NANOTECHNOLOGY

Syllabus

Introduction to nanoscience and technology, Increase in surface to volume ratio for

nanomaterials, Quantum confinement in one dimension, two dimension and three dimension-
Nano sheets, Nano wires and Quantum dots, Properties of nanomaterials-mechanical, electrical
and optical, Applications of nanotechnology

Introduction to nanoscience and technology

Nanoscience is the study of the fundamental principles of molecules and structures with atleast
one dimension roughly between 1nm and 100nm. Nanotechnology is an emerging engineering
discipline that applies methods from nanoscience to create products.

The difference between nanoscience and nanotechnology is that between theory

and practice. Nanoscience is the study of phenomena and objects at the nanoscale and
nanotechnology deals with the ability to develop and use the technology to manipulate and
observe at nanoscale. In short, nanoscience is the study of nanostructures and nanotechnology is
the application of this knowledge in different industries.

Nanoscale and its significance

The word nano is derived from a Greek word meaning dwarf or extremely small and is equal to
one billionth (10-9) part of a unit. A length of a nanometer can accommodate 10 hydrogen atoms.

Most of the properties of a solid depend on size of the solid. For bulk material,
properties like resistivity, density, elastic modulus etc are averaged properties. When size of the
material becomes smaller and smaller this averaging no longer works and the properties of
materials change drastically in nanometer range. Two main factors that causes significant change
in the properties of nanomaterials from their bulk counterpart is increased surface to volume
ratio and quantum effects. These factors can enhance properties such as resistivity, strength and
electrical characteristics.

Surface to volume ratio for nanomaterials

The surface area to volume ratio for a material or substance made of nanoparticles has a
significant effect on the properties of the material. Materials made of nanoparticles have a
relatively larger surface area when compared to the bulk material (material made up of larger
number of particles).

For a spherical nanoparticles surface to volume ration is,

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Surface area of the sphere = 4𝜋𝑟 2
4
Volume of the sphere= 3 π𝑟 3

4𝜋𝑟 2
Surface area to volumeratio is, Surface area/ volume = 4𝜋𝑟3
3

3
=
𝑟
It means that the surface area to volume ratio increases as the radius of sphere decreases, since it
is inversely proportional to radius. It also means that when a given volume of material is made
up of smaller particles, the surface area of the material increases. Therefore as particles size
decreases a greater proportion of the particles are found at the surface compared to those inside.
Thus nanoparticles have a much greater surface area to volume ratio as compared with the larger
particle. This leads to nanoparticles being more chemically reactive. As chemical reactions occur
between that are on the surface, a given mass of nanomaterial will be more reactive than the bulk
material.

Quantum confinement

Quantum confinement is the spatial confinement of electron in one or two dimensions within a
material. Or quantum confinement is the restricted motion of randomly moving electron in
specified energy levels, when the dimension of a material approaches the de-Broglie
wavelength of electron. When this occurs the properties change significantly because energy
levels become discrete and motion of electrons become restricted. And this increase or widens up
the band gap and ultimately band gap energy also increases. Based on the number of dimensions
that are confined, nanostructures are classified as quantum well (nanosheet), quantum wire
(nanowire) and quantum dots.

A. Nanosheet (quantum confinement in one dimension)

In nanosheets confinement is present in only one dimension (one dimension is reduced to

the nanometer ranges). That is carriers are allowed to move freely along a two
dimensional plane.

Suppose confinement is present along z direction to a small distance L z and free to move
along X and Y directions. Schrödinger equation in this case is

−ћ2 𝜕2
⌈ + 𝑉 (𝑧)⌉ 𝛹 (𝑧) = 𝐸𝛹(𝑧)
2𝑚 𝜕𝑧 2

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 The wavefunction and energy in this case is,
1
2 2 𝑛𝑧 𝜋𝑧 𝑖𝑘 𝑥 𝑖𝑘 𝑦
𝛹𝑛 (𝑥, 𝑦, 𝑧) = ( ) sin ( )𝑒 𝑥 𝑒 𝑦
𝐿𝑧 𝐿𝑧

𝑛𝑧 2 𝜋 2 ћ 2 ћ 2 𝑘 𝑥 2 ћ 2 𝑘 𝑦 2
𝐸𝑛 = + +
2𝑚𝐿𝑧 2 2𝑚 2𝑚

B. Nanowire (quantum confinement in two dimension)

In a nanowire, carriers are confined in two dimensions and allowed to move freely along
one dimension. Two dimensions are in nanometer range.
Suppose the carriers are confined in Y and Z directions to small distances Ly and Lz
respectively and free to move in X direction. Then the wavefunction and energy will be,
1 1
2 2 2 2 ny πy 𝑛𝑧 𝜋𝑧 𝑖𝑘 𝑥
𝛹𝑛 (𝑥, 𝑦, 𝑧) = ( ) ( ) sin ( ) sin ( )𝑒 𝑥
𝐿𝑦 𝐿𝑧 Ly 𝐿𝑧

𝑛𝑧 2 𝜋 2 ћ 2 𝑛𝑦 2 𝜋 2 ћ 2 ћ 2 𝑘 𝑥 2
𝐸𝑛 = + +
2𝑚𝐿𝑧 2 2𝑚𝐿𝑦 2 2𝑚

𝜋 2 ћ2 𝑛𝑦 2 𝑛𝑧 2 ћ2 𝑘𝑥 2
𝐸𝑛 = ⌈ + 2⌉ +
2𝑚 𝐿𝑧 2 𝐿𝑦 2𝑚

Motion of carriers in carbon nanotube is an example for this kind of confinement.

C. Quantum dot (quantum confinement in three dimension)

If the carriers are confined in three dimensions, then the nanostructure is called a
quantum dot. Means all three dimensions reach the nanometer range. Electrons cannot
move freely along any dimension.

In this case Schrödinger’s equation is

−ћ2
⌈ 𝛻 2 + 𝑉 (𝑟)⌉ 𝜳(𝒓) = 𝐸𝜳(𝒓)
2𝑚

The corresponding wave function and energy is

1 1 1
2 2 2 2 2 2 𝑛𝑥 𝜋𝑥 ny πy 𝑛𝑧 𝜋𝑧
𝛹𝑛 (𝑥, 𝑦, 𝑧) = ( ) ( ) ( ) sin ( ) sin ( ) sin ( )
𝐿𝑥 𝐿𝑦 𝐿𝑧 𝐿𝑥 Ly 𝐿𝑧

𝑛𝑥 2 𝜋 2 ћ2 𝑛𝑦 2 𝜋 2 ћ2 𝑛𝑧 2 𝜋 2 ћ2
𝐸𝑛 = 2 + 2 +
2𝑚𝐿𝑥 2𝑚𝐿𝑦 2𝑚𝐿𝑧 2

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 Classification of quantum confined structures
Structure Quantum confinement Number of free dimension
Bulk 0 3
Quantum well 1 2
Quantum wire 2 1
Quantum dot 3 0

Excitons
An exciton is a bound pair of electron and hole, which are attracted each other by the
electrostatic Coulomb force. An exciton can form when a material absorbs a photon of
higher energy than its band gap. This excites an electron from the valence band into the
conduction band. In turn, this leaves behind a positively charged hole. The excitons can
move through solid. The size of the exciton depends on the nature of the material. An
exciton can move through the crystal and transport energy; it does not transport charge
because it is electrically neutral.
The negatively charged electron attracts the positively
charged hole through the coulomb interaction and can become bound to form a hydrogen
type atom. The exciton radius can be taken as an index of the extent of confinement
experienced by a nanoparticle. Two limiting regions of confinement can be identified on
the basis of the dimension‘d’ of the nanoparticle to the exciton radius ‘a eff’.
d>aeff weak confinement
d<aeff strong confinement
d>>aeff no confinement
Under weak confinement conditions, the exciton can undergo unrestricted
translational motion and in strong confinement condition translational motion is
restricted.

Properties of nanomaterials

Nanomaterials show remarkable specific properties that are different from their bulk counterpart.
This can be due to large fraction of surface atoms, large surface energy, spacial confinement and
reduced imperfections. Properties of nanomaterials depend on the size of atom that constitutes
the material.

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Mechanical properties

In nanomaterials mechanical properties like hardness, Young’s modulus, yield strength,

fracture toughness etc enhances.
Nanomaterials have lower melting point
Nanomaterials have high mechanical strength it is mainly due to reduced probability of
defects.

Optical properties

The reduction of material dimension has pronounced effect on its optical properties. This is
mainly due to two reasons. One is increased energy level spacing as the system becomes more
confined and other is surface Plasmon resonance. The energy level separation in a nanocluster
depends on size of nanoclusters, which affect the energies needed for the transition of electrons
to excited states. Clusters of different sizes will have different absorption spectra. Hence clusters
of different size exhibit different colours.

Eg; nanoscale gold particles can be orange, purple, red or greenish depending on the size of the
cluster.

Surface Plasmon resonance is the coherent excitation of all the free electrons within the
conduction band upon interaction with an electromagnetic field leading to an inphase oscilation.
This takes place when size of the nanoparticle is smaller than wavelength of incident radiation.

Electrical properties

Size plays an important role in the electrical properties of nanomaterials which is based on four
mechanisms. They are surface scattering, change of electronic structure, quantum transport
and effect of microstructure. Electrical conductivity decreases with a reduced dimension due to
increased surface scattering and change of electronic structure. As the bulk material reduces its
size, continuous energy bands are replaced by discrete energy levels and band gap increases as
the size decreases. As a result some metal nanowires undergo transition to become
semiconductors and semiconductors might become insulators when their diameters are reduced
below a critical diameter.

Applications of nanotechnology

1. Using nanomaterials we can improve the efficiency of solar cells.

2. By designing zeolite catalysts at the nanoscale, we can access and use fossil fuels much
more efficiently.
3. Nanomaterials with greater surface area helps in the development of super capacitors
with increased energy density and power output than conventional materials.

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 4. Nanomaterials have environmental applications Nanomaterials can be used as catalysts
to react with harmful and toxic gases like carbon monoxide and nitrogen oxide in
automobile catalytic converters. This can avoid environmental pollution from burning
petrol and coal.
5. Medical applications
When nanoscale robots called ‘nanobots’ are released into the bloodstream in a
programmed manner, cancer can be detected in a very early stage.
Nanoparticles can be used for antibacterial treatments.
Naoparticles are used in bone tissue engineering and for detection of proteins.
Nanoparticles can be used for tumour destruction via heating.
Nanoparticles can be used to deliver drug to specific type of cells such as cancer
cells. These partiles can be engineered so that they are attracted to diseased cells
which reduce damage to healthy cells in the body.
6. Nanomaterials can be used for making sunscreen lotion, self cleaning glass, stain resistant
clothing, scratch resistant coatings on cars, eye glass lenses etc.
7. Carbon nanotube based alloys are being examined as a replacement for automobile
frames due to their high strength and reduced weight.
8. Nano-powders and coatings will increase durability of paint coating.
9. Cutting tools made of nanocrystalline materials are much stronger, harder, wear resistant
and erosion resistant.
10. Sensors made of nanocrystalline materials are highly sensitive to changes in environment.
They have applications as smoke detectors, ice detectors in air craft wings, automobile
engine performance sensor etc.
11. Nanotechnology holds a strong promise for use in defence field.
It helps to develop smaller, lighter and more effective weapons. Also helps to produce
new materials for military purpose.

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