Unit 6- Introduction to Nanoscience

Contents:
 Introduction of Nanotechnology and Nanoparticles
 Properties of Nanoparticles
 Applications of Nanotechnology
Introduction to “ NANO” world

Nano-Derived from Greek word “nanos”

–Extremely small.
Nanoparticles:
At least one dimension in nanometer in size.

Nanotechnology :The science of designing, production of

nanosized particles for device fabrication in applications.

A nanometer is one billionth of a meter

At the nanoscale, the physical, chemical, and biological
properties of materials differ in fundamental and
valuable ways from the properties of individual atoms
and molecules or bulk matter.
“There‟s Plenty of Room at the Bottom”

Richard Feynman’s famous presentation “There’s

Plenty of Room at the Bottom” was in the 1959 at
the American Physical Society.
What has happened when reduced to the nanoscale?
 Small size effect (Quantum size effect/Quantum
Confinement)
 Quantum Mechanics
 Large surface to volume ratio
 Contain very small number of atoms(molecules)
 Discrete energy levels
 Quantum Size Confinement Effect
 When the dimension of the material is reduced to only a few tens of nanometer,
energy levels of electrons can no longer remain continuous. But these energy levels
now become discrete.
 There exist a small and finite separation between energy levels.
 This situation of discrete energy levels is known as quantum size confinement.
 In nanometer range specific behavior of individual atom dominates.
 The behavior of individual atoms is very different from the bulk material.
 Nanosystems that include quantum well, quantum dot, quantum wire etc.
When the systems are quantum defined only in one dimension to nanoscale, while the
other two dimensions remain large (as in thin films, layers) then the system is quantum
well (2D). Here electrons are free to move in two dimensions and restricted along third
direction.
If two dimensions are quantum confined to nanoscale and third dimension remains large
then the resulting system is quantum wire (1D).
When all three dimensions are quantum confined into nanoscale regime, then the resulting
system is quantum dot (0D)
Discrete Energy Levels
Surface to Volume Ratio in Nanoparticles
Surface area to volume ratio in nanoparticles have a significant effect on the
nanoparticles properties.
Surface to volume ratio is large in case of nanoparticles
Firstly, nanoparticles have a relative larger surface area when compared to the same
volume of the material.
For example, let us consider a sphere of radius r:

The surface area of the sphere = 4πr2

The volume of the sphere = 4/3(πr3)
Therefore, the surface area to the volume ratio will be 4πr2/{4/3(πr3)} = 3/r
It means that the surface area to volume ratio increases with the decrease in
radius of the sphere and vice versa. It can also be concluded here that when given
volume is divided into smaller piece, the surface area increases. Therefore, as
particle size decreases, a greater portion of the atoms are found at the surface
compared to those inside.
Therefore, nanoparticles have a much greater surface area per unit volume
compared with the larger particles. It leads to nanoparticles more chemically
reactive.
Exploring the World through Microscopes
Properties of Nanoparticles
Contents:
 Optical properties
 Electrical properties
 Mechanical Properties
 Magnetic Properties
Optical Properties
Metallic Nanoparticles
Semiconductor Nanoparticles
Why change in colour
Size Dependent Properties (color changes with different sizes)
Why change in colour: Metallic NP
Metallic Nanoparticles: Mie Theory- 1908
 In case of metals as the size of particles decreases we start observing

oscillations of electron gas on the surface of nanoparticles.

 These oscillations are called Surface Plasmons (SP) which is the

origin of the color of metal nanomaterials

 If nanoparticles are exposed to electromagnetic wave (light) having a

wavelength comparable to or greater than the size of nanoparticles
and light has a frequency close to that of surface plasmon then
surface plasmon would absorb energy.

 Thus nanoparticles exhibits different colours as their size changes

and frequency of surface plasmon changes with it.
 At nanoscale, as size of the nanoparticles changes, there is change in the length
of medium and thus the values of μ and x changes.

 This changes the color of nanoparticles at different nanoscale region.

 Mie theory successfully explained absorption of light of visible wavelength for

nano-particles, but for particle size less than ~10 nm, there is need to consider
dielectric constant which depends also on particle size.
Semiconductor Nanoparticles: Size dependent properties.
 Critical size: Below this size, properties are defined-Quantum
confinement Effect.

 In semiconductor nanoparticles, as the particles become smaller

and smaller, the energy gap increases and absorption peak shifts
towards higher energy/frequency values.
- This leads to shift in the absorption spectrum and change in color
of particles.

 In bulk form, absorption spectrum is unique but in nanoparticle the

spectrum changes and it undergoes a blue shift means shift towards
smaller wavelength.
 The most striking property of nanoparticles made of semiconducting elements is the
pronounced changes in their optical properties compared to those of the bulk material. There
is significant shift in the optical absorption spectra toward the blue (shorter wavelength) as
the particle size is reduced. In a bulk semiconductor a bound electron-hole pair, called an
exciton, can be produced by a photon having energy greater than that of the band gap of the
material. The band gap is the energy separation between the top filled energy level of the
valence band and the nearest unfilled level in the conduction band above it. The photon
excites an electron from the filled band to the unfilled band above. The result is a hole in the
otherwise filled valence band, which corresponds to an electron with an effective positive
charge. Because of the Columb attraction between the positive hole and the negative
electron, a bound pair, called an exciton, is formed that can move through the lattice.
The separation between the hole and the electron is many lattice parameters. The
existence of the exciton has a strong influence on the electronic properties of the
semiconductor and its optical absorption. An exciton can move in the crystal whose center of
mass motion is quantized.
Different kinds of excitons are identified in a variety of materials.
When the electron-hole pair is tightly bound with distance between electron and hole
comparable to lattice constant then it is called Frenkel exciton.
At the other extreme, one may have an exciton with electron-hole separation much
larger compared to lattice constant. Such a weakly bound electron-hole pair is called Mott-
Wannier exciton.
For example,CdS bulk semiconductor with energy gap of 2.42 eV is orange in
color. As the particles become smaller and energy gap increases it becomes
yellowish and ultimately white.
Electrical Properties
 Electrical properties are characterized by the mean free path of

electron (path of the electron collision due to atoms or ions).

 The mean free path changes at nanoscale due to collision and

tunneling within the conductor.

I-V Characteristics of bulk conductor

 The resistivity (or conductivity) in bulk conductor can be measured

in principle by connecting electrically conducting wires to bulk

conductor, applying a voltage difference across it and measuring the
current flowing through it. Current flowing through it is given by
Ohm’s law and shows linear variation.

Fig: I-V graph of bulk conductor

Fig: I-V graph of nanosized conductor
Electrical resistivity:
 The materials of nano-sized grains have larger number of grain
boundaries than corresponding polycrystalline materials.
 Electrical resistivity of materials having nano-sized grain is larger
than the polycrystalline materials due to scattering of electrons at
grain boundaries.

 nano zinc oxide have superior UV blocking properties and so used

in cosmetics.
Mechanical Properties
 Mechanical properties like hardness, elasticity, ductility depend

upon bonds between atoms. Imperfections in crystal structure &

impurities results in changes in these properties.

 As nanoparticles are highly pure & free from imperfections, they

show different mechanical properties than the bulk material.

 The measurements of elasticity, hardness, ductility show different

behavior as compared to the bulk material.
For example, in the case of metallic nanocrystalline materials,
elastic modulii reduce dramatically.

 Magnesium bulk material has Young’s modulus Y = 4100 N/mm2

and when magnesium is in nanoscale, it has Young’s modulus Y =
3900 N/mm2
 Plastic deformation in nanocrystalline materials strongly differ from that of
polycrystalline bulk material i.e. if stress is removed the recovery to original
shape/size is recovered more effectively.

 Hardness of materials is also related to the grain size. In the nanometer size
range, the hardness increases with decrease of particle size.

Magnetic properties
Material shows magnetic properties due to orbital and spin motions of electrons.
Electron has spin and orbital magnetic moment.
- The vector sum of all the moments of electrons gives the total moment of the
atom.
Iron, cobalt and manganese, have a net magnetic moment.
- Crystals of these atoms become ferromagnetic in which magnetic moments
aligned in the same direction.

Fig: Variation of Hardness with particle size (Copper material)

Hysteresis B-H curve for bulk and nanoparticles

In bulk ferromagnetic materials, the magnetic moment is less than the moment in
the bulk material. Presence of 'domains' in one direction but moments of different
domains are in different directions.
- When bulk ferromagnetic materials are subjected to alternating magnetic fields,
they show hysteresis for which the B-H curve.
- In nano sized ferromagnetic particles, essentially consisting of a single domain
there is no hysteresis and the B-H curve, as shown in Fig.20(b).
- This variation in the magnetisation is due to change in cohesive forces between
the atoms when material is in the nano particle form.
Dependence of magnetic moment on the dimension
- There is an increase in magnetic moment per atom as we decrease the
dimensionality of the system. In small systems, a large fraction of atoms is at surface.
Surface atoms have lower coordination number than bulk atoms.
- As coordination number increases the magnetic moment decreases. Small clusters
have lower coordination number hence magnetic moment of a very small cluster is
more than bulk material.
- This is indicative of fundamental differences in magnetic behaviour between nano
structures and bulk materials.
- This effect is important as surface spins are usually not ordered along the same
directions as the spins in the interior of the material, thus we expect nano crystals with
more surface to have less per atom than bulk materials purely based on surface
effect.
Methods of Preparation of Nanoparticles
Physical Methods
1. High Energy ball Milling
2. Physical vapour deposition (PVD)
3. Chemical vapour deposition (CVD)

Chemical Methods
1. Solution phase method
High Energy Ball Milling
High Energy Ball Milling
Advantages:
1. Nanopowders of 2 to 20 nm in size can be produced. The size of
nanopowder also depends upon the speed of the rotation of the balls.
2. It is an inexpensive and easy process.

Disadvantages:
1. As the process is not so sophisticated, therefore the shape of the
nanomaterial is irregular.
2. There may be contaminants inserted from ball and milling additives. .
Chemical Vapor Deposition (CVD):
Chemical vapor deposition, a hybrid method using chemicals in vapour phase is
conventionally used to obtain coatings of a variety of inorganic or organic materials.
Basic CVD process can be considered as a transport of reactant vapour or reactant
gas towards the substrate kept at some high temperature where reactant cracks
into different products which diffuse on the surface , undergo some chemical
reaction at appropriate site nucleate and grow to form desired material film. The
byproducts created on the substrate have to be transported back to the gaseous
phase removing them from substrate.
Vapors of desired material may be often pumped into reaction chamber using
some carrier gas.
There are various processes such as reduction of gas, chemical reaction between
different source gases or oxidation by which CVD can proceed.
It is preferable that reaction occurs at the substrate rather than in gas phase.
Usually ~ 300 to 1200 0C temperature is used at substrate .
There are two ways „hot wall‟ and „cold wall‟ by which substrates are heated.
In hot wall set up, deposition can take place even on reactor walls. This is
avoided in cold wall design. Besides this, the reaction can take place in gas
phase with hot wall region which is suppressed in cold wall set up. When two
types of atoms or molecules say P & Q are involved in the desired film, there are
two ways in which growth can take place. In Langmuir- Hinshelwood mechanism
both P & Q type of atoms/molecules are absorbed on the substrate surface and
interact there to produce the product PQ. When one species is absorbed in
excess of the other, the growth depends on availability of adsorption sites for both
P & Q as shown in fig. The other approach in which reaction can occur is that one
species say P adsorbs on the substrate and the species Q from gas phase
interacts with P. Thus there is no sharing of sites. This type of mechanism is Elay-
Riedel mechanism
Applications of Nanoparticles
• Energy
• Automobile
• Medical
• Introduction of Qunatum Computing
• Introduction to Aerogels
High efficiency light weight solar cells is invention of nanotechnology
Energy
Satellites or spacecrafts are mainly powered by solar energy. Currently
solar cells have reached an efficiency of 30 - 40 %. Using luminescent dye
sensitized nanoparticle based or nanoparticle-based solar cell arrays have
potential to reduce the weight of solar cells as well as increase in
efficiency.
Nanoparticles are useful to increase density of rechargeable batteries,
which are used in laptops and mobiles.
Nanotechnology is being used to reduce the cost of catalysts used in fuel
cells.
These catalysts produce hydrogen ions from fuel such as methanol.
Nanotechnology is also being used to improve the efficiency of membranes
used in fuel cells to separate hydrogen ions from other gases, such as
oxygen.
Nanomaterials can be used in a variety of ways to reduce energy
consumption. Nanoparticle fuel additives can also be of great use in
reducing carbon emissions and increasing the efficiency of combustion
fuels.
Cerium oxide nanoparticles have been shown to be very good at catalyzing
the decomposition of unburnt hydrocarbons and other small particle
emissions due to their high surface area to volume ratio
 Medical
• Advancement in nanotechnology have helped to change medical norms in
disease prevention, diagnosis, and treatment.
• The traditional drug delivery system, the drug is distributed to the affected
tissues or organs of the patient‟s body as well as to the healthy tissues or
organs. This leads to the side effects.
• In the targeted drug delivery system, the drug is dissolved, entrapped,
encapsulated or attached to a nanoparticle. The system is then embedded in a
capsule which is guided towards the affected part of the body.
• The capsule is opening at the specific tissues or organs controlled by externally
applied magnetic field or infrared light or physiologically.
• Then drug can be delivered in controlled manner.
• Cancer therapy is one of the most common uses of nanotechnology for many
people. There have been many new advances in nanotechnology for screening
and treatment to remove colon and prostate cancer.
• The goal is to use tiny molecules (nanoparticles) to transport drugs within cancer
cells, allowing direct treatment of these cells, without compromising healthy cells
and tissues. However, this is just one of many ways nanotechnology can be
used to eliminate cancer.
II Automobiles
Nanotechnology has a wide range of applications in automobiles.
Nanomaterials in various forms are used for designing sturdy structural parts,
smooth and non-scratch paints, self-cleaning windows, better tires, reduction of
harmful emission, etc. A few of them are listed below:

1. Sturdy structural parts

Various body parts of vehicles are made up of steel, some alloys, rubbers,
plastics etc. Nanotube composites have mechanical strength better than steel.

2. Smooth and non-scratch Paints

Cars are spray painted with fine particles. Nanoparticle paints provide smooth,
non-scratch thin attractive coating.

3. Self cleaning glass for windows

Self cleaning glass can be made by dissolving small amount of titania (TiO2)
nanoparticles while manufacturing glass. Titania is able to dissociate organic dust in
presence of UV light available in the sunlight.
Drops of waters on glass give hazy look, but TiO2-containing glass can spread
water evenly giving clear sight.
4. Small motor parts
Small motors are needed in vehicle (such as wipers, window glass movements,
etc). Very powerful electric motors are made using shape memory alloys using
nanoparticles of materials like Ni–Ti. They require less power and gives better
performance.

5. Better tires
Tires of vehicles undergo wear and tear with use and also increase its weight.
By using nanoparticle clay, better, light weight, less rubber consuming thinner tires
are possible that can reduce the overall weight, increase in fuel consumption and
speed.

6. Controlling harmful emission

Use of efficient nanomaterial catalysts is one solution to convert harmful
emission into less harmful gases. Large surface area of nanoparticles is useful to
produce better catalysts. They are capable of absorbing emission of particles and
poisonous gases like CO and NO from vehicle exhausts.
7. Hydrogen fuel
Instead of using conventional petro fuels, there are numerous advantages of
using hydrogen as a fuel. When hydrogen fuel is burned it can only produce
harmless water vapor. Hydrogen gas is normally stored in a metal cylinder under
high pressure.
Nanocylinders of carbon nanotubes have potential to store hydrogen in very small
space.
Introduction of Qunatum Computing
• Classical computing relies on principles of Boolean algebra and logic gates.
• Data is processed in binary system that is, either 0 (off/false)or 1 (on /true)that
are called as bits. The transistors and capacitors in CPU can only be in one
state at any point either in 0 or 1.
• For more processing power, we need small dimensional transistors in large
density on chip of the processor.
• Thus, we need to reach very smaller dimension of materials in the range of
few nanometers. At this nano scale, a threshold is reached and quantum
mechanical effects such tunneling, uncertainty principle comes becomes
dominant. Hence, there is limit to the size of transistors at nanolevel and also
on its processing power
Principle of quantum computing
• Quantum computing applies the properties of quantum physics to process
information. A number of elemental particles such as electrons or photons can be
used for storing the information.
• Either the charge of particles or polarization acts as a representation of 0 and/or
1.
• Each of these particles is known as a quantum bit, or qubit.

• A qubit is a unit of quantum information.

• Quantum computer uses mainly two principles of quantum mechanics

superposition and entanglement
Superposition: A qubit can hold both values (0 and 1) at the same time which
known as a superposition state. Thus, at one time the number of
computations possible in a quantum computer is 2n, where n is the number
of qubits used.
For example, a quantum computer consisting of 500 qubits has a potential to
perform 2500 calculations in a single step
Entanglement:
Entanglement is correlation between particles acting as q-bits such as photons,
electrons. By knowing the spin state of one entangled particle (up or down) we can
know the spin of its correlated particle. Quantum entanglement allows qubits
separated by distances to interact with each other instantaneously. When multiple
qubits act coherently, they can process multiple operations simultaneously. Thus,
large information is processed within a fraction of the time
 Potential Applications of Quantum Computing
Currently, quantum computers are in the stage of development. Based on estimation, it is
predicted that quantum computers has tremendous potential to deal with many challenges that
are almost impossible to handle by the existing classical computers.
• Artificial intelligence: Artificial intelligence requires analysis of data from images, videos
and text. This data is available in vast quantity. For analyzing and processing this huge
data, traditional computers would require thousands years. Quantum computers would be
able to process this data in few seconds.
• Drug Design: For many of the drugs, it requires trial and error methods to understand how
they will react. These methods are very expensive, complex and require much processing
time. Using quantum computers the process can be simulated more effectively.
• Financial Optimization: Currently classical computers are analyzing many financial tasks
such as market analysis, estimated returns, risk assessment, financial transactions, etc. It
requires complex algorithms and tremendous computational time. By utilizing quantum
technology great improvements could be achieved in terms of time saving and more
accuracy.
• Development of new materials
• Cyber Security
• Dealing with encryption
• Software testing, Fault Simulation
Aerogels:
Introduction of Aerogels:
Aerogels are highly porous materials having ultra-low density.
These monolithic materials are formed by interconnection of particles of
nanometer size, to form a nanoporous solid. The pores themselves are usually
nonuniform with sizes from 10 to 100 nm.
Aerogels are synthesized by sol-gel method and dried by special procedures to
retain their porous structure.
Aerogels were first synthesized by an American scientist Samual Kistler in 1930s.
Aerogels can be made of a wide variety of substances, including: Silica, transition
metal oxides (for example, iron oxide), lanthanide and actinide metal oxides,
several metal oxides (for example, tin oxide), Semiconductor nanostructures
(such as cadmium selenide quantum dots, titanium dioxide), Carbon, Carbon
nanotubes ,Metals (such as
copper and gold).

Fig: Aerogel is transparent, highly insulating material

• Properties of Aerogels:
• One of the best known and most useful physical properties of aerogel is its incredible
lightness-it typically has a density between 0.0011 to 0.5 g cm-3, with a typical average of
around 0.020 g cm-3.
• It is possible to have very high porosity (80–90 %), very low density and high surface area
(500–1,500 m2 /g) for these aerogels.
• They have very low index of refraction (1–1.05) and very low speed of sound through
them (20 m/s).
• Young’s modulus in these materials is quite low (106–107 N/m2).
• Very low value of thermal conductivity (0.003 W/m.K) which is lower than most
commonly used insulators make them best available thermal insulator.
• It can be Transparent or opaque or can be coloured.
Applications of Aerogels:
It was assumed in last decades that use of aerogel is difficult commercially because of number of reasons like risky
supercritical drying process, expensive synthesis procedure and their low fracture toughness etc.
It is progressive development of cost effective synthesis routes and technological development sand demands,
interest in aerogels is increasing. Applications of aerogels are based on their properties.
They are nontoxic and biodegradable making them eco-friendly.
Their unique properties such as very low thermal conductivity makes them best thermal insulators for various
applications such as insulation of space vehicles, automobile engines etc.
Aerogels have been commercially used in jackets and blankets to be used under extreme low temperature
conditions.
Large windows of aerogels are being used in houses and buildings in some places to control the temperature in the
interior.
The transparency and heat insulation properties are used.
Indeed it is possible to make aerogel-textile composites so as to make blankets, coats etc. by making them rollable.
They can be obtained in the form of thin films, molds and tiny balls.