Nanotechnology

Definition:

This is a term that has entered into the general and scientific vocabulary only recently but has been used at
least as early as 1974 by Taniguchi. Nanotechnology is defined as a technology where dimensions and
tolerances are in the range of 0.1-100 nm (from size of the atom to about the wavelength of light) play a
critical role.
Popular definition for Nano technology is: “Nano technology relates to the ability to build functional devices
based on the controlled assembly of nano scale objects for specific technological applications.”

Difference between Nano science and Nano technology:

Study on fundamental relationships between physical properties and phenomena and material dimensions in
the nanometer scale referred to as Nano science.
But Nano technology is the application of these nano structures and principles behind them to make nano
scale devices and to produce new materials.

Introduction:
Some notes on scale
1A0=10-10m
1 nm=10-9m 1 µm=10-6m 1mm=10-3m
Atomic/crystallographic micro structure macro structure
1cm=10-2m

Role of Bottom-up and Top-Down approaches in Nanotechnology

Figure: Schematic representation of the building up of Nanostructures.

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 The biggest problem with top down approach is the imperfection of surface structure and significant
crystallographic damage to the processed patterns.
 These imperfections which in turn leads to extra challenges in the device design and fabrication.
 But this approach leads to the bulk production of nano material. Regardless of the defects produced by
top down approach, they will continue to play an important role in the synthesis of nano structures.

Bottom up approach also promises a better chance to obtain nano structures with less defects, more
homogeneous chemical composition. On the contrary, top down approach most likely introduces internal
stress, in addition to surface defects and contaminations.

SIZE DEPENDANT PROPERTIES OF NANOMATERIALS

 Thermal properties

As size decreases surface energy increases also melting point decreases – This is due to the fact that the
surface atoms requires less energy to move as they are in contact with less atoms with the surface.
E.g. Nano crystals of CdSe of 3mm size have melting point 700K whereas the CdSe bulk material will melt
at 1678 K.

 Mechanical properties

Surface and interfacial forces becomes dominant at nano scale level – Like adhesion, capillary and strain
forces will be high compared that in the macroscopic length scales. This results in changes in malleability,
ductility and plasticity.
Nano phase ceramics are more ductile at elevated temperatures compared to that of coarse grained (usual)
ceramics.

 Optical Properties

Optical properties of material depends upon it electronic structure, changes in the band gap (VB-CB) and
zone structure of the material leads to changes in absorption and emission of the light by the material.
Eg. Bulk gold appears yellow in colour whereas nano sized gold appears different colour based on their size.
– This is explained as in bulk gold electrons are free to move throughout the metal hence they are free and
absorption wavelength resulting in yellow colour.
However in case of nano gold electrons are restricted for their movement resulting in absorption of light at
wavelength otherthan that the bulk gold will absorb.

 Catalytic activity
 When we compare bulk material with that of nano material of same weight, the surface area available in
case of nanomaterials is some thousand times more than bulk material.
 This enhanced surface of the nano materials makes them active catalysts in many reaction
 Many nano materials are used as heterogeneous catalysts.
Certain nano structured metal clusters have shown effective catalysis in hydrogenation reactons.
They can be made as electrodes for certain reactions leading to selective product formation

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Liquid solid reactions (Precipitation method)

Precipitation is a technique in which two reagents mixed to get a insoluble material in the solid form which
precipitates out of the solution and settles down.

The precipitation technique of preparation of nano materials involves two steps

 Formation of the nuclei: Here the nuclei refers to group of atoms together – Initially as the precipitation
starts few particles will approach each other forming a small mass (called nucei).
 Growth step: In the growth step the above formed nuclei attracts the particles present in the solution thus
increasing its size itself.
 The growth step decides that the material to be formed is a nano material or bulk material.
 By monitoring and restricting the growth of the nuclei we can prepare nano size particles. If the growth
is not controlled, leads to precipitation of bulk mass.
 The growth of the nuclei can be controlled by maintaining suitable concentrations, pH of the medium and
temperature.
For example, TiO2 powders have been produced with particle sizes in the range 70-300 nm
from titanium tetraisopropoxide.

Fullerene

 Fullerenes are the third allotropic forms of carbon apart from crystalline diamond and graphite, which
was discovered in the year 1985.
 It consists of hexaognal rings and alternating pentagonal rings of carbonclosed in the for of hallow
spheres like foot ball which is well known as bucky ball.
 The fullerene with 60 carbon atoms arranged as 12 pentagons and 20 hexagons in the form of a sphere is
called as Buckminster fullerene named after the inventor Richard Buckminster Fuller
 Fullerenes were first isolated from soot of chimneys and extracted with solvents in the form of red
crystals
 The hybridization of carbon in fullerene is proposed to be between sp2 and sp3 as it show symmetrical
nature in bond lengths and bond angles

Types of fullerens

1. Bucky ball clusters- Fullerenes having less than 300 carbon atoms are known as Bucky balls the
smallest known bucky ball is with 20 carbon atoms(C20)
2. Nano tubes –they are hallow cylindrical tubes of carbon which are few nanometer in diameter and up
to several microns in length
3. Mega tubes –These are the tubes with larger diameter than nanotubes and their walls are made up of
varying thickness.
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 4. Poly fullerenes –Polymers of fullerenes are made of C60, C70 balls linked to each other by covalent
bonds in different ways.

Characteristics of Fullerenes

1. An important characteristic of C60 molecule is its high symmetry with 120 symmetry operations.
Each carbon bond with three other carbon atoms using sp2 hybridization
2. Chemically fullerens stable breaking the balls requires a temperature above 1000oC, However
fullerens are quite reactive as they possess π electrons.
3. Fullerens are insoluble in water, sparingly soluble in many other solvents and more soluble in toluene
and carbon disulphide.
4. Fullerens themselves are non toxic but some of their derivatives are toxic.

Applications of fullerenes

1. They act as powerful antioxidants, can find applications in health and personal care areas
2. Due to the small size, room temperature operation and high sensitivity – they find application as
coating materials on some chemical sensors.
3. Field emission display (FED’s) using carbon nanotubes are the next generation replacement for LCD,
Plasma with decreased cost and increased power.
4. Fullerenes blended with polymers are used in phogtovoltaics.
5. Their use in water purification, catalysis and fuel cell are also being explored

Carbon Nanotubes (CNT’s )

They are also called as bucky tubes –they posses extraordinary strength and electrical and thermal properties.

Types of carbon nanotubes

1. Single Walled Nano Tubes (SWNT’s)

Which is of diameter approximately 1nm and with tube length several million times longer
The structure of SWNT’s is imagined to be a wrapping of one atom thick layer of graphite into a cylindrical
shape.

2. Multi Walled Nano Tubes (MWNT’s)

Consists of multiple rolled layers carbon – sheets of graphite are arranged in concentric cylindrical form.

Characteristics of Carbon Nanotubes.

1. Strength: These are strongest and stiffest materials known, the strength result from covalent sp2 bonds
and its tensile strength tested is greater than that of high carbon steel.

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2. Hardness: A super hard material can be prepared by compressing SWNT’s to above 24 GPa at room
temperature which show a hardness of 52 GPa compared by taking hardness reference as diamond and
boron nitride with hardness 150 GPa and 62 GPa respectively.
3. Kinetic: MWNT’s which consists of concentric multiple cylindrical structures which can glide inside and
out without any friction, hence creating atomically perfect linear rotational bearings
4. Thermal: All nanotubes shows good thermal conducting property along the tube, but they are good
insulators laterally to the tube axis – shows very high thermal conductivity along the carbon length
compared to that of copper.

Nano wires
A nano wire is a wire like structure with a diameter of the order of one nanometre and an unconstrained
longitudinal size. At these magnitudes quantum mechanical effects are important, nano wires are also known
as quantum wires. Nanowires can be made up metallic (Ni, Pt, Au), semiconducting (Si, GaN) and insulating
material (SiO2, TiO2).
They have high density, high diameter dependant band gap, enhanced surface scattering high excitation
binding energy high surface area to volume ratio this makes unique in their electrical thermal optical
magnetic and chemical properties

Figure: Silver nanowires

Applications of nanowires
 They find lot of applications in electronics, optics, magnetic medium and sensor devices.
 They are used in magnetic information storage medium.
 They are used as Rectifiers, junction diodes, memory cells and switches, transistors, LED’s and inverter
etc. ,
 Nano wires are used to coat titanium implants which can reduce the risk of implant failure in biomedical
field.

Nanorods

Nano rods ranges in the dimension from 1-100nm they can be prepared directly by taking metals and
semiconductor (Vapour phase method) materials important examples are ZnO and Gold Nanorods – Where
metal oxide is reduced to metal vapours and is reoxidized to get nanorods.

Figure: ZnO nanorods

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Applications of nanorods
 They are used in display technology- Because of the their change in reflectivity with change of
orientation with an applied electric field.
 They also used as (MEMS) Microelectromechanical.
 Nano rods are selectively absorbed by cancerous cells and gets heated up when is irradiated with IR
radiation and gets destroyed.
 They will be employed in energy harvesting system (semiconductor nanorods) and in LED’s

Bio medicals (Dendrimers)

These are typical organic nano particles are new class of polymeric materials
A dendrimer means a tree like structure in Greek consists of molecular chains branching out from a common
centre
They form a tightly packed ball like structure unlike linear polymer, hence have significantly lower viscosity.
Compared to linear polymers these have significantly better chemical properties – this is due to presence of
large surface groups and the ability of host guest mechanism due to the presence of internal cavities (Shape
and size of the cavities decides number of guest molecules can be entrapped)

Applications of Dendrimers
 They are used in in-vitro diagnosis of cardiac problems.
 They are used as contrasting agents in Magnetic Resonance Imaging (MRI).
 They serve as carriers to take genes through the cell membrane into the nucleus also in targeted delivery
drugs.
 They are used as nano scale catalyst as they are highly soluble and also provide large surface area.
 They are used in making liquid membranes for stabilizing aqueous-organic emulsion which helps to
extract chemical compound between two phases.
 They are also used as Proton sensors in the determination of pH.