UNIT – IV

Nanotechnology
Origin of Nanotechnology, Nano Scale, Surface to
Volume Ratio, Quantum Confinement, Bottom-up
Fabrication, Sol-gel, Precipitation, Chemical vapor
Deposition (CVD); Top-down Fabrication; Thermal
evaporation, Ball Milling, Characterization of Nano
materials (XRD&TEM), carbon nano tubes (CNTs),
Applications of Nano Materials.
Introduction:
Richard Feynman was the first person to introduced
nanoscience in 1959.
Prof. Norio Taniguchi of Japan in 1974 used the word nano
technology.
 The word “nano” is a Greek word and meaning is dwarf(small).
 The prefix nano means “ one billionth” or 10-9 meter.
Size limitation of nano material is the 1-100 nm range.

Materials when reduced down to 100 nm show drastic changes in

respect of Physical, Chemical, Optical, Magnetic, Mechanical and
Electrical properties.
All these leads to exciting applications in Bioscience, Medical,
Environmental science, Electronics, Security and Cosmetics etc.
Materials reduced to the nano-scale can show different
properties compared to what they exhibit on the macro-
scale
They are very hard
 They are exceptionally strong
 They are ductile at high temperatures
 They are chemically very active
 They are wear and erosion resistant
 Opaque substances may become transparent
(copper)
 stable materials turn combustible (aluminum);
 insulators become conductors (silicon); and
 solids turn to liquids at room temperature (gold)
……
Nanoscience is the study of phenomena and manipulation of
materials at atomic, molecular and macromolecular scales, where
properties differ significantly from those at a larger scale.

Nanotechnology is the design, characterization, production and

application of structures, devices and systems by controlling shape
and size at the nanometer scale.

The properties of materials can be different at the nanoscale for

two main reasons:
1. Increased surface area to volume ratio
2. Quantum Confinement effect
3. Dominance of electromagnetic forces
4. Random molecular motion
1. Surface area to Volume ratio:
Nano-materials have a relatively larger surface area when
compared to the larger form of the material of same volume.
For a sphere of radius r, the surface area and its volume can be
given as

Sphere Volume Formula =

Sphere Surface area =

Surface to Volume ratio =

3/r
Thus, we find that when the given volume is divided into smaller
parts, surface area increases.
 Single Box Ratio
6 m2
= 6 m2/m3
1m 3

Smaller Boxes Ratio

12 m2
= 12 m2/m3
1m 3

Neglecting spaces between the smaller boxes, the volumes of the box on
the left and the boxes on the right are the same but the surface area of the
smaller boxes added together is much greater than the single box.
Quantum Confinement Effect

When the dimensions of a potential well or a box concerned

with a particle are reduced to the order of de Broglie wavelength of
electron (within few tens of nanometres), then energy levels of
electrons change. This effect is called quantum confinement.
At reduced dimensions, they are said to be either a quantum well, a
quantum dot, or a quantum wire.
The physics at these dimensions is entirely different.
Actually, when the size of the grains is reduced to nano-level, then
overlapping of wave function and quantum confinements occurs.
If d is the diameter of the grain size (group of cluster), then
the energy goes up by factor 1/d2
Dominance of Electromagnetic forces:

Out of nuclear, gravitational, electric and magnetic forces, at nano scale electric and
magnetic forces become more predominant.

As we know that gravitational forces are mass dependent. Hence, at nano scale the
mass of the particles is very small and gravitational forces becomes insignificant.

Nuclear forces (Strong, Weak) are significant over the distance of 10 -5 nm, which is
extremely shorter than nano scale, so they are insignificant.
Random molecular motion:

In microscopic scale the random molecular motion is in significant, where as in nano

regime the random molecular motion becomes more predominant.
Electronic band structure at nano scale
The behaviour of matter at the nanoscale - particularly affecting the
following properties

1.Optical: Spectral shift of optical absorption and fluorescence,

increase in efficiency of semiconductor crystal.

2.Electrical: Increase in conductivity in ceramics and magnetic

nanocomposites.

3.Magnetic behaviour of materials: Increase in magnetic

coercivity

4. Mechanical properties – increased hardness

5. Chemical properties – increases reactivity

6. Catalytic: Better catalytic efficiency due to high surface area.

DIFFERENT TYPES OF NANOSTRUCTURES: (CONFINEMENT
DIMENSIONS 0-D, 1-D, 2-D, AND 3-D)
•0-D (Delocalisation dimensions)
All dimensions (x, y, z) at nanometric scale; the other dimension is
large.
Example: Nanoparticles
•1-D (Delocalisation dimensions)
Two dimensions (x, y) at nanometric scale; the other dimension is large.
Example: Nanorods, nanotubes

•2-D(Delocalisation dimensions)
One dimension (t measured along z-axis) at nanometric scale;two other
dimensions (Lx, Ly) are large.
Example: Thin nanofilms
•3-D (Delocalisation dimensions)
All of the three dimensions (Lx, Ly, Lz) are not at nanometric scale.
Example: Nanocrystalline and nanocomposite materials.
A bulk conductor has all its three dimensions more than
100 nm.
Quantum dot : The extreme case of this process of size
reduction in which all three dimensions reach at the
nanorange is called quantum dot ( O-dimension).

Quantum wire:If two dimensions are reduced and one

remains large, the resulting structure is referred to as
the quantum wire (1-Dimension).

Quantum well: If one dimension is reduced to the

nano range while the other two dimensions remain
large, then we get a structure known as quantum
well. ( 2-Dimension)
 SYNTHESIS OF NANOMATERIALS

Nanomaterials can be synthesized by ‘Top down’

and ‘Bottom up’ techniques.
Top-Down Process
Under this process of fabrication, bulk materials are broken into
nano-sized particles.
In this approach, there is no control over the size and the
morphology of particles.
Some common methods of top-down method are as follows.
(i) Ball milling method
(ii) Plasma arcing
(iii) Laser sputtering
(iv) Vapour deposition method
Bottom-Up Process
Bottom-up approach refers to the building up of a material from the
bottom, i.e., atom by atom, molecule by molecule, or cluster by
cluster.
Colloidal dispersion is a good example of bottom-up approach in the
synthesis of nanoparticles.
There are different methods used for the synthesis are:
(i) Sol–gel method
(ii) Colloidal method
(iii) Electrodeposition
(iv) Solution phase reductions
The most important feature of this process is that the size and
morphology of fabricated nanoparticles are well controlled.
Ball Milling method:
Ball milling is a top-down approach of nanoparticle
synthesis which includes mechanical breakdown of large
substances into smaller one. It is used in producing metallic
as well as ceramic nanomaterials.
The size of the nano powders produced by this technique
depends on the speed of rotation of the balls and the
dimensions of 2 to 30 nm can be achieved.

This method holds the advantage of low temperature

synthesis as against the traditional methods employing high
temperature synthesis for producing materials.
The working of a ball mill can be understood as follows:

a.It consists of stainless steel chamber and several small iron, silicon carbide, hardened
steel, or tungsten carbide balls to rotate inside the mill.
b.Powder of material is put in the steel chamber.

c.Small balls are allowed to rotate around the inside of chamber and then fall on solid
material with gravity force and crush the solid into nano crystalline.

a.A magnet is positioned outside the chamber to apply pulling force on the material. This
force raises milling energy as the milling chamber or container rotates the metallic balls.
b.The ball and material - mass ratio is generally kept at 2:1.
c.These metallic balls impart very high energy to the powder resulting in crushing of the
powder. The ball milling process generally takes 100 to 150 hrs to give uniformly crushed
fine powder.
d.It is mechanical processing technique; consequently the structural as well as chemical
changes are caused by the mechanical energy.
Ball Milling method
2.Chemical vapor deposition
3.Physical vapor deposition
Chemical Vapour Deposition:

 In this method, nanoparticles are deposited from the gas phase.

Materials are heated to form a gas and then allowed to deposit on solid
surface usually under vacuum conditions.
 The deposition may be either physical or chemical. In deposition by
chemical reaction new product is formed. Nano powder of oxides and
carbides of metals can be formed, if vapours of carbon or oxygen are
present with the metal.

 These materials include: silicon, carbon fiber, carbon nanofibers,

filaments, carbon nanotubes, SiO2, silicon-germanium, tungsten, silicon
carbide, silicon nitride, silicon oxynitride and titanium nitride.
 CVD process is also used to produce synthetic diamonds.
 Chemical Vapor Deposition

Reaction chamber

Hot Chamber

Metal organic Precursor

Rotating belt

Block Diagram of CVD

Working Concept
A metal organic precursor is introduced into the hot zone of the
reactor using mass flow controller.
The precursor is evaporated either by resistive or inductive heating.
The carrier gas such as Ar or Ne is introduced into hot chamber to
carries the hot atoms (precursor) to the reaction chamber.
The hot atoms collide with cold atoms (other reactants) undergo the
condensation process through nucleation and form small clusters
Then these clusters are allowed to condense on a moving belt
arrangement with scrapper to collect the nanoparticles (range 1–100 nm)
Ultimately, the particles are collected and may be compacted to
produce a dense nano material.

In this process, other reactants are used to control the reaction rate.
And the particle size can be controlled by varying the inert gas pressure.
inside the chamber.
Advantages:
They increased yield of nanoparticles.
A wider range of ceramics including nitrides and carbides can
be synthesized.
More complex oxides such as BaTiO3 or composites structures
can be formed.
In addition to the formation of a single phase nanoparticles by
CVD of a single precursor the reactor allows the synthesis of
a) Mixtures of nanoparticles of two phases or doped
nanoparticles by supplying two precursors at the front end of the
reactor
b) Coated nanoparticles, i.e n-ZrO2 coated with n-Al2O3 or
vice versa, by supplying a second precursor at a second stage of
the reactor.
Physical Vapour Deposition Method:
In PVD, the material goes from a condensed phase (as
precursor) to a vapor phase and then back to the
condensed phase (deposited as thin films).
In PVD, the film is deposited over the entire exposed
area of the object. It is basically a vaporization coating
method involving atomic scale transport of the material to
be coated.
The gas phase precursor condenses onto the substrate,
thereby creating the required layer. No chemical reactions
occur during the deposition process.
The process is performed under vacuum and comprises the
following steps
Evaporation: The target (material to be coated/deposited) is
incident with high energy source like an electron/ion beam. The
atoms are released from surface under go in to the vapour phase.
Transport: These atomic vapours are moved towards the surface of
the substrate requiring coating.
Deposition: Atomic vapours are deposited on the surface of the
substrate.
*Reaction: If the target materials is in the form of compounds such
as metal oxides, nitrides, carbides and the like materials,
intentionally introduced a gas which react with compounds of the
target material under go into the vaporization during the transport
before deposition on the substrate.
Physical vapour deposition Technique
Advantages of PVD