Nanotechnology

Introduction

• Nano phase material or Nanomaterials are the nano structured materials having a
characteristic length from 1 nm to 100 nm.

• A cluster of nanoparticle contains less than 104molecules or atoms.

• Nanomaterials have nonlinear optical and magnetic properties.

Nanoscience
It is defined as the study, manipulation and engineering of matter, particles and structures on the
nanometer scale, where properties differ significantly from those at a larger scale.

Nanotechnology:
It is defined as the design, characterization, production and application of structures, devices
and systems by controlling shape and size at the nanometer scale.
Basic principles of Nano science and technology
What makes the properties of materials change when taken to nano size?
The properties of nanoscale materials are very much different from those at a larger scale. Two
principal factors cause the properties of nanomaterials to differ significantly from other
materials.
- increased surface area to volume ratio
- quantum confinement effect
Increase in surface area to volume ratio:
Nanomaterials 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 is 4 r2
Volume is 4 r3/3
Surface area to its volume ratio= (3/r)
Thus when the radius of the sphere decreases, its surface area to its volume ratio increases.
The increase in surface to volume ratio can be shown as given under by dividing a cube into 8
small cubes.
Area= 6 x 1m2

=6 m2
Quantum confinement effect
When atoms are isolated, the energy levels are discrete. When a bond is established
between a group of atoms, the energy levels split and form bands which are commonly
called as Energy bands. Nanomaterials represent intermediate stage where the energy levels
are neither completely isolated nor merged.
 or
From the study of particles in a potential box or well, when the dimensions of such wells
or boxes are of the of de-Broglie wavelength of electrons or mean free path of electrons (i.e. ,
within few tens of nanometer), energy levels of electrons change. This effect is called
Quantum confinement.
The above mentioned effects change the properties of nanomaterials then when
compared with that of bulk form.
Fabrication of Nano materials
There are two approaches for the fabrication of nano materials viz.,
1. Top down approach
2. Bottom up approach
1. Sol-gels process (Bottom up fabrication)
1. Preparation of sol: Formation of different stable solutions of alkoxide or solvated metal precursor
2. Gelation: Gelation resulting from the formation of an oxide – or alcohol-bridged network by a poly condensation.
3. Aging of gel: During which the polycondensation reactions continue until the gel transforms into a solid mass
(Aerogel or xerogel depends on drying conditions).
4. Drying of the Gel: Water and other volatile liquids are removed from the gel network by thermal evaporation.
5. Dehydration Process: During which surface –bound M-OH groups are removed. By heating of monomers to form
particles.
6. Densification and decomposition of the gels can be done at high temperature (T > 800 degree centigrade)
4. Chemical Vapour deposition
technique (Bottom up approach)
This method involves depositing nanoparticulate material
from the gas phase. Material is heated to form a gas and
then allowed to deposit on a surface under vacuum. The
deposit can be direct or by chemical reaction.
This process forms nano powders of oxides and carbides
of metals in vapours of oxygen and carbon.
This process can also be used to grow surfaces. Object to
be coated is taken as substrate in the presence of chemical
vapour. The first layer of atoms or molecules deposited
may or may not react with the surface but act as a
template on which material can grow.
Various types of CVD techniques involve low-pressure
CVD(LPCVD), Plasma enhanced CVD(PECV D), and
laser enhanced CVD(LECVD).
Carbon nanotubes can also be grown by CVD techniques.
Advantage of this method is that nanomaterials of high chemical homogeneity with ultrahigh purity and high surface area can
be realized. Spherical particles, fibres, thin films as well as coatings can be prepared.

Ball Milling Method: (Top down

approach)
This method is also called as Mechanical crushing
method. This process was developed by Benjamin
This method is most suitable to prepare elemental
and oxide powders eg., iron nitriles, cerium oxide,
zinc oxide etc., In this process powder mixture is
placed in the canister or milling bowl and the bowl is
made to rotate at high revolutions per minute. The
bowl rotates at very high speed simultaneously
imparting its kinetic energy to the material through
the grinding balls(WC-balls). The grinding balls are
made up of either stainless steel or tungsten carbide.
3. Physical Vapour deposition (Top
down approach)
This method relies on solid and molten sources. It is a
physical process involving gas transport. The source
atoms enter the gas phase by evaporation or collision
and then deposit on the substrate.
The source material in the form of vapour reacts with
the gaseous medium and form cluster/ions. The vapour
and gas mixture is cooled down to realize nanometric
crystal formation.
This technique requires high vacuum.
Various types of nano materials 2D, 1D, 0D
Characterization of nanomaterials
For characterization of nanoparticles, the most widely used techniques
are

X-ray diffraction(XRD),

Scanning electron microscope (SEM) and

Transmission electron microscope(TEM).

1. XRD (X-ray
diffraction analysis)
X-ray scattering or diffraction
techniques reveal information
about the crystallographic
structure, chemical composition,
and physical properties of
materials and thin films.
These techniques are based on
observing the scattered intensity
of an X-ray beam hitting a
sample as a function of incident
and scattered angle, polarization,
and wavelength or energy. The
output of xrd technique consists
of a graph between counts (Intensity) versus
diffraction angle (2θ) as shown in the figure
of xrd of NaCl sample.
In the graph peak of the
diffraction is very important. If
‘θ’ is the angle of diffraction for
which the intensity is maximum
(peak value) the average particle
size can be estimated using
Debye Scherrer formula

0.9 ∗ λ
𝐷=
𝑤 𝑐𝑜𝑠𝜃

Where λ is the wave length of

the X-ray and ‘W’ FWHM ( Full
width at half maximum) and ‘D’
is the particle diameter (size of
particle)
Scanning Electron Microscope (SEM)
Signals produced from electron-sample interaction:
The types of signals produced by an SEM include
• Secondary electrons,
• Back-scattered electrons (BSE),
• Characteristic X-rays,
Secondary electrons: The signals result from interactions of the electron
beam with atoms at or near the surface of the sample (inelastic scattering).
The SEM can produce very high-resolution images of a sample surface,
revealing details about less than 1 to 5 nm in size. Due to the very narrow
electron beam, SEM micrographs have a large depth of field yielding a
characteristic three-dimensional appearance useful for understanding the
surface structure of a sample.

Back-scattered electrons (BSE) : are beam electrons that are reflected

from the sample by elastic scattering. The intensity of the BSE signal depends
on the atomic number (Z) of the specimen, BSE images can provide
information about the distribution of different elements in the sample.
 Characteristic X-rays : are emitted when the electron beam removes an inner
shell electron from the sample, causing a higher energy electron to fill the shell
and release energy. These characteristic X-rays are used to identify the
composition and measure the abundance of elements in the sample.
Transmission Electron Microscope (TEM): Schematic of TEM is shown in figure
below
**Applications of
Nano materials**
Quantum effects:
According to band theory, solid materials have energy bands and
isolated atoms possess discrete energy levels. Nanomaterials are in
intermediate to the above two cases as shown in figure.
For nanomaterials, if the dimensions of potential wells are of the order
of the de-Broglie wavelength of electrons or mean free path of
electrons, then the electrons will behave as quantum particles and the
energy levels of the electrons will change (not remain continuous but
discrete set of energy levels) and ‘e’ will remain confined to a small
region.
Thus when size of the system is small quantum effects are dominating.

This can affect the

optical, electrical and
magnetic and physical
properties of materials
General properties of Nano materials
1. Physical Properties :
The change in interparticle spacing and the large surface- to -volume ratio in particles
have a combined effect on material properties. The melting point decreases with size and at
very small sizes the decrease is faster. The interatomic spacing decreases with size.

2. Chemical Properties:
The large surface- to -volume ratio, the variation in geometry and the electronic structure have
a strong effect on catalytic properties. Another important possible application is hydrogen in
metals. It is well known that most metals do not absorb hydrogen, and even among those that
do, hydrogen is typically absorbed dissociatively on the surfaces with a hydrogen- to- metal
atom ratio of 1. For a small positively charged clusters of Ni, Pd, and Pt containing between 2
and 60 atoms can absorb up to 8 H- atoms per metal atom. The number of absorbed atoms
decreases with increasing cluster size.
2. Electrical Properties:

Ionization potential at small sizes are higher than that for the bulk and show
marked fluctuations as a function of size. Due to quantum confinement the electronic
bands in metals become narrower. In nanoceramics and magnetic nanocomposites, the
electrical conductivity increases with reduction in particle size whereas in metals
electrical conductivity decreases.

4. Optical Properties :
Suppose we have a suspension of nanoparticles in a host. Depending on the
particle’s size, different colours are seen. Gold nanospheres of 100 nm
appears orange in colour, while 50 nm nanospheres appear green in colour.
The particles can be made to emit or absorb specific wavelengths (colours)
of light, merely by controlling their size.
5. Magnetic Properties :
The strength of a magnet is measured in terms of coercivity and saturation
magnetization values. These values increase with a decrease in grain size and an increase in
the specific surface area (surface area per unit volume) of the grains. Small particles are more
magnetic than the bulk material. Nanoparticles of even non-magnetic solids are found to be
magnetic. In addition to free clusters, clusters of nonmagnetic elements supported on metal
substrates have also been proposed to be magnetic. Ferromagnetic and antiferromagnetic
multilayers have been found to exhibit giant-magneto resistance (GMR-Change in the
resistance of the material upon application of magnetic field is called magneto resistance.