
nanotubes. Carbon arc method can produce single-walled
nanotubes of diameters 1-5nm with a length of 1µm.
Sputtering

Sputtering is a process that uses gaseous plasma to

dislodge atoms from the surface of a solid target material.
The atoms are deposited to form an extremely thin
coating on the surface of the substrates. It is a technique
often used to deposit thin films of semiconductors, CDs,
disk drives, and optical devices. Sputtered films exhibit
excellent uniformity, density, purity and adhesion. It is
possible to produce alloys of precise composition with
conventional sputtering, or oxides, nitrites and other
compounds by reactive sputtering.
Process of sputtering:
•Ions of inert gas are accelerating into target
•Target is eroded by the ions via energy transfer and is ejected in the form of
neutral particles
•Neutral particles from the target traverse and are deposited as a thin film onto
the surface of the substrates
The substrate is placed in a vacuum chamber with the source
material (target) and an inert gas (such as argon) is introduced
at low pressure. The gas plasma is struck using an RF power
source, causing the gas to become ionized. The ions are
accelerated towards the surface of the target, causing atoms of
the source material to break off from the target in vapor form
and condense on all surfaces including the substrate. As for
evaporation, the basic principle of sputtering is the same for all
sputtering technologies.
Sputtering

Sputtering is a process that uses gaseous plasma to

dislodge atoms from the surface of a solid target material.
The atoms are deposited to form an extremely thin
coating on the surface of the substrates. It is a technique
often used to deposit thin films of semiconductors, CDs,
disk drives, and optical devices. Sputtered films exhibit
excellent uniformity, density, purity and adhesion. It is
possible to produce alloys of precise composition with
conventional sputtering, or oxides, nitrites and other
compounds by reactive sputtering.
Process of sputtering:
•Ions of inert gas are accelerating into target
•Target is eroded by the ions via energy transfer and is ejected in the form of
neutral particles
•Neutral particles from the target traverse and are deposited as a thin film onto
the surface of the substrates
The substrate is placed in a vacuum chamber with the source
material (target) and an inert gas (such as argon) is introduced
at low pressure. The gas plasma is struck using an RF power
source, causing the gas to become ionized. The ions are
accelerated towards the surface of the target, causing atoms of
the source material to break off from the target in vapor form
and condense on all surfaces including the substrate. As for
evaporation, the basic principle of sputtering is the same for all
sputtering technologies.
Applications of Nanomaterials
Carbon nanotubes can be used in making flat panel displays and
vacuum tube lamps by exploiting the field emission property of
carbon nanotubes.

A plastic composite of carbon nanotubes can be used as a light

weight shielding material against electromagnetic radiations because
of the conducting property of carbon nanotube.

Carbon nanotubes can be used in fabricating high speed switching

components for computers.

Carbon nanotubes have applications in battery technology.

Carbon nanotubes can be used as sensitive detectors for various

gases.

Carbon nanotubes can be used as catalyst for chemical reactions.

Tensile strength of metals and polypropylene can be increased if
carbon nanotubes are incorporated in these materials in specific
percentage.

Carbon nanotubes can be used as heat sinks for chips used in

advanced computing.

Carbon nanotubes have been used to develop far more tougher

type of ceramic.

Carbon nanotubes have been used to develop super strong fibre

which has many commercial applications.

Nano crystalline materials such as tungsten carbide, tantalum

carbide and titanium carbide are being used in making tougher
and harder cutting tools.
Performance and properties of paints are improved when
nanoparticles are incorporated in them.

Nanosized titanium oxide and zinc oxide are currently being

used in sun screens as they absorb and reflect ultraviolet rays.

Nanospheres of inorganic materials can be used as lubricant as

they act as nano sized ball bearings.

Nanoengineered membranes can be exploited to develop more

energy efficient water purifier.

Nanomaterials may be used for making state of art battle suits

which can withstand blast waves.
Medical Implants:
Current medical implants such as orthopedic implants and heart
valves are made of titanium and stainless steel alloys because
they are biocompatible. But these implants may wear out within
the life time of the patient. Nano crystalline zirconium is hard,
wear resistant, bio-corrosion resistant and biocompatible. It
therefore, presents an attractive material for medical implants.
Silicon carbide may be used for making heart valves because of
its low weight, high strength and inertness.
Applications of nanomaterials in defence:
Sensors for Warfare Agents - The detection of chemical and
biological warfare agents, radiological agents, and other
hazardous vapors has significant import for both the military
and homeland security efforts. Small, lightweight, portable, and
high sensitive sensors based on nanomaterials are currently
being developed and evaluated.

Destruction of Warfare Agents - Destruction of stockpiled

warfare agents and decontamination of exposed personnel is
equally important to the military and for homeland defense.
Both magnetic nanoparticles and nanocrystalline metal oxides
have been investigated for this purpose.
Tagging and Tracking - Tagging and tracking of materials also
has potential military and security applications. The use of
nanoparticles to create ‘smart’ barcodes is under
investigation. Ink containing gold nanoparticles encapsulated
in an alkanethiol can be deposited with an inkjet printer in a
specific circuit pattern onto paper, plastic, or cloth. The
circuits form radio frequency identification (RFID) tags and
include both passive (inductors, capacitors, wires) and active
(transistors, diodes) components. The heat of the printing
process drives off the alkanethiol, leaving behind a
concentrated pattern of gold nanoparticles.
Applications of nanomaterials in automobiles -
Nanotechnology will likely emerge as a key technology in
automotive manufacture, especially in the materials
replacement arena. Today, the nanomaterials are being used in
the automobile industry as nanocomposites, coatings and
paints, nanocatalysts, nanodispersions and nanoadditives in
lubricants, fuels, and coolants etc.