Nano Pre Class

Engineering Chemistry
Pre class notes- Atomic and Molecular Nano Chemistry
Learning Objectives
At the end of the lecture the students are able to
1. Recall the various atomic models, formation of molecular orbitals from atomic
orbitals.
2. Define nanochemistry.
3. Distinguish between molecules, nanoparticles and bulk materials.
4. Understand the importance of nanotechnology
5. Appreciate uniqueness of “nano scale”.
6. Classify the types of nanomaterials: Nano rods, Nano wires, Nano belts,
Nano tubes,fullerene, quantum dots etc.
7. Understand and appreciate size dependent properties of nano particles.
8. Learn various physical and chemical methods used for the synthesis of
nanomaterials.
9. Know the applications of nanotechnology in diverse fields.
Material prepared by: Chemistry faculty 1

INTRODUCTION
James C Maxwell “The mind of man has perplexed itself with many hard questions.
Is space infinite, and in what sense? Is the material world infinite in extent? Do
atoms exist or is matter infinitely divisible?
ATOM –TIMELINE
Matter is composed of indivisible building blocks. This idea was recorded as

early as the fifth century BCE by Leucippus and Democritus. Indian sage and
philosopher named Acharya Kanada also proposed indivisible matter -anu. The
Greeks called these particles atomos, meaning indivisible, and the modern word
“atom” is derived from this term.
The concept of the atom was revisited and elaborated upon by many
scientists and philosophers, including Galileo, Newton, Boyle, and Lavoisier. English
chemist and meteorologist John Dalton is credited with the first modern atomic
theory.
Dalton’s atomic theory
1. Everything is composed of atoms, which are the indivisible building
blocks of matter and cannot be destroyed.
2. All atoms of an element are identical.
3. The atoms of different elements vary in size and mass.

4. Compounds are produced through different whole-number combinations

of atoms.
5. A chemical reaction results in the rearrangement of atoms in the

reactant and product compounds.
J.J. Thomson's atom model: Plum Pudding model
Ernest Rutherford's model: Nuclear model

Niels Bohr's model: Planetary model
Erwin Schrödinger's model: Electron Cloud Model/Quantum Model

Quantum mechanical model of atom

1. The energy of electrons in atoms is quantised
2. The existence of quantized electronic energy levels is a direct result of the wave
like properties of electrons. The solutions of Schrodinger wave equation gives the
allowed energy levels (orbits).
3. According to Heisenberg uncertainty principle, the exact position and momentum
of an electron can not be determined with absolute accuracy. As a consequence,
quantum mechanics introduced the concept of orbital. Orbital is a three dimensional
space in which the probability of finding the electron is maximum.
4. The solution of SchrOdinger wave equation for the allowed energies of an atom
gives the wave function ψ, which represents an atomic orbital. The wave nature of
electron present in an orbital can be well defined by the wave function ψ.
5. The wave function ψ itself has no physical meaning. However, the probability of
finding the electron in a small volume dxdydz around a point (x,y,z) is proportional to
|ψ(x,y,z)|2 dxdydz is known as probability density and is always positive.
ORBITAL
An orbital is a three-dimensional region around the nucleus that indicates the
probable location of an electron.
Two ways of showing a simple atomic orbital are presented.
Probability of finding the electron is Surface within which the electron can be
proportional to the density of the cloud. found a certain percentage of the time,
conventionally 90%.

Shapes of s,p and d orbitals
QUANTUM NUMBERS
The electron in an atom can be characterised by a set of four quantum
numbers, namely principal quantum number (n), azimuthal quantum number (l),
magnetic quantum number (m), and spin quantum number (s). When Schrodinger
equation is solved for a wave function Ψ, the solution contains the first three
quantum numbers n, l and m. The fourth quantum number arises due to the spinning
of the electron about its own axis.

ORBITALS IN MOLECULES- MOLECULAR ORBITALS

We know that the atomic orbitals are represented by the wave function Ψ. Let
us consider two atomic orbitals represented by the wave function ψA and ψB with
comparable energy, combines to form two molecular orbitals. One is bonding
molecular orbital(ψbonding) and the other is antibonding molecular
orbital(ψantibonding). The wave functions for these two molecular orbitals can be
obtained by the linear combination of the atomic orbitals ψA and ψB as below.
Constructive interaction: The two 1s orbitals are in phase and have the same sign.
Destructive interaction The two 1s Orbitals are out phase

Linear Combination of atomic orbitals

Bonding in some di-atomic molecules


NANOTECHNOLOGY
The term nano originated from the Greek nanos which means ‘dwarf’. It is
one billionth of a meter (10-9 of a meter). So, whenever we think about
nanotechnology, very small objects come to the mind. Indeed, this technology deals
with materials having at least one spatial dimension in the size range of 1 to 100
nm.
HOW SMALL IS NANO??
Here are a few illustrative examples:
• There are 25,400,000 nanometers in an inch
• A sheet of newspaper is about 100,000 nanometers thick
• A human hair is approximately 80,000- 100,000 nanometers wide
• A single gold atom is about a third of a nanometer in diameter
• One nanometer is about as long as your fingernail grows in one second
Nanotechnology definition (NASA)

The creation of functional materials, devices and systems through control of matter
on the nanometer length scale (1–100 nm) and exploitation of novel phenomena and
properties (physical, chemical, biological) at that length scale.

A very succinct definition for nanotechnology is simply “engineering with atomic

precision”.
HISTORY
Carl Sagan - "Somewhere, something incredible is waiting to be known."

Physics Nobel Laureate Richard Feynman gave the first
lecture regarding the applications for nanoscale materials. His
talk, entitled “There’s Plenty of Room at the Bottom,” was
delivered on 29 December 1959 at the annual American
Physical Society meeting on the campus of Caltech.
Feynman pointed out that designing materials atom-by-

atom is a real possibility, as it would not violate any physical
laws. He also predicted such sci-fi accomplishments as writing
24 volumes of the Encyclopedia Britannica on the head of a pin.
Richard P. Feynman- “They walk around; they wiggle; and they do all kinds of
marvelous things – all on a very small scale.”
NANOTECHNOLOGY –AN INTERDISCIPLINARY SCIENCE

NANOTECHNOLOGY TIMELINE
4th Century
The Lycurgus Cup (Rome) is an example of dichroic glass; colloidal gold
and silver in the glass allow it to look opaque green when lit from outside but
translucent red when light shines through the inside.
1857
Michael Faraday discovered colloidal “ruby” gold, demonstrating that
nanostructured gold under certain lighting conditions produces different-
colored solutions.
1947
John Bardeen, William Shockley, and Walter Brattain at Bell Labs
discovered the semiconductor transistor which laid the foundation for
electronic devices and the Information Age.
1958
Jack Kilby of Texas Instruments originated the concept of, designed, and
built the first integrated circuit (Nobel Prize in 2000).
1959
Richard Feynman of the California Institute of Technology gave what is
considered to be the first lecture on technology and engineering at the
atomic scale, "There's Plenty of Room at the Bottom" at an American
Physical Society meeting at Caltech.
1974
Prof.Norio Taniguchi coined the term nanotechnology to describe
materials to within atomic-scale dimensional tolerances.

1981
Gerd Binnig and Heinrich Rohrer at IBM’s Zurich lab invented

the scanning tunneling microscope, allowing scientists to
"see" (create direct spatial images of) individual atoms for the
first time. Binnig and Rohrer won the Nobel Prize for this
discovery in 1986.
1985
Rice University researchers Harold Kroto, Sean O’Brien,

Robert Curl, and Richard Smalley discovered
the Buckminsterfullerene (C60), commonly known as the
buckyball, which is a molecule resembling a soccerball in
shape and composed entirely of carbon. (1996 Nobel Prize)
1991
Sumio Iijima of NEC is credited with discovering the carbon

nanotube (CNT), although there were early observations of
tubular carbon structures by others as well.
1999– till date Consumer products making use of nanotechnology began

appearing in the marketplace.
Lightweight golf balls, stiffer tennis rackets and baseball bats,

nano-silver antibacterial socks, wrinkle resistant clothing,
scratch-resistant glass coatings, improved displays for
televisions, cell phones, and digital cameras.

NANOTECHNOLOGY: GENERATIONS
Classification of Nanomaterials
Nanomaterials can be nanoscale in zero dimension (atomic clusters, filaments and

cluster assemblies), one dimension (eg. surface films), two dimensions (eg.
strands or fibres), or three dimensions (eg. particles). They can exist in single,
fused, aggregated or agglomerated forms with spherical, tubular, and irregular
shapes. Common types of nanomaterials include nanotubes, dendrimers, quantum
dots and fullerenes.

Examples of Nanomaterials
Nanomaterials (gold, carbon, metals, meta oxides and alloys) with variety of
morphologies (shapes) are depicted in the figure below.
Comparison of 0D Nanoarchitectures with Traditional Colloids

Nanoparticles/nanoclusters Colloids
Size: 1–100 nm (nanoclusters: 1–10 nm) Typically>10 nm
Homogeneous molecular composition Heterogeneous molecular composition
Reproducible synthesis (control over Nonreproducible, uncontrollable
size, shape, and composition) morphology/composition
Soluble in polar/nonpolar organic Typically only soluble in polar solvents
solvents (depending on stabilizing agent)

WHY AND HOW IS NANOPARTICLES DIFFERENT FROM OTHER

PARTICLES?
Nanoparticles are larger than individual
atoms and molecules but are smaller
than bulk solid. Hence they obey neither
absolute quantum chemistry nor laws of
classical physics and have properties
that differ markedly from those expected.
The reasons for their difference in
behaviour are (i) large fraction of surface
atoms; (ii) high surface energy; (iii) spatial confinement; (iv) reduced imperfections,
which do not exist in the corresponding bulk materials.
Some features exclusive to nano size
Electromagnetic forces: Due to the smallness of nanomaterials, their mass

is extremely small and gravitational forces become negligible. Instead
electromagnetic forces are dominant in determining the behaviour of atoms
and molecules.
Wave-corpuscle duality of matter: For objects of very small mass such as
nanoparticles the wave nature has a more pronounced effect.
Quantum tunneling: Tunnelling is the penetration of an electron into an
energy region that is classically forbidden.
Quantum confinement: In a nanomaterial electrons are confined in space
rather than free to move in the bulk of the material.
Quantisation of energy: Electrons can only exist at discrete energy levels.
Quantum dots are nanomaterials that display the effect of quantisation of
energy.
Random molecular motion: Molecules move randomly due to their kinetic
energy. At the macroscale this motion is very small compared to the sizes of
the objects and thus it is not influential on how the object moves. At
nanoscale, however, these motions can be of the same scale as the size of

the particles and thus have an important influence on how they behave. One
example of a random kinetic motion is the Brownian motion.
Increased surface-to-volume ratio: One of the distinguishing properties of
nanomaterials is that they have an increased surface area.
Size-dependent properties
At the nanometer scale, properties become size-dependent.
Some of the major size dependent properties are
(1) Thermal properties – melting temperature
(2) Optical properties – absorption and
scattering of light
(3) Chemical properties – reactivity, catalysis
(4) Mechanical properties – adhesion,
capillary forces
(5) Electrical properties – tunneling current
1. THERMAL PROPERTY (REDUCED MELTING POINT)
A solid melts when thermal energy (kT) is comparable with its lattice energy so that
the particles vibrate at higher amplitude from its mean position and eventually it
melts at higher temperature.
Bulk: At macroscopic dimensions, melting point is size independent. For example,

an ice cube and a glacier both melt at same temperature.
Nanoscale: Nanomaterials may have a significantly lower melting point or phase

transition temperature and appreciably reduced lattice constants (spacing
between atoms is reduced), due to a huge fraction of surface atoms in the total
amount of atoms. The difference in melting point can be as large as 1000°C(!!!!!).
Surface atoms require less energy to move because they are in contact with
fewer atoms of the substance. (Surface energy to volume energy ratio changes
dramatically)

Nanocystal size decreases  Surface energy increases  Melting point

decreases
Example: 3 nm CdSe nanocrystal melts at 700 K compared to bulk CdSe at 1678 K
Melting point as a function of size
2. OPTICAL PROPERTY (ABSORPTION & SCATTERING OF LIGHT)
The optical properties of nanomaterials depend on parameters such as feature size,

shape, surface characteristics, and other variables including doping and interaction
with the surrounding environment or other nanostructures.
Nanoscale gold illustrates the unique properties. Nanoscale gold particles are not
the yellow color with which we are familiar; nanoscale gold can appear red or purple.

Reason
At the nanoscale, the motion of the gold’s electrons is confined. The particles are so
small that electrons are not free to move about as in bulk gold. Because this
movement is restricted, the particles react differently with light when compared to
larger-scale gold particles.
Colour generation from nanoparticles and nanostructures
Reason for color Example for nanoparticle
Butterfly wings (photonic crystals within).

The cuticle on the scales of butterfly wings are
Interference: The color is based on the composed of nano-sized, transparent, chitin-
constructive interference of light wavelengths and-air layered structures that can absorb and
as they interact with the nano material. reflect certain light wavelengths.
Liquid crystals (e.g., soap).
liquid crystals change color as a result of
nanoscale shifts in the arrangement of their
molecules
Scattering: The colours arises from the fact
that different particle sizes scatter different
Colloids (milk)
wavelengths.
Surface plasmons (SP):
A SP is a natural oscillation of the electron gas
Metal colloids (nano-gold)
inside a metal nanosphere. SP frequency
depends on the dielectric function of the metal,
and the shape of the nanoparticle.
Quantumfluorescence: The quantum
confinement in nano-sized semiconductors
leads to discrete energy levels from which Semiconductor quantum dots (QDs)
energy can be emitted (fluorescence) after it
has been absorbed by the semiconductor.

Applications
Gold particles size and optical properties can be put to practical use. Nanoscale gold
particles selectively accumulate in tumors, where they can enable both precise
imaging and targeted laser destruction of the tumor by means that avoid harming
healthy cells.
Nano-Gold particles of vary in color based on particle size and concentration. Ruby
red or purple is the most potent as medicine.
3. CHEMICAL PROPERTY – (CATALYSIS)
A catalyst is a substance that increases a chemical reaction rate without being

consumed or chemically altered. Greater the surface area of the heterogeneous
catalyst, the more efficient will be the catalyst. Active site is the site where the
reaction takes place. The ‘active site’ increases when the size of the catalysts is
decreased: the smaller the catalyst
particles, the greater the ratio of
surface-to-volume. The spatial
organisation of the active sites in a
catalyst is also important.

• Bulk gold is a noble metal: it is stable, non-toxic, and resistant to oxidation

and chemical attack.
• Nanoscale gold particles can catalyse chemical reactions. Finely dispersed
gold nanoparticles on oxide supports are catalytically very active. In many
cases the catalytic activity and selectivity of dispersed gold nanoparticles
exceed those of the commonly used transition metal catalysts such as Pt,
Rh, and Pd. This is an exciting result because metals like Pt and Pd
(commonly used in catalysis such as automobile catalytic converters) are
toxic and are also very rare metals, hence more expensive than gold.
4. MECHANICAL PROPERTIES
• Mechanical properties of nanomaterials may reach the theoretical strength,
which are one or two orders of magnitude higher than that of single crystals in the
bulk form. The enhancement in mechanical strength is simply due to the reduced
probability of defects.
• Filling polymers with nanoparticles or nanorods and nanotubes, respectively,
leads to significant improvements in their mechanical properties. Such
improvements depend heavily on the type of the filler and the way in which the filling
is conducted.
• Some nanomaterials have inherent exceptional mechanical properties which
are connected to their structure. One such material is carbon nanotubes (CNT):
these are extremely small tubes having the same honey-comb structure of graphite,
but with different properties compared to graphite. They can be single-walled or
multi-walled. Carbon nanotubes are 100 times stronger than steel but six times
lighter!! The different structures, properties and potential applications of carbon
nanotubes are discussed bit later.

5. ELECTRICAL PROPERTIES
Substances can be
classified into insulators,
semiconductors and
conductors based on the
energy separation
between valence band
and conduction band. The
electrons present in the
conduction band leads to
conduction.
For nanomaterials, Quantum confinement causes the energy of the bandgap to
increase as illustrated in figure below. Also, at very small dimensions when the
energy levels are quantified, the band overlap present in metals disappears and is
actually transformed into a bandgap. This explains why some metals become
semiconductors as their size is decreased.
The increase of bandgap
energy due to quantum
confinement means that more
energy will be needed in order
to be absorbed by the
bandgap of the material.
Higher energy means shorter
wavelength (blue shift). The
same applies for the
wavelength of the fluorescent light emitted from the nano-sized material, which will
be higher, so the same blue shift will occur. This gives a method of tuning the optical
absorption and emission properties of a nano-sized semiconductor over a range of
wavelengths by controlling its crystallite size.

Some nanomaterials
exhibit electrical
properties that are
truly exceptional.
Their electrical
properties are related
to their unique
structure. Two of
these are fullerenes
and carbon
nanotubes. For
instance, carbon nanotubes can be conductors or semi-conductors depending on
their nanostructure. These materials are discussed later.
Nanoclusters
Nanoclusters constitute an intermediate state of matter between molecules and
solids. Nanocluster sizes range from sub-nanometer to about 10 nm in diameter and
are of technological interest in numerous areas of applied science (e.g. materials
science, catalysis, electronics). Often one differentiates between: (i) nanoclusters
consisting of up to a couple of hundred atoms, and (ii) larger aggregates containing
103 or more atoms which are more often called nanoparticles. The properties of
nanoparticles gradually approach those of bulk materials or extended surfaces, i.e.
are scalable with size. Nanoclusters, however, have properties and structures which
are very sensitive to their composition and size (i.e. “every atom counts”) which can
lead to new and interesting properties not realised in the corresponding bulk
material.

Applications
Nanoclusters have potential applications in microelectronics, magnetic storage,

optical data storage, spintronics devices, telecommunications, sensors, transducers,
biological markers, switches, electroluminescent displays, chemical reactors,
catalysts, etc.
Nanorods
Nanorods are nanostructures,
shaped like long sticks or dowels with
a diameter in the nanoscale but
having a length that is longer.
Standard aspect ratios (length
divided by width) are 1-20. Each of
their dimensions range from 1–100
nm. If length to width ratio exceeds
20, they are called nanowires.
The optical properties of metallic nanorod depend on shape This is due to the
absorption of visible light both along the length of the nanorod and along the width of
the nanorod.
Applications
Gold nanorods are useful materials for sensing, photo thermal therapy, and imaging.
It is also used for the treatment of cancer.

Carbon Nanotubes
What are carbon nanotubes?
◼ CNT can be described as a sheet of graphite (grapheme) rolled into a cylinder
◼ Constructed from hexagonal rings of carbon
◼ Can have one layer or multiple layers
◼ Can have caps at the ends making them look like pills
History
Carbon nanotubes were discovered in 1991 by the Japanese electron microscopist
Sumio Iijima who was studying the material deposited on the cathode during the
arc-evaporation synthesis of fullerenes. He found that the central core of the
cathodic deposit contained a variety of closed graphitic structures including
nanoparticles and nanotubes, of a type which had never previously been observed.
Types of CNT
◼ Single Wall CNT (SWCNT)
SWNT is formed by wrapping a one-atom-thick
layer of graphene into a seamless cylinder.
Most single-walled nanotubes (SWNT) have a
diameter of close to 1 nanometer, with a tube
length can be many thousands of times longer.
◼ Multiple Wall CNT (MWCNT)

Multi-walled carbon nanotubes can be seen as
several concentric cylinders and the interlayer

space is about 0.34 nm. The diameter of MWNTs is generally within 10 to 20 nm.
There are three unique geometries of carbon nanotubes. The three types are
armchair, zig-zag and chiral. These types can be classified by how the carbon
sheet is wrapped into a tube (see pictures below).
PROPERTIES OF CNT
The physical properties carbon nanotubes based on the length and diameter
of the nano tube as well as the twist (also known as the chirality).
Due to their hollow cylindrical structure, carbon nano tubes are significantly
lighter than conventional engineering materials.
Tensile strength – 10-50 times higher than steel and Young's modulus of the
some nanotubes can be five times higher than steel.
Because of tremendously high surface area (~1000 m2/g) CNT have good
electrical conductivity. It can be conducting or semi conducting according to
its structure.
Due to the tubular structures of carbon nano tubes, they have extreme high
thermal conductivity in axial directions, leaving high anisotropy in the heat
transport in the materials.

APPLICATIONS OF CNT
Structural Support
Hydrogen storage
devices
Supercapacitors
Display devices
Water and oil purifiers
Catalysts
Medicine
Biosensors
Fuel cells
Nanowire and nanobelts
Nanowires exhibit aspect ratios

(length-to-width ratio) of 1000 or more.
They are often referred to as 1-
Dimensional materials. Nanobelts are
a class of nanostructure often viewed
as a type of nanowire. Nanobelts form
ribbon-like structures with widths of 30-
300 nm, thicknesses of 10-30 nm, and
lengths in the millimeter range.
Figure (a) Nanowire (b) Nanobelt

Fullerene
”The most symmetrical large molecule”
◼ Discovered in 1985
◼ Nobel prize Chemistry 1996, Curl, Kroto, and Smalley
◼ C60, also 70, 76 and 84.
◼ 32 facets (12 pentagons and 20 hexagons)
SYNTHESES OF NANOPARTICLES
Nanotechnologists have offered two approaches for synthesis

and fabricating materials or manipulating devices using
nanotechnology: top down and bottom up.
Top down approach involves the breaking down of the bulk

material into nano sized structures or particles. These techniques
are an extension of those that have been used for producing
micron- sized particles. By nature, this methos is not cheap and
quick to manufacture. Slow and not suitable for large scale
production.
An example of such a technique is high-energy wet ball milling.

Basic top-down approaches in nanofabrication
– Pattern transfer (lithography)

– Deposition (or film growth)
– Etching ( or removal of material)

Bottom up approach refers to the build up of a material from the bottom: atom-by-
atom, molecule-by-molecule, or cluster-by-cluster. This has the potential of
creating less waste and hence the more economical, is the ‘bottom- up’.
Basic bottom-up approaches in nanofabrication
– Chemical vapor growth: vapor-solid-liquid growth
– Self assembly: colloidal chemistry
Characteristics of Nano particles that should posses by any fabrication

technique:
Getting merely a small size is not the only requirement. It should have
i. Identical size of all particles (also called mono sized or with uniform size
distribution.
ii. Identical shape or morphology.
iii. Identical chemical composition and crystal structure that are desired among
different particles and within individual particles, such as core and
composition must be the same.
iv. Individually dispersed or mono dispersed i.e., no agglomeration.
SYNTHESIS OF NANOSTRUCTURED MATERIALS (NSM)

1. LASER ABLATION (PHYSICAL
METHOD)
• Synthesis of nanomaterials like CNT could
be carried out in a horizontal flow tube under a
flow of inert gas at controlled pressure.
• In this set-up the flow tube is heated to
~1200°C by a tube furnace. Laser pulses enter

the tube and strike a target consisting of a mixture of graphite and a metal catalyst
such as Co or Ni.
• SWNTs condense from the laser vaporization plume and are deposited on a
collector outside the furnace zone.
2. THERMOLYSIS (CHEMICAL METHOD)
• Nanoparticles can be made by
decomposing solids at high temperature
having metal cations, molecular anions or
metal organic compounds. The process is
called thermolysis. For example, small
lithium particles can be made by
decomposing lithium azide, LiN3. The
material is placed in evacuated quartz tube,
and heated upto 400ᵒC as shown in the
figure. At 370ᵒC decomposes releasing nitrogen gas, which is observed by the
increase in pressure in the vacuum gauge. In few minutes the pressure drops back
to the original low value, indicating that all nitrogen has been removed. The
remaining lithium atoms coalesce to form small colloidal metal particles. Particles of
less than 5 nm can be obtained using this method.
Similarly, metal complexes can be decomposed to obtain nano particles.

3. HYDROTHERMAL SYNTHESES (CHEMICAL METHOD)
• Hydrothermal synthesis is a method to produce different chemical

compounds and materials using closed-system physical and chemical processes
flowing in aqueous solutions at temperatures above 100°C and pressures above 1
atm.
•
The method is based on the ability of water to dissolve substances which are
practically insoluble under normal conditions under high temperature (500°C) and
pressure (10-80 MPa) (eg: some oxides, silicates, sulphides). The synthesis is
carried out in autoclaves which are sealed steel cylinders that can withstand high
temperatures and pressure for a long time.
The main factors that influence hydrothermal synthesis are the initial pH of the
medium, the duration and temperature of synthesis, and the pressure in the system.
Nanopowders are normally produced by means of either high temperature hydrolysis
reactions of various compounds directly in the autoclave.
Advantages: Ability to synthesize crystals of substances which are unstable near
the melting point, and the ability to synthesise large crystals of high quality.
Disadvantages: High cost of equipment and the inability to monitor crystals in the
process of their growth.
Solvothermal synthesis has been used in laboratory to make nanostructured titanium
dioxide, graphene, carbon and other materials.

4. ELECTRODEPOSITION (CHEMICAL METHOD)
Electrodeposition is a method
to deposit metal layers on a
conducting substrate. Ions in
solution are deposited onto the
negatively charged cathode,
carrying charge at a rate that
is measured as a current in
the measured as a current in
the external circuit. The
process is relatively cheap and
fast and allows complex
shapes.
The layer thickness simply depends on the current density and the time for which the
current flows. The deposit can be detached if the substrate is chosen to be soluble
by dissolving it away.
Electrodeposition is relatively cheap and can be performed at low temperatures. The

film thickness can be controlled by monitoring the amount of charge delivered.
Electrodeposition is now used to make complex 3D electrical interconnects in
computer chips.
5. CHEMICAL VAPOUR DEPOSITION (CHEMICAL METHOD)
• In this method the material to be deposited is first heated to its gas form and
then allowed to deposit as a solid on a surface. This method is usually performed
under vacuum. The deposition can be direct or through chemical reaction so that
the material deposited is different from the one volatilized. This method is usually
used to prepare the nanopowders of oxides and carbides of metals if carbon and
oxygen are present in the metal. This method can be used for the preparation of
nanopowders of pure metals, though not easily.

• Chemical vapour deposition is usually used to deposit a material on a flat

surface. When a surface is exposed to a chemical vapour, the first layer of atoms
or molecules that deposited on the surface can act as a template on which
material can grow. The structures of these materials are often aligned.Aligned
structure starts to grow vertically. This is an example of self assembly.
6. SOL-GEL PROCESS (CHEMICAL METHOD)
This method is performed in liquid phase. It is an useful self assembly process for
fabricating nanoparticles as well as nano structured surfaces.
A “sol” is a type of colloid in dispersed solid phase is mixed in a homogenous liquid
medium. As the name suggests, sol-gel process involves the evolution of networks
through the formation of colloidal suspension (sol) and the gelation of sol to form a
network in a continuous liquid phase(gel).
1. Synthesis of colloids (Metal alkoxide precursor commonly used). Hydrolysis of
the precursor (-OR replaced by –OH) in presence of a catalyst.
2. Condensation and polymerization of sol. Particles grow and then
agglomerate.
3. Formation of network throughout the liquid medium, results in thickening,
which forms the gel.
This method is most commonly used to make silica gel.

7. PRECIPITATION PROCESS (CHEMICAL METHOD)
• Precipitation of a solid from a solution is a common technique for the

synthesis of fine nanoparticles. The general procedure involves reactions in
aqueous or nonaqueous solutions containing the soluble or suspended salts.
Once the solution becomes supersaturated with the product, the precipitate is
formed by either homogeneous or heterogeneous nucleation. The formation
of a stable material with or without the presence of a foreign species is
referred to as heterogeneous or homogeneous nucleation. The growth of
the nuclei after formation usually proceeds by diffusion, in which case
concentration gradients and reaction temperatures are very important in
determining the growth rate of the particles.
Concentration of reactants, reaction temperature, pH, and the order of addition of

reactants to the solution are important in this method.

IS NANO ALL GOOD????

Health impacts of nano particles are yet to be understood properly. It is quite
possible that nanoparticles can have adverse health effects.
Since these particles are very small, problems can actually arise from the
inhalation of these minute particles, much like the problems a person gets
from inhaling minute asbestos particles.
Atomic weapons can now be more accessible and made to be more powerful
and more destructive. These can also become more accessible with
nanotechnology.

FUN FACT
HOW TO PREPARE GOLD NANO PARTICLES IN THE LAB????
1. Heat a solution of chloroauric acid (HAuCl4) up to reflux (boiling). HAuCl4 is a

water soluble gold salt.
2. Add trisodium citrate, which is a reducing agent.
3. Continue stirring and heating for about 10 minutes.

During this time, the sodium citrate reduces the gold salt (Au 3+) to metallic
gold (Au0) . The neutral gold atoms aggregate into seed crystals. The seed
crystals continue to grow and eventually form gold nanoparticles.
MECHANISM OF NANOPARTICLE FORMATION

GLOSSARY
Atomic force microscope (AFM): A scientific instrument for analyzing the surface of
a rigid material all the way down to the level of the atom. AFM uses a mechanical
probe to magnify surface many fold, and it produces 3-D images of the surface.
Bottom Up: Building larger objects from smaller building blocks. This use atoms and
molecules as those building blocks to prepare nano sized material.
Buckyball: A familiar, nontechnical synonym for fullerene.
Carbon nanotube (CNT): An allotrope of carbon, cylindrical carbon molecules with
hexagonal rings and have novel properties that make them useful in a wide variety of
applications in nanotechnology, electronics, optics and materials science.
Chemical Vapour Deposition (CVD): A technique used to deposit coatings, where
chemicals are first vaporized, and then applied using an inert carrier gas such as
nitrogen.
Fullerene: A category of roughly spherical carbon nanoscale structures named after
Buckminster Fuller’s geodesic spheres.
Nanocomposite: A material composed of two or more substances, of which at least
one has a nanoscale dimension, such as nanoparticles dispersed throughout another
solid material.
Nanocrystals: also known as nanoscale semiconductor crystals. "Nanocrystals are
aggregates of anywhere from a few hundred to tens of thousands of atoms that
combine into a crystalline form of matter known as a "cluster."
Nanofabrication: General terms for methods to create, assemble, or otherwise form
nanoscale structures.
Nanometer: A distance unit representing one-billionth of a meter, or one-millionth of a
millimetre.
Nanoporous: Substances that have holes or pores on the nanoscale, used, for
example, to separate particles or molecules by size.
Nanosensor: A device for sensing radiation, forces, chemicals, or biological agents,
in which some portion of a device operates at the nanoscale, for example, by having

receptors into which the particular molecules to be sensed fit.

Quantum dot: A nanoscale crystal with a diameter that is typically between 2-20 nm,
having unique electrical and optical properties that are dependent on its size. They find
commercial applications in new light sources, enhanced medical imaging, and being
explored as compenents in quantum computers etc.
Quantum Tunneling: When electrons pass through a barrier, without overcoming it or
breaking it down.
Scanning tunneling microscope: This can make images of nanoscale details on an
electrically conductive surface by moving a sharp metal probe very close to that
surface, passing a low-voltage electric current across it, and measuring tiny
fluctuations in the current as the probe is scanned across the surface.
Self-assembly: A process in which a given nanostructure spontaneously constructs
itself, generally limited to very specific structures in chemical environments precisely
defined in order to promote self-assembly.
Vapor deposition: A chemical process commonly used in the semiconductor industry
to apply thin films of one substance onto a surface composed of another substance.
Books for your reference

1. Nanostructured Materials and Nanotechnology: Edited by Hari Singh
Nalwa, Academic Press, 2002.
2. Introduction to Nanotechnology: Charles P. Poole Jr. and Frank J. Owens,

John Wiley & Sons, 2003.
3. Introduction to nanoscience and nanotechnology: Banerjee A. N,
Chattopadhyay K. K, Phi Learning, 2009.
4. Nanotechnology: RK Rathi, S. Chand Publisher, 2009.

Websites for your reference

1. http://crnano.org/whatis.htm
2. www.nano.gov
3. http://www.azonano.com/
Must watch youtube videos

1. http://www.youtube.com/watch?v=xlYIex2TF5g
2. http://www.youtube.com/watch?v=FhiFamF-M0c
3. http://www.youtube.com/watch?v=WOqEk440JZ8
4. http://www.youtube.com/watch?v=icHRs3qMj9g
In brief
Nano is one billionth of a meter (10-9 of a meter). Nanotechnology deals with
materials having at least one spatial dimension in the size range of 1 to 100
nm.
Nanomaterials can be nanoscale in zero dimension (atomic clusters,
filaments and cluster assemblies), one dimension (eg. surface films), two
dimensions (eg. strands or fibres), or three dimensions (eg. particles).
Nanomaterials differ from bulk due to (i) large fraction of surface atoms; (ii)
high surface energy; (iii) spatial confinement; (iv) reduced imperfections,
which do not exist in the corresponding bulk materials.
At the nanometer scale, properties become size-dependent. Thermal,
optical, mechanical, magnetic, chemical properties of nano scale are all size
dependent.
Nanomaterials can be nanocluster, nanorod, nanowire, nanobelt etc.
Top down and bottom up approaches are used to prepare nanomaterials.
Top down method involves the breaking down of the bulk material into nano
sized structures or particles. Bottom up approach refers to the build up of a
material from the bottom: atom-by-atom, molecule-by-molecule, or cluster-by-
cluster.

Many physical and chemical methods are used for the synthesis of
nanomaterials. These include hydrothermal, solvothermal, chemical vapour
deposition, sol-gel method etc.
CONCLUSION

CHECK YOUR UNDERSTANDING

Question 1: The prefix "nano" comes from a ...
French word meaning billion
Greek word meaning dwarf
Spanish word meaning particle
Latin word meaning invisible
Question 2: Who first used the term nanotechnology and when?

Richard Feynman, 1959
Norio Taniguchi, 1974
Eric Drexler, 1986
Sumio Iijima, 1991
Question 3: What is a buckyball?

A carbon molecule (C60)
Nickname for Mercedes-Benz's futuristic concept car (C111)
Plastic explosives nanoparticle (C4)
Concrete nanoparticle with a compressive strength of 20
nanonewtons (C20)
Question 4: Which of these historical works of art contain nanotechnology?

Lycurgus cup
Medieval stained glass windows in churches
Damascus steel swords
All of the above

Question 5: Richard Feynman is often credited with predicting the potential of

nanotechnology. What was the title of his famous speech given on December 29,
1959?
There is a tiny room at the bottom
Things get nanoscopic at the bottom
Bottom? What bottom?
There is plenty of room at the bottom
Question 6: How many oxygen atoms lined up in a row would fit in a one nanometer
space?
None; an oxygen atom is bigger than 1 nm
One
Seven
Seventy
Question 7: Which one of these statements is NOT true?

Gold at the nanoscale is red
Copper at the nanoscale is transparent
Silicon at the nanoscale is an insulator
Aluminum at the nanoscale is highly combustible

Question 8: Which of these consumer products is already being made using

nanotechnology methods?
Fishing lure
Golf ball
Sunscreen lotion
All of the above
Question 9: What is graphene?

A new material made from carbon nanotubes
A one-atom thick sheet of carbon
Thin film made from fullerenes
A software tool to measure and graphically represent
nanoparticles
Question 10: Nanorobots (nanobots)...

Do not exist yet
Exist in experimental form in laboratories
Are already used in nanomedicine to remove plaque from
the walls of arteries
Will be used by NASA in the next unmanned mission to
Mars
Question 11: And what exactly is a quantum dot?

A semiconductor nanostructure that confines the motion of
conduction band electrons, valence band holes, or excitons
in all three spatial directions.
The sharpest possible tip of an Atomic Force Microscope
A fictional term used in science fiction for the endpoints of
wormholes
Unexplained spots that appear in electron microscopy
images of nanostructures smaller than 1 nanometer

ANSWERS
1. Greek word meaning dwarf

2. Norio Taniguchi, 1974
3. A carbon molecule (C60)
4. All the above
5. There is plenty of room at the bottom
6. Seven (The diameter of one oxygen atom is approximately 0.14 nanometers)
7. Silicon at the nanoscale is an insulator.
8. All of the above
9. A one-atom thick sheet of carbon
10. Do not exist yet
11. A semiconductor nanostructure that confines the motion of conduction band
electrons, valence band holes, or excitons in all three spatial directions.

Nano Pre Class

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Engineering Chemistry

Pre class notes- Atomic and Molecular Nano Chemistry

At the end of the lecture the students are able to

3. Distinguish between molecules, nanoparticles and bulk materials.

4. Understand the importance of nanotechnology

5. Appreciate uniqueness of “nano scale”.

7. Understand and appreciate size dependent properties of nano particles.

9. Know the applications of nanotechnology in diverse fields.

Material prepared by: Chemistry faculty 1

Pre class notes- Atomic and Molecular Nano Chemistry

Matter is composed of indivisible building blocks. This idea was recorded as

2. All atoms of an element are identical.

3. The atoms of different elements vary in size and mass.

Material prepared by: Chemistry faculty 2

Pre class notes- Atomic and Molecular Nano Chemistry

4. Compounds are produced through different whole-number combinations

5. A chemical reaction results in the rearrangement of atoms in the

J.J. Thomson's atom model: Plum Pudding model

Ernest Rutherford's model: Nuclear model

Material prepared by: Chemistry faculty 3

Pre class notes- Atomic and Molecular Nano Chemistry

Niels Bohr's model: Planetary model

Erwin Schrödinger's model: Electron Cloud Model/Quantum Model

Material prepared by: Chemistry faculty 4

Pre class notes- Atomic and Molecular Nano Chemistry

Quantum mechanical model of atom

Material prepared by: Chemistry faculty 5

Pre class notes- Atomic and Molecular Nano Chemistry

Shapes of s,p and d orbitals

Material prepared by: Chemistry faculty 6

Pre class notes- Atomic and Molecular Nano Chemistry

ORBITALS IN MOLECULES- MOLECULAR ORBITALS

Destructive interaction The two 1s Orbitals are out phase

Material prepared by: Chemistry faculty 7

Pre class notes- Atomic and Molecular Nano Chemistry

Linear Combination of atomic orbitals

Material prepared by: Chemistry faculty 8

Pre class notes- Atomic and Molecular Nano Chemistry

Material prepared by: Chemistry faculty 9

Pre class notes- Atomic and Molecular Nano Chemistry

Nanotechnology definition (NASA)

Material prepared by: Chemistry faculty 10

Pre class notes- Atomic and Molecular Nano Chemistry

A very succinct definition for nanotechnology is simply “engineering with atomic

Carl Sagan - "Somewhere, something incredible is waiting to be known."

Feynman pointed out that designing materials atom-by-

NANOTECHNOLOGY –AN INTERDISCIPLINARY SCIENCE

Material prepared by: Chemistry faculty 11

Pre class notes- Atomic and Molecular Nano Chemistry

Material prepared by: Chemistry faculty 12

Pre class notes- Atomic and Molecular Nano Chemistry

Gerd Binnig and Heinrich Rohrer at IBM’s Zurich lab invented

Rice University researchers Harold Kroto, Sean O’Brien,

Sumio Iijima of NEC is credited with discovering the carbon

1999– till date Consumer products making use of nanotechnology began

Lightweight golf balls, stiffer tennis rackets and baseball bats,

Material prepared by: Chemistry faculty 13

Pre class notes- Atomic and Molecular Nano Chemistry

Nanomaterials can be nanoscale in zero dimension (atomic clusters, filaments and

Material prepared by: Chemistry faculty 14

Pre class notes- Atomic and Molecular Nano Chemistry

Comparison of 0D Nanoarchitectures with Traditional Colloids

Material prepared by: Chemistry faculty 15

Pre class notes- Atomic and Molecular Nano Chemistry