Fundamentals of Nano

Science
Jesco projects
Text book
• A.S. Edelstein and R.C. Cammearata, eds., “Nanomaterials: Synthesis,
Properties and Applications”, Institute of Physics Publishing, Bristol and
Philadelphia, 1996.
• N John Dinardo, “Nanoscale charecterisation of surfaces & Interfaces”, 2nd
edition, Weinheim Cambridge, Wiley-VCH, 2000
• REFERENCES:
• G Timp (Editor), “Nanotechnology”, AIP press/Springer, 1999.
• Akhlesh Lakhtakia (Editor),“The Hand Book of Nano Technology,Nanometer
Structure, Theory, Modeling and Simulations”. Prentice-Hall of India (P) Ltd,
New Delhi, 2007.
• ASIM .K.DAS.Mahua Das-CBS Publishers
• Ramprasad and S.Venkatanarayanan.Gurukarthik Babu-AR publishers
Unit-1-Introduction
• Nanoscience or Nanoscale science is the study on fundamental
relationships between physical properties and phenomenon and
material dimensions in the nano meter scale is referred to as nano
science. roughly 1-100 nanometers.
• Nano technolgy is defined as the design, characterization, production
and application of structures, devices and systems by controlling shape
and size at nanometer scale.
 So what is a nanometer?
• a nanometer is one billionth of a meter that is 10-9m.
To understand the nano scale let us have a comparison between macro,
micro and nanoscale.
• So let us see one example macro, so the average person of height is
like 180cm which is equal to 2 billion nanometer, and apple which is
size of 8cm it is equal to 80 million nanometer.
• An ant the size is 5cm, and it is equal to 5 million nanometer.
• So let us see the micro scale, here the approximate size of human hair
is 80,000 nanometer and the smallest, the eye can see is only 10,000
nanometer.
• And the normal e-coli bacteria, so the size of e-coli bacteria is in the
range of 2 micrometer that is equal to 2000 nanometer.
• we can see the population of India is 1 billion, so 1 billion is equal to
100 crores that is 10-9. So each Indian you or me is nano in
comparison to the total population of India.
• So when you compare yourself with the total population of India like
100 crores you are nano.
• So let us see another example, another simple example if someone
ask you what is nano, you can tell them it is equal to 1rupee in 100
crore rupees
• So here the 1 rupee is nano, so this 1 rupee in 100 crores is a scale
difference you can understand how small the nano is and materials
with small dimension show new physical phenomena
 Actual physical dimensions relevant to
Nanosystem

Nanoscience

0.1nm 1nm 10nm 100nm 1m 10 m

Size and shape dependent

properties

Nanometer scale : The length scale where corresponding

property is size & shape dependent.
 Length Scale
• Bohr radius = 0.5292Å ≈ 0.05 nm
• C atom (VdW radius)=0.17 nm
• In a 1nm line: 3C atoms
• In a 1nm x 1nm surface: 9C atoms
• In a 1nm x 1nm x 1nm cube: 27 C
atoms
• In a 100 nm x 100 nm x 100 nm cube:
2.7 x 107 C atoms

• In a 1m x 1m x 1m cube: 2.7 x 1028 C atoms

Typical nanosystems may contain from hundreds to tens of
thousands of atoms.
 Nanosystems: % of Surface atoms
Example of Gold Nano particle:

 Sphere of radius 12.5 nm contains total approx. 480,000 atoms.

surface contains approx. 48,000 atoms.
So, approx. 10% atoms are on the surface.

 Sphere of radius 5 nm contains total approx. 32,000 atoms.

surface contains approx. 8000 atoms.
So, approx. 25% atoms are on the surface.

Surface atoms have unused electrons – so very reactive

(can be used for catalysis)
 Surface to Volume Ratio Increases
As surface to volume ratio increases

• A greater amount of a substance

comes in contact with surrounding
material.

• This results in better catalysts, since

a greater proportion of the material is
exposed for potential reaction.
Nanoparticles exhibit unique properties because of
• Increased relative surface area
• Surface area considerably increases compared to the volume of the
material, so more actions can be carried on the surface.
• Quantum confinement
• When materials are narrowed down to nanoscale dimensions, the
electrons are squeezed into a space smaller than they actually were.
So nanomaterials display the effect of quantization of energy.
Quantum confinement

• Properties of materials are strongly influenced by their size of their particles.(eg-carbon

is a non-metal,but when considered in nano scale single layer graphene is a good
conductor.)
• The phenomenon that can be used to explain the size dependent characteristic of
materials is Quantum confinement.
• QC effects are generally observed when size of particles is smaller comparable to
Debrogellie wavelength of an electron
• Silicon ,cadmium selenide /cadmium sulfide
• The effect which describes the phenomenon resulting due to the squeezing of particles
which may be electrons /holes into a dimensions that approaches a classical limit.so that
various Quantum effects are manifested. So in this regime the energy of particle is no
longer continuous but it is discrete. QC effects are observed in low dimensions 2,1or 0
dimensions.
• When the particles is confined in one dimensions then particle motion is confined /or
free to move in x-y directions.
Characteristics of Nanoscale materials
• Fiber that is stronger than spider web
• Metal 100 times stronger than steel and 1/6 of its weight
• Catalysts that respond more quickly and to more agents
• Plastics that conduct electricity
• Materials that change color and transparency on demand
• Materials that are self repairing, self cleaning and never need
repairing
Implications for Physics
• Nano scale materials mass is extremely small and gravitational force
becomes negligible .Electro magnetic forces are dominant in
determining the behavior of atoms and molecules.
• Wave particle is duality of matter: for objects of very small mass, such
as electron they exhibit wave like nature.
• Quantum confinement: In a Nano material such as metal ,electron are
confined in space rather than free to move in the bulk material.
• 2D –lead to quantum wire
• 3D –to quantum dot
• Quantum Dot
• 0 Degree Of Freedom
• 3 dimensional confinement

• Quantum Wire
• 1 Degree Of Freedom
• 2 dimensional confinement

• Quantum Well
• 2 Degrees of Freedom
• 1 Dimensional Confinement
Bulk Well Wire Dot

Bulk Well Wire Dot

Quantum dots
• Quantum dots are tiny semiconductor crystals.
• They might conduct electricity or resist depending on the purity of semiconductor and
temperature.
• Quantum dots range in size from to 2-10 nm
• Because of their smaller size thwy are governed by quantum mechanics
• Their size ,energy levels and emission color quantum dots are precisely controlled and
used for various applications
• Unique properties of quantum dots is their emission colour
• It doesn’t depends on the material.
• Bigger the quantum dots longer the wave length and smaller frequency it will emit.
• Bigger dots emits red and smaller one blue and all colours are in btw them
• Smaller dots require large energy level because their bandgap is more and energy level
to enter the electrons in the excited state.
Physical implications
• Photovoltic solar cells,fuel cells and portable power to provide
inexpensive clean energy.
• Nano particles reinforced polymers or Nano composites: requirement
of increased fuel economy in vechicles,demand the use of new light
weight materials(plastic can replace metals)
• Weight reduction in turn reduce the fuel and co2 emissions
• Nano composites find use in non-automotive applications such as
pipes and fittings for the buildings and construction industry,
referigerator liners, business ,medical and consumer equipment
housings,
Physical implications
• Lithium ion batteries –replaced by nano technology power
sources(cell phone,fuel cell, cost and having high power densities)
Implication for chemistry
• Nano material is forms of at least a cluster of atoms or cluster of
molecules
• Intra-Molecular bonding(Chemical interactions)-changes in the
chemical structure of the molecules.(ionic covalent and metallic
bonds)
• Inter-molecules bonding (physical interactions):does not involve
change in chemical structure of the molecules. They include ion-ion
and ion-dipole interactions. Ex-Vander waals interactions,hydrogen
bonds,hydrophobic interactions,repulsive forces.
• Nano materials often arise from a number of molecules held together
or large molecules that specific three dimensional structures through
intermolecular bonding. In Nano structure where materials can have
large surface areas and consequently small forces can be applied to
very large areas.
• Nano particles exhibit greater vapor pressures ,chemical potentials
and solubility relative to bulk materials.
• Molecular caps are used to restrict particle growth and aggregations
which in turn used to terminate and stabilize the nanostructure's.
• Ionization potential increases as the transition metal atom cluster
drops to nano scale applied to heterogeneous catalysts.
• In oil industries self assembled monolayers on mesoporous supports
with pore sizes in the range of nanometers is widely used for the
removal of ultra fine contamination.
• Nano fluidics –study of behavior ,manipulation and control of fluids
that are confined to the structures of nanometer characteristics.
• The above will proceed to integrate a complete laboratory into a
silicon waver or a plastic chip.
• Commercial applications-enzymatic analysis and DNA sequencing
• Supramolecular chemistry: construction of nanostructures molecules-
by-molecules introduces the distinct advantage that organization and
functionality can be manipulated by chemical design( )
covalent bonds

• Catalysis: Nano –will lead to drastic reduction of the amount of

material used with resulting economic and environmental benefits.
• Used in chemical,petroleum,automotive ,pharmaceutical and food
industries.
• Sustainability: Nano tech will improve agricultural yields for an
increased population ,more economical water filtration and
desalination and enable renewable energy sources –solar energy
conversions.
• The nano tech based lighting advances have the potential to reduce
world wide consumption of energy by more than 10%.
• Reduce the need for scarce material resources and diminish pollution
for a cleaner environment.
Implications for biology
• Nano fabricated surfaces and devices are used for detecting genes
expression and genome sequencing.
• Characterize an individual genetic makeup have revolutionized
diagnostics an therapeutics.
• New formulations and routes for drug delivery ,implantable devices
,advanced drug delivery systems ,capable of sensoring drug level
• Medical diagnostics tools such as cancer tagging mechanism and lab
on a chip is used in real time
• Artificial inorganic and organic nanoscale materials are introduced
into cells for diagnostics.
• Nano engineered gels and other materials are used to replace lost
tissue or to provide structure for the regeneration of natural tissue.
Current applications include bone replacement and nano structures
that help in the regrowth of nerves.
• Detection: Detection reaction occurs at the material interface. The
detection of a specific chemical or biological compound within a
mixture represents the basis for the operation of numerous
devices,like chemicalsensors,biosensors and microarrays.
• The rate,specificity and accuracy of this reaction can be improved by
using nano materials than bulk materials in the detection area.
• Multiplex detection devices –can test and detect more than one
analyte at the time.
• The molecular building blocks of life proteins,nucleic acid,lipids
carbs,and their non biological mimics are example of materials that
possess unique properties determines by their sizes,folding and
patterns at the nano scale. Bio synthesis and bio processing offer
fundamentally new ways to manufacture chemicals and
pharmaceuticals products. Imitation of biological systems provides a
major area of research in several disciplines. BIO-MIMETIC chemistry
is based on this approach.
• Nano tech –contributes to agriculture in biodegradable chemicals for
nourshing plants and protecting against insects. Genetoc
improvement of animals and plants.
• Delivery of genes and drugs to animals and Nano-array based techs
for DNA testing-will allow scientist to know which genes are
expressed in a plant when it is exposed to drought stress.
Implications in Engineering
• Better fuel cells and photovoltaics as a better alternative energy sources
into new and bigger markets
• Simulation in nano –shows increase in computational power for developing
biocompatible implants and for studying drug delivery process.
• New way to store and transport energy –new architectures for the power
grid
• Nano engineered catalysts –better extract oil or turn oil into fuel for cars
• Wear resistant tyres-nanometer scale particles of inorganic clays and
polymers (replacing carbon black)
• Significant changes in lighting technologies are expected
semiconductors used in the preparation of LED for lighting can be
increasingly sculpted on nanoscale dimensions.(reduction in carbon
emission apart from saving energy)
• Chemotheraphy –replaced by nanoparticles that kill cancer cells with
minimal side effects for the patient.
• Mobile communications –nanoparticles
• Medical imaging –improvised
• Nerve cells grow back ,stents and artificial blood cells
• Transportation :lighter ,faster and safer vehicles ,cost effective
roads,bridges runways ,pipelines and rail systems.
• Industry based applications
• Aerospace:temp,space,-
• Automotive:Zirconia and alumins liners are used to retain heat in
cylinders and improve combustion
• Batteries:nano engineered plates can store more energy than
conventional plates
• Building materials:aerogels –used as excellent insulating materials
• Machine tools: carbide materials provide longer lasting materials for
drills and cutting machinery.
• Televisions and monitors:zinc,cadmium,and lead naomaterials are
used to produce smaller phosphors in crt displays for better
resolution.
• Regenerative medicine:tissues can easily bond with nanoporous bone
subsitutes and nerve healing is improved .But the fact is
nanomaterials integrate well into natural body structures may cause
body malfunctions or even new diseases.
• Nanomaterials are classified as
• Quantum dots
• Nanowires
• Ultra thin films
• Multi layered films
Properties of nano particles
• Color-gold is example
• Melting temp-gold nano melt fast than slab
• Optical absorption-absorption of solar radiation in nano is higher
.Zinc oxide particles is found to be superior UV blocking properties
compared to its bulk substitute,so it is used in sunscreen lotions
• Chemical reactivity: suspension of nano particles are possible since
the interaction of the particle surface with the solvent is strong
enough (or else it will float or sink)
• Electrical conductivity: conductivity of bulk gold disappears when the
particle is reduced to nano.
• Magnetism: Super paramagnetism is a form of magnetisimwhere
permeability several times greater than ferro magnetic materials.
• Mechanical strength:clay nano partcles when incorporated into
polymer increases reinforcement leading to stronger plastics.
Nano particle of gold is purple in colour.
Nanoparticles exhibit unique characteristics known as quantum
confinement. This is because electrons are squeezed into a space smaller
than they actually were. Because of this property nano gold exhibits different
colours at different sizes. And the smallest gold nanoparticle exhibits violet
colour
Define quantum dots
A quantum dot is a structure which is sufficiently small in all the directions
that electrons contained on it have no freedom to move in classical sense
and are forced to exhibit quantum characteristics, occupying discrete energy
states. Quantum dots are also referred as artificial atoms.
• Why nanoparticles behave differently from its bulk counterparts
Nanoparticles exhibit unique properties because of
• Increased relative surface area
• Surface area considerably increases compared to the volume of the
material, so more actions can be carried on the surface.
• Quantum confinement
• When materials are narrowed down to nanoscale dimensions, the
electrons are squeezed into a space smaller than they actually were.
So nanomaterials display the effect of quantization of energy.
What are nanomaterials? Explain the different nanostructures namely
quantum dots, nanowires, ultrathin films and multi layered films with their
applications.
• These are particles between 1 and 100 nanometer in size.
Quantum dots:
Quantum dots are extremely small semiconductor structures, usually ranging from
2-10 nanometers (10-50 atoms) in diameter.
A quantum dot is a structure that is sufficiently small in all directions that electrons
contained on it have no freedom to move in a classical sense and are forced to
exhibit quantum characteristics, occupying discrete energy states just as they would
in an atom. Indeed, quantum dots have sometimes been referred to as artificial
atoms.
The energy band gap increases with a decrease in size of the quantum dot.
QDs obey quantum mechanical principle of quantum confinement.
They exhibit energy band gap that determines required wavelength of
radiation absorption and emission spectra. Requisite absorption and resultant
emission wavelengths dependent on dot size.

The size, shape and number of electrons can be precisely controlled. In some
quantum dots even if one electron leaves the structure there is a significant
change leaves the structure there is a significant change in the properties
Synthesis
• Sol-Gel Method:
• Process in which solid particles are dispersed in a liquid (a sol )and
agglomerate together to form a continuous three dimensional network
extending throughout the liquid (the gel)
• Sol-Gel Method Involves
• Hydrolysis
• Condensation
• Gelation
• Ageing
• Drying
• Densification
• A stable dispersion of colloidal particles of precursors in a solvent is known as Sol
• The metal salts or metal alkoxides form metal hydroxide.

• M-OR+H20=M-OH+ROH
• (conversion of homogenous solution into a sol)
• Gel: Colloidal solution is kept for ageing and condensation process leads to Gel ,Gel is an interconnected
,rigid and porous inorganic network covered completely with liquid phase. This transformation is called sol-
gel.

• Drying of Gel: It involves removal of liquid phase from Gel network.

Different ways of drying gel:
If the gel medium is dried by removing the liquid solvent (under hyper critical conditions)without destroying the
gel network, "aerogel “ is produced.

If the solvent is dehydrated by under ambient conditions (removal of R-OH groups) xerogel are produced.
If the gel network is sintered at high temperature (800c) densification,decompositionof gel results in complete
collapse of gel net into powder.
The Sol particles are there in a liquid and to
make a Gel, by allowing them to interconnect.
when they interconnect they form kind of a 3 D
structure which still has some liquid inside.
By super critical extraction you can get the zero
Gel or on normal drying the liquid without
disturbing the three dimensional porous
structure and you get the aerogel.
You can heat the zero Gel into the dense solid or
you can make a film like from the Sol, you can
make a film which is called a zero Gel film and
you can make a dense film.
After heating this, you can just get powders .
if you dry the Sol, you will get the powders which
may be nanocrystalline. So, you get a
nanocrystalline powders, you can make
nanocrystalline films depends on your
application.
• Sol consists of, liquid with colloidal particles which are not dissolved, but
do not agglomerate or sediment, they have particles, which are not going
to come down and sediment. So, that is a Sol and the agglomeration is due
to Van der waals forces and in order to counter the Van der waals forces,
because you want to keep the particles separate there must be repulsive
forces. These repulsive forces are important in a Sol to keep it highly, you
know the particles to be highly separated and mono disperse this repulsive
force can be due to electrostatic repulsion.
• This electrostatic repulsion is caused due to the absorption of charged
species on the surface of the particles. So, when you have charges on the
surface of the particles there will be repulsion between the particles and
agglomeration will be prevented. This is very important for colloidal
systems, where you have particles and these particles have a surface
charge. These surface charges prevent the particle from agglomerating and
in turn keep the size of the particles small. That is what you want when you
want to synthesize nanomaterials, the other way or one method as I said is
using charge the other way is using some steric hindrance
Synthesis methods
• Electro spinning
• Template base synthesis
• Electro Spinning:
• Used for the growth of 1D nano structures.
• Electro spinning is based on the electric field force acting on the
polymer melt which can be regarded as the variant of the electro
spray process. The resulting electric field causes fibers to be pulled
from the droplets at the end of the syringe tip on to the grounded
collector plate.
Electro-spinning
 Uses an electrical charge to draw very fine (typically on the micro or nanoscale) fibres from a liquid.
• Sufficiently high voltage is applied to a liquid droplet and the body of the liquid becomes charged.
• Voltage applied to droplet which reduces the surface tension resulting in a thin fiber being drawn out.
• Voltage applied is inversely proportional to diameter of fibre
• When the electrostatic repelling force overcomes the surface tension force of the polymer solution, the
liquid spills out of the spinneret and forms an extremely fine continuous filament.
• These filaments are collected onto a rotating or stationary collector with an electrode where they accumulate
and bond together to form nanofiber fabric.
• Use in fabrication of nano rods, nanowires, and nanotubes of polymers, metals, semiconductors, and oxides.
• Some porous membrane with nano-size channels(pores) are used as templates to conduct the growing of
nanowires.
• Pore size ranging from 10 nm to 100 mm can be achieved.
 Template Base synthesis

• Use in fabrication of nanorods, nanowires, and nanotubes of

polymers, metals, semiconductors, and oxides.
• Some porous membrane with nano-size channels(pores) are used as
templates to conduct the growing of nanowires.
• Pore size ranging from 10 nm to 100 mm can be achieved.
Synthesis method
• Spin coating or spin casting, uses a liquid precursor, or sol-gel
precursor deposited onto a smooth, flat substrate which is
subsequently spun at a high velocity to centrifugally spread the
solution over the substrate. The speed at which the solution is spun
and the viscosity of the sol determine the ultimate thickness of the
deposited film. Repeated depositions can be carried out to increase the
thickness of films as desired. Thermal treatment is often carried out in
order to crystallize the amorphous spin coated film. Such crystalline
films can exhibit certain preferred orientations after crystallization on
single crystal substrates.
• Atomic layer deposition (ALD) uses gaseous precursor to deposit
conformal thin films one layer at a time. The process is split up into
two half reactions, run in sequence and repeated for each layer, in
order to ensure total layer saturation before beginning the next layer.
Therefore, one reactant is deposited first, and then the second
reactant is deposited, during which a chemical reaction occurs on the
substrate, forming the desired composition. As a result of the
stepwise, the process is slower than CVD, however it can be run at
low temperatures, unlike CVD.
 Applications:
• Thin film solar cells: Thin-film technologies are also being developed as a means of substantially reducing the
cost of solar cells. Thin film solar cells are cheaper to manufacture owing to their reduced material costs,
energy costs, handling costs and capital costs. This is especially represented in the use of printed electronics
(roll-to-roll) processes. Other thin-film technologies, that are still in an early stage of ongoing research or with
limited commercial availability, are often classified as emerging or third generation photovoltaic cells and
include, organic, dye-sensitized, and polymer solar cells, as well as quantum dot, copper zinc tin sulfide,
nano-crystal and perovskite solar cells.
• Thin-film batteries: Thin-film printing technology is being used to apply solid-
• state lithium polymers to a variety of substrates to create unique batteries for specialized applications. Thin-
film batteries can be deposited directly onto chips or chip packages in any shape or size. Flexible batteries can
be made by printing onto plastic, thin metal foil, or paper
• Further applications are:
• microelectronics - electrical conductors, electrical barriers, diffusion barriers . . .
• magnetic sensors - sense current (I), Magnetic flux density (B) or changes in them
• gas sensors, SAW devices
• tailored materials - layer very thin films to develop materials with new properties
• optics - anti-reflection coatings
• corrosion protection
• wear resistance
Multilayered materials
• Multilayered materials are hetero structures composed of many alternating layers
that are generally stacked in a periodic manner.

• The combined thickness of two adjacent layers is called the bilayer repeat length
or bilayer period. The principal characteristic of multilayers is a composition
modulation, that is, a periodic chemical variation.multilayers are often referred to
as compositionally modulated materials and the bilayer repeat length is often
called the composition modulation wavelength.
• Multilayers composed of single-crystal layers that possess the same crystal
structure and where the interfaces are in perfect atomic registry are called super
lattices.
• Electronic and magnetic properties of the nano structured materials
• Quantum dots
• What is MOMBE
• Top down approach with an example
• Give two examples for materials and their specific properties which change when synthesized as
nanomaterials
• Brief classification of nano materials
• Two main approached followed for nanometer synthesis
• Implications,adv and disadva of materials in nanoscience
• Effect of length scale on the properties of various materials.
• Explain any two methods of thin film deposition and their advantages.
• Distinguish btw nano wires and nano films.
• Why do nano particles exhibit a low melting point when compared to the respective bulk materials
• List any four day today live commercial applications of nanotech
• How does the mechanical property of material vary in nano regime.
• Write about the optical ,thermal properties of nano materials
• Explain the different ways of classifying nano materials with example.
• How does the optical property of material vary in nano regime?
• What are Nano wires
• Discuss the effect of nanotization on the properties of materials
• What are nanostructured materials ?classify nano structured
materials with suitable examples
• Write notes on sputtering and MOMBE
• Enumerate the different chemical methods of synthesis of nano
materials and state its advantaged and disadvantages
• What do you mean by self assembly of mechanical milling
• Discuss the interdisciplinary aspects of nano science
• Mocvd and atomic layer epitaxy
• What is nano clays