Physics (BPH-151/152)

Dr. Alok Singh

School of Basic & Applied Sciences

Department of Physics
Harcourt Butler Technical University, Kanpur

B.Tech. First Year Course

 Module 4:
Nano-Materials
 Nano
❑‘Nano’ is a Greek word means dwarf (small).
❑Nano- (symbol n).
❑Unit prefix meaning "one billionth".
❑The nano prefix denotes a factor of
10−9 or 0.000000001.
❑Used primarily with the metric system,
❑One nanometer = 1x 10−9 meter
❑ One nanosecond= 1x 10−9 second
❑It is frequently encountered in science and
electronics for prefixing units of time and length.
 History of Nanotechnology
❑The American Physicist Richard Feynman lectured,
“There’s Plenty of Rooms at the Bottom,”
at an American Physical Society meeting
at Caltech on December 29, 1959,
which is often held to have provided
inspiration for the field of
nanotechnology.
Richard Feynman gave a 1959 talk
which many years later inspired the
conceptual foundations of
nanotechnology.
❑The Japanese scientist called Norio Taniguchi
of Tokyo University of Science was first to use the
term "nano-technology" in a 1974 conference, to
describe semiconductor processes such as thin film
deposition and ion beam milling exhibiting
characteristic control on the order of a nanometer.
❑His definition was, "'Nano-technology' mainly
consists of the processing of, separation,
consolidation, and deformation of materials by one
atom or one molecule."
 Nano-science
❑The word Nano-science refers to the study,
manipulation and engineering of matter, particles
and structures on the nanometer scale (one
millionth of a millimeter, the scale of atoms and
molecules).
❑Important properties of materials, such as the
electrical, optical, thermal and mechanical
properties, are determined by the way molecules
and atoms assemble on the nano-scale into larger
structures. Moreover, in nanometer size structures
these properties often different than on macro-scale,
because quantum mechanical effects become
dominant.
 Nanotechnology
• The technology of design, synthesis, characterisation and
applications of materials on nano-scale is called Nano
technology.
• Nanotechnology is the application of nano-science leading
to the use of new nano-materials and nano-size components
in useful products. Nanotechnology will eventually provide
us with the ability to design custom-made materials and
products with new enhanced properties, new nano-
electronics components, new types of “smart” medicines
and sensors, and even interfaces between electronics and
biological systems.
• These newborn scientific disciplines are situated at the
interface between physics, chemistry, materials science,
microelectronics, biochemistry, and biotechnology. Control
of these disciplines therefore requires an academic and
multidisciplinary scientific education.
 Nano-materials
❑The materials in which a single unit small sized (in
at least one dimension) between 1 and 100 nm.
❑Nanomaterial is defined as the "material with any
external dimension in the nano-scale or having
internal structure or surface structure in the nano-
scale", with nano-scale defined as the "length range
approximately from 1 nm to 100 nm". This
includes both nano-objects, which are discrete
pieces of material, and nanostructured materials,
which have internal or surface structure on the
nano-scale; a nanomaterial may be a member of
both these categories.
Scale of Measurement
 Types of Nano-materials

Layers, thin films, surface coating,

1D Quantum well

2D Nanowires, Nanotubes, Quantum wires

3D Nanoparticles, Quantum dots

Carbon

OD
Diamond
sp3 hybridized
carbon
Nanodiamond 3D-sp3

Graphite (3-D)
1D
Buckminsterfullerene
(0-D)
sp2 hybridized 3D-sp2
carbon
CNT, CNF (1-D)

Graphene (2-D) 2D

Mixed Amorphous carbon

 Properties of Nano-materials
❑Nanomaterials are hard.
❑Nanomaterials are exceptionally strong.
❑Nanomaterials are ductile at high temperature.
❑Nanomaterials are chemically very active.
❑Nanomaterials are wear resistant.
 Reason behind property change at nanoscale
➢ Increase in Surface Area to Volume Ratio:
The properties of materials are drastically changed at
nanoscale due to increased surface area to volume
ratio.
Let us consider a large sphere of radius R, volume V
and surface area S then, surface area to volume ratio is
given by,

Which means that when radius decrease at nanoscale,

surface area to volume ratio increases.
➢ Hence, nanomaterials are chemically very reactive.
➢Quantum Confinement Effect:
The quantum effects are begins to dominate at lower
nanoscale which cause the change in optical,
electrical, magnetic and mechanical properties.
Some examples at nanoscale are as follows;
❖Opaque materials can become transparent, e.g.,
cooper.
❖Inert material can become catalyst, e.g., platinum.
❖Stable material can turn combustible, e.g.,
aluminium.
❖Solids can turn into liquids at room temperature,
e.g., gold.
❖Insulator becomes conductor, e.g., silicon.
 Fabrication at Nanoscale-The Nanomaterials
➢ Top Down Approach:
➢ Top-down approach involves the breaking down of the bulk
material into nanosized structures or particles.
➢ Top-down synthesis techniques are extension of those that
have been used for producing micron sized particles.
➢ Top-down approaches are inherently simpler and depend
either on removal or division of bulk material or on
miniaturization of bulk fabrication processes to produce the
desired structure with appropriate properties.
➢ The biggest problem with the top-down approach is the
imperfection of surface structure.
➢ For example, nanowires made by lithography are not smooth
and may contain a lot of impurities and structural defects on
its surface. Examples of such techniques are high-energy wet
ball milling, electron beam lithography, atomic force
manipulation, gas-phase condensation, aerosol spray, etc.
➢ Bottom Up Approach
➢ The alternative approach, which has the potential of
creating less waste and hence the more economical, is
the ‘bottom- up’.
➢ Bottom-up approach refers to the build up of a
material from the bottom: atom-by-atom, molecule-by-
molecule, or cluster-by cluster.
➢ Many of these techniques are still under development
or are just beginning to be used for commercial
production of nanopowders.
➢ Oraganometallic chemical route, revere-micelle route,
sol-gel synthesis, colloidal precipitation, hydrothermal
synthesis, template assisted sol-gel, electrodeposition
etc, are some of the well- known bottom–up
techniques reported for the preparation of luminescent
nanoparticals.
➢ When particle sizes of solid matter in the visible scale are
compared to what can be seen in a regular optical
microscope, there is little difference in the properties of the
particles.
➢ But when particles are created with dimensions of about 1–
100 nanometers (where the particles can be “seen” only
with powerful specialized microscopes), the materials’
properties change significantly from those at larger scales.
➢ This is the size scale where so-called quantum effects rule
the behavior and properties of particles. Properties of
materials are size-dependent in this scale range.
➢ Thus, when particle size is made to be nanoscale, properties
such as melting point, fluorescence, electrical conductivity,
magnetic permeability, and chemical reactivity change as a
function of the size of the particle.
➢ Nanoscale gold illustrates the unique properties that occur at
the nanoscale. Nanoscale gold particles are not the yellow
color with which we are familiar; nanoscale gold can appear
red or purple.
➢ At the nanoscale, the motion of the gold’s electrons is
confined. Because this movement is restricted, gold
nanoparticles react differently with light compared to larger-
scale gold particles.
➢ A fascinating and powerful result of the quantum effects of the
nanoscale is the concept of “tunability” of properties.
➢ That is, by changing the size of the particle, a scientist can
literally fine-tune a material property of interest (e.g.,
changing fluorescence color; in turn, the fluorescence color of
a particle can be used to identify the particle, and various
materials can be “labeled” with fluorescent markers for
various purposes). Another potent quantum effect of the
nanoscale is known as tunneling which is a phenomenon that
enables the scanning tunneling microscope and flash memory
for computing.
 Categories of Nanomaterials
Nanomaterials are generally fall into two categories:
➢Fullerenes
• A fullerene is an allotrope of carbon whose
molecule consists of carbon atoms connected by
single and double bonds which conceptually a
graphene sheets (isolated one-atom thick layer of
graphite) rolled into tubes or spheres.
• Fullerenes with a closed mesh topology are
informally denoted by their empirical formula Cn,
where n is the number of carbon atoms.
Graphene sheet
➢Nanoparticles:
➢A nanoparticle or ultrafine particle is usually
defined as a particle of matter that is between 1
and 100 nanometres (nm) in diameter.
➢Nanoparticles are usually distinguished
from microparticles (1-1000 µm), "fine
particles" (sized between 100 and 2500 nm),
and "coarse particles" (ranging from 2500 to
10,000 nm), because their smaller size drives
very different physical or chemical properties,
like colloidal properties and optical or electric
properties.
 Buckyballs
➢Buckyballs also known as Buckminsterfullerene is a
type of fullerene with the formula C60.
➢It has a cage-like fused-ring structure that resembles
a soccer ball, made of twenty hexagons and
twelve pentagons.
➢Each carbon atom has three bonds.
➢It is a black solid that dissolves in hydrocarbon
solvents to produce a violet solution.
➢The compound has received intense study, although
few real world applications have been found.
 Creation of Buckyballs
➢Arc Discharge method
Buckyballs can be created by vaporizing carbon
placed between two carbon electrodes.
When an arc is generated between two carbon
electrodes placed very near to each other in a reaction
chamber filled with low pressure of Helium or Neon
or Argon, Buckyballs are created along with carbon
soot. They are separated using solvents such as
benzene.
Arc Discharge Experimental Setup
Properties of Buckyballs
 Applications of Buckyballs
Some potential applications for fullerenes include:
❑ Superconductors (Buckyballs doped with potassium or cesium)
❑ Lubricants
❑ Catalysts due to their high reactivity
❑ Drug delivery systems, pharmaceuticals and targeted cancer therapies.
❑ Hydrogen storage as almost every carbon atom in C60 can absorb a
hydrogen atom without disrupting the Buckyballs structure, making it more
effective than metal hydrides. This could lead to applications in fuel cells.
❑ Optical devices
❑ Chemical sensors
❑ Photovoltaics
❑ Polymer electronics such as Organic Field Effect Transistors (OFETS)
❑ Antioxidants
❑ Polymer additives
❑ Cosmetics, where they “mop up” free radicals.
❑ Diamonds, fullerenes have been used as precursors to produce diamond
films
 Carbon Nanotubes

➢Carbon Nanotubes, long, thin cylinders of carbon,

were discovered in 1991 by Sumio Iijima. These
are large macromolecules that are unique for their
size, shape, and remarkable physical properties.
They can be thought of as a sheet of graphite (a
hexagonal lattice of carbon) rolled into a cylinder.
they are less than 100 nanometers in diameter and
can be as thin as 1 or 2 nm while they can be upto
several millimeter in length
Carbon Nanotubes
 Types of Carbon nanotubes
Nanotubes can be of two types;
➢ Single Walled Carbon Nanotubes (SWNT/SWCNT);
➢ Single Walled Carbon Nanotubes are defined as a one
dimensional, cylindrically shaped allotropes of carbon that
have a high surface area and aspect ratio (length to diameter
ratio). They are made of one-atom-thick nano carbon sheet
that forms a tube shape.
➢ Multi-Walled Carbon Nanotubes (MWNT/MWCNT);
➢ Multi-walled carbon nanotubes (MWCNTs) are a special
form of carbon nanotubes in which multiple single-walled
carbon nanotubes are nested inside one another. Although
MWCNTs are still classed as a 1-dimenional form of
carbon.
 Production (Synthesis) of Carbon Nanotubes
Commercially, nanotubes are being produced with a number
of methods. Two of these methods are discussed here,
➢ High-Pressure Carbon Mono-oxide Deposition (HiPCO);
This method involves a heated chamber through which
carbon mono-oxide gas and small clusters of iron atoms flow.
When carbon mono-oxide molecules land on the iron clusters,
the iron acts as catalyst. This helps a carbon mono-oxide
molecule to break up into a carbon atom and an oxygen atom.
This carbon atom bonds with other carbon atoms and a
nanotube lattice is formed. The oxygen atom combines with
another carbon mono-oxide molecule to form carbon dioxide.
This carbon dioxide gas the floats off into the air.
High-Pressure Carbon Mono-oxide Deposition Setup
➢ Chemical-Vapour Deposition (CVD);
In this method, a substrate is prepared with a layer of
metal catalyst particles such as nickel, cobalt or iron.
The substrate is heated to approximately 700ºC in a
chamber. To initiate the growth of nanotube, two gases
are blown into the chamber. One is process gas such as
ammonia, nitrogen or hydrogen. Other is carbon
containing gas such as methane. Methane contains one
carbon atom and four hydrogen atoms. The high
temperature in the chamber breaks the bonds between
the carbon atoms and the hydrogen atoms in the methane
molecules. These carbon atoms attach to catalyst
particles where they bond to other carbon atoms. This
results in the formation of nanotubes.
Chemical-Vapour Deposition (CVD)
 Structure of Carbon Nanotubes
When viewed with transmission electron microscope
carbon nanotubes appears as planes. A SWNT appears
as two-planes whereas in MWNT more than two
planes are observed.
The naming scheme of SWNT is done by a pair of
indices (n, m) called the chiral vector.
The integers n and m denote the number of unit
vectors along two directions in the honeycomb crystal
lattice of graphene.
T denotes tube axis and a1 and a2 are the two unit
vectors of graphene sheet in real space.
Graphene sheet
As the graphene sheets can be rolled in different
ways, this leads to three types of nanotubes as under;
➢Armchair (n, n): There is a line of hexagons
parallel to the axis of nanotube.
➢Zig-Zag (n, 0); There is a line of carbon bonds
down to the center. Here, m=0.
➢Chiral (n, m); They exhibit a twist or spiral (called
chirality) around the nanotube.
Wrapping of (10,0) SWNT

(0,0)
Ch = (10,0)

(n,0) or (0,m)
θ- 00

y
a1 Zig-zag
a2
x
Wrapping of (10,10) SWNT

(0,0)

n=m
θ- 300

Ch = (10,10)
y
a1
a2
x
Armchair
Wrapping of (10,5) SWNT

(0,0)

n≠m Ch = (10,5)

00<θ<300

y
a1
a2
x
Chiral