Physics of Nano

• Introduction to nanomaterials,
• Properties of nanomaterials,
• Types of nanomaterials,
• Synthesis of Nanomaterials- Top-down and Bottom-up approaches,
• Quantum confinement, Quantum well, Wire and Dot,
• Carbon Nano tubes (CNTs),
• Nanotechnology for medical and industrial applications.
 Nanomaterials: Introduction
Ultrafine microstructures of grain size of order nanometer (10-9m)
called nanostructured materials (NSMs).
Currently, wider meaning,
Any material containing grains or clusters below 100 nm, or
layers or filaments of that dimension, called as NSMs.
Stimulated Interest in these materials owing to
Small size of building blocks (particle, grain, or phase)
High surface-to-volume ratio
Expected to demonstrate unique
Mechanical
Optical
Electronic
Magnetic properties
 Nanomaterials: Introduction
Properties of NSMs depend on
Fine grain size and size distribution (« 100 nm)
Chemical composition of constituent phases
Presence of interfaces, more specifically
Grain boundaries
Heterophase interfaces
Or free surface
Interactions between constituent domains.
Presence and interplay of these four features largely determine
unique properties of NSMs
Size relationship of Chemistry, Nanoparticles and SSP
Chem. & Phy. fields evolved in intermingled way & still inseparable
in any practical sense
Chemistry - atoms and molecules, a realm of matter whose
dimensions are generally < 1 nm
Chemistry Nanoscale regime Solid State Physics

One 10 100 1000 10000 1x106 Bulk

Atom Atom Atom Atom Atom Atom

0 1 2 3 5 7 10 100

Diameter (nm)
Size relationship of chemistry, nanoparticles, and solid-state physics

Physics - solids essentially of infinite array of bound atoms or

molecules >100 nm
Significant gap exist between regimes of Chem. & Phy.
 Nanomaterials…….

• Natural nanomaterials—A nanomaterial made by nature through

(bio)geochemical or mechanical processes, without direct or
indirect connection to a human activity or anthropogenic process.
• Incidental nanomaterials—A nanomaterial unintentionally
produced as a result of any form of direct or indirect human
influence or anthropogenic process.
• Engineered nanomaterials—A nanomaterial conceived, designed,
and intentionally produced by humans.
• Anthropogenic nanomaterials—Both incidental and engineered
nanomaterials.
 Shapes of Nanoparticles

• Nanosheets or nanofilms have one dimension in this size range;

(e.g., clay minerals)
• Nanorods have two dimensions in this size range
• Nanoparticles have three dimensions in this size range
• Nanotubes are nanoscale materials that have a tube-like structure;
e.g., carbon nanotubes in the accompanying figure.
Shapes of Nanoparticles
Size is a Material Property?

The gold we know: The gold we are discovering:

Material properties don’t Material properties (such as optical

change with size Absorption, shown here) change
- resistivity with the size of the gold
- melting point nanoparticle.
- optical absorption
 Unique Characteristics of Nanoparticles
• Large surface to volume ratio
• High percentage of atoms/molecules on the surface
• Surface forces are very important, while bulk forces are not as
important.
• Metal nanoparticles have unique light scattering properties and
exhibit plasmon resonance.
• Semiconductor nanoparticles may exhibit confined energy states in
their electronic band structure (e.g. quantum dots)
• Can have unique chemical and physical properties
• Same size scale as many biological structures
Examples of Unusual Properties

• Lowered phase transition temps

• Increased mechanical strength

• Different optical properties

• Altered electrical conductivity

• Magnetic properties

• Self-purification and self-perfection

 Physical Properties of Nanoparticles

• Physical properties of nanoparticles are dependent on:

– Size
– Shape (spheres, rods, platelets, etc.)
– Composition
– Crystal Structure (FCC, BCC, etc.)
– Surface ligands or capping agents
– Medium in which they are dispersed
 Size of Nanoparticles
# of atoms
• Molecules, nanoparticles, and bulk 1
Molecules
materials can be distinguished by the 10
number of atoms comprising each
type of material. 102
• Note: these are very approximate 103
numbers! Nanoparticles
104

105

106
Bulk
Size of Nanoparticles
• Nanoparticles exhibit unique properties due to their high surface
area to volume ratio.
• A spherical particle has a diameter (D) of 100nm.
– Calculate the volume (V) and surface area (SA)

4 3 πD 3
V = πr = SA = 4 πr 2 = πD2
3 6
π(100 × 10 -9 )3 SA = π(100 × 10 -9 )2
V=
6 SA = 3.141 × 10 -14 m2
V = 5.24 x10 -22 m3
 Surface Area: Volume Ratio

• Approximate surface area to volume ratio of >107:1

• significantly larger than a macro sized particle.

• Increased surface area to volume ratio- increased percentage of

atoms at the surface and surface forces become more dominant.

• Generally accepted material properties are derived from bulk, where

the percentage of atoms at surface is miniscule.

• These properties change at the nanoscale.

 Surface Area: Volume Ratio

In this graph:
SA = nm2
Vol = nm3

SA:Vol Ratio = nm2/nm3

Ratio increases dramatically when nanoparticle diameter drops below

about 100 nm
 Electronic Structure

• When atoms form a lattice, the discrete energy levels of the atoms
are smudged out into energy bands.
• Density of states refers to number of energy levels in a given interval
of energy.
• When a metal particle having bulk properties is reduced in size to a
few hundred atoms, the density of states in the conduction band
containing electrons, changes dramatically.
• Continuous density of states in the band is replaced by a set of
discrete energy levels, which may have energy level spacings larger
than thermal energy kBT, and a gap opens up.
Electronic Structure

• Small cluster is analogous to a molecule having discrete energy levels

with bonding and antibonding orbitals.
• Eventually a size is reached where the surfaces of the particles are
separated by distances, which are in the order of the wavelengths of
the electrons.
• Energy levels can be modeled by the quantum-mechanical treatment
of a particle in a box. This is referred to as the quantum size effect.
 Electronic Structure

• The quantum size effect occurs in semiconductors at larger sizes

because of the longer wavelength of conduction electrons and holes
in semiconductors due the larger effective mass.
• In a semiconductor the wavelength can approach one micrometer,
whereas in a metal it is in the order of 0.5nm.
 Electronic Structure

• Color of a material is determined by wavelength of light that is

absorbed by it.
• Absorption occurs because electrons are induced by photons of the
incident light to make transitions between lower-lying occupied
levels and higher unoccupied energy levels of materials.
• Clusters of different sizes will have different electronic structures,
and different energy-level separations.
• Light-induced transitions between these levels determines the color
of the materials.
• Clusters of different sizes can have different colors, and the size of
the cluster can be used to engineer the color of a material.
 Size of Nanoparticles
• Increased percentage of atoms at surface change mechanical,
optical, electrical, chemical, and magnetic properties.
– Ex. optical properties (color) of gold and silver change, when
spatial dimensions are reduced, and concentration is changed.
 Bulk to nano transition
• In a cluster with less than 100 atoms, amount of energy needed to
ionize it, that is, to remove an electron from the cluster, differs from
the work function.
• Work function is the amount of energy needed to remove an electron
from the bulk solid.
• Clusters of gold have been found to have same melting point of bulk
gold only when they contain 1000 atoms or more.
• Different physical properties of clusters reach the characteristic
values of solid at different cluster sizes.
• Size of the cluster where the transition to bulk behavior occurs
appears to depend on the property being measured.
Size of Nanoparticles
Melting point versus particle size
• Nanoparticles have a lower melting point than their bulk
counterparts

Melting point of gold nanoparticles as a function of size.

 Size of Nanoparticles
Melting point versus shape

• Particles: May sinter together at lower-than-expected temperature.

• Rods: Can melt and form spherical droplets if heated too high.
• Films: Thin films can form pin-holes. Continued heating can lead to
de-wetting behavior and island formation.
 Crystal Structure
• Most solids are crystalline with their atoms arranged in a regular
manner.
– Impacts the functionality of the material.
• Some solids have this order presented over a long range as in a
crystal.
• Amorphous materials such as glass and wax lack long range order,
but they can have a limited short-range order, defined as the local
environment that each atom experiences.
 Size & Crystal Structure
• How does crystal structure impact nanoparticles?

• Nanoparticles have a “structural magic number”, that is, the

optimum number of atoms that leads to a stable configuration
while maintaining a specific structure.

• Structural magic number = minimum volume and maximum

density configuration

• If the crystal structure is known, then the number of atoms per

particle can be calculated.
Close-Packed Magic Number Clusters

• Magic Number = Cluster has a complete, regular outer geometry

• Formed by successively packing layers around a single metal atom.
• Number of atoms (y) in shell (n): y = 10n2 + 2 (n = 1,2,3…)
• Maximum number of nearest neighbors (metal-metal hcp packing)
• Decreasing percentage of surface atoms as cluster grows
 Size & Crystal Structure

• For n layers, the number of atoms N in an approximately spherical

FCC nanoparticle is given by :

N = 1/3[10n3 – 15n2 + 11n - 3]

• The number of atoms on the surface Nsurf

NSurf = 10n2 – 20n +12

Size & Crystal Structure Example Calculations:

How many atoms (N) are in

idealized Au NP’s with the
following diameters?

5 nm Au NP:
With 9 shells, n = 9 and
NP diameter = 17d = 4.896 nm
N = 1/3[10n3 – 15n2 + 11n - 3] N =
2057

Other Approximate Values

10 nm = 17,900
20 nm = 137,000
30 nm = 482,000
40 nm = 1.1 million
50 nm = 2.2 million
 Optical Properties
• The size dependence on the optical properties of nanoparticles is the
result of two distinct phenomena:

– Surface plasmon resonance for metals

– Increased energy level spacing due to the confinement of

delocalized energy states. Most prominent in semiconductors

Poole, C., Owens, F. Introduction to Nanotechnology. Wiley, New Jersey. 2003

 Optical Properties

Surface Plasmons
• Recall that metals can be modeled as an arrangement of positive
ions surrounded by a sea of free electrons.

• The sea of electrons behaves like a fluid and will move under the
influence of an electric field

-- - -- -- - --- - -- -- - - ----------------- ----------

- + - + - + - + - -- -- - -- --
------------- -- + - + - + - + --
- - - - ---------------
- + - + -- + - + - - - - -
------------ + + - + +
E-field
 Optical Properties
Surface Plasmons
• If the electric field is oscillating (like a photon), then the sea of
electrons will oscillate too.
• These oscillations are quantized and resonate at a specific
frequency. Such oscillations are called plasmons.

Resonance at a metal surface

Resonance in metal NP

Source: MRS Bulletin 2005, 30(5), 338.

 Optical Properties
Surface Plasmons
• Formal definition: Plasmons are the coherent excitation of free
electrons in a metal.
• The plasmon resonance frequency (f) depends on particle size,
shape, and material type.
• It is related to the plasmon energy (E) by Planck’s constant. E = h*f
• Surface plasmons are confined to the surface of the material.
• Optical properties of metal nanoparticles are dominated by the
interaction of surface plasmons with incident photons.
 Optical Properties

Surface Plasmons
• Metal nanoparticles like gold and silver have plasmon frequencies in
the visible range.
• When white light impinges on metal nanoparticles the wavelength
corresponding to the plasmon frequency is absorbed.
• The spectral locations, strengths, and number of plasmon
resonances for a given particle depend on the particle’s shape and
size.
 Optical Properties
• Absorption spectra of spherical Au nanoparticles

Optical absorption spectrum of 20- and 80-nm gold nanoparticles embedded in glass.
[Adapted from F. Gonella et al., in Handbook of Nanostructured Material and Nanotechnology,
H. S. Nalwa, ed., Academic Press, San Diego, 2000, Vol. 4, Chapter 2, p.85.]
 Optical Properties
Surface Plasmons: Shape dependence
of absorption spectra
• Amount of light that is scattered
into the far field is described by the
scattering cross section (SCS).
• SCS is plotted against wavelength
of light used to illuminate a particle
from a specific angle.
• Arrows indicate the illumination
angle, and their colors correspond
to the different plot lines.
Martin, Olivier J.F. “Spectral response of plasmon resonant
nanoparticles with non-regular shape”. Optics Express Col. 6. No. 11
May 2000
 Optical Properties
Surface Plasmons: Shape dependence of absorption spectra

Martin, Olivier J.F. "Plasmons". Plasmons. 22 Mar. 2006. Ecole

Polytechnique Fédérale de Lausanne. 26 Jan. 2003.

• Triangular shaped nanoparticles produce plasmons with altered

frequency and magnitude
Optical Properties
Energy levels: from atoms to bulk materials…
• The Pauli Exclusion Principle states that electrons can only exist in
unique, discrete energy states.
• In an atom the energy states couple together through spin-orbit
interactions to form the energy levels.
• When atoms are brought together in a bulk material, the energy
states form nearly continuous bands of states, or in
semiconductors and insulators, nearly continuous bands separated
by an energy gap.

Atoms: Discrete Energy Levels Bulk Materials: Band Structures

Energy
Energy

N
Optical Properties
Energy levels
• In semiconductors and insulators, the valance band corresponds to
the ground states of the valance electrons.
• In semiconductors and insulators, the conduction band corresponds
to excited states where electrons are a free to move about in the
material and participate in conduction.
• In order for conduction to take place in a semiconductor, electrons
must be excited out of the valance band, across the band gap into
the conduction band. This process is called carrier generation.
• Conduction takes place due to the empty states in the valence band
(holes) and electrons in the conduction band.
Ec

band gap

Ev

Electron excited into conduction band

 Optical Properties
Energy level spacing
• In semiconductors and insulators, a photon with an energy equal to
the band gap energy is emitted when an electron in the conduction
band recombines with a hole in the valance band.
• The electronic band structure of a semiconductor dictates its optical
properties.
• GaP, a material commonly used for green LEDs, has an intrinsic band
gap of 2.26 eV. Carrier recombination across the gap results in the
emission of 550 nm light.

Eg = 2.26 eV

λ=550 nm
 Optical Properties
Energy level spacing and quantum confinement
• The reduction in the number of atoms in a material results in the
confinement of normally delocalized energy states.
• Electron-hole pairs become spatially confined when the dimensions
of a nanoparticle approach the de Broglie wavelength of electrons in
the conduction band.
• As a result the spacing between energy bands of semiconductor or
insulator is increased (Similar to the particle in a box scenario, of
introductory quantum mechanics.)
Bulk Materials
Energy Nano Materials

Eg Increased
Eg
band gap
Optical Properties
Energy level spacing and quantum confinement
• Semiconductor nanoparticles that exhibit 3 dimensional
confinement in their electronic band structure are called
quantum dots.
• What does this all mean?
• Quantum dots are band gap tunable.
• We can engineer their optical properties by
controlling their size.
• For this reason quantum dots are highly desirable for
biological tagging.
Optical Properties

• Energy level spacing and quantum confinement

– As semiconductor particle size is reduced the band gap is
increased.
– Absorbance and luminescence spectra are blue shifted with
decreasing particle size.

CdSe quantum dots

Jyoti K. Jaiswal and Sanford M. Simon. Potentials and pitfalls of fluorescent quantum
dots for biological imaging. TRENDS in Cell Biology Vol.14 No.9 September 2004
 Semiconducting nanoparticle-optical properties

• In a bulk semiconductor a bound electron-hole pair, called an exciton, can be

produced by a photon having an energy greater than that of the band gap of the
material.
• Photon excites an electron from filled band to unfilled band above.
• Result is a hole in filled valence band, which corresponds to an electron with an
effective positive charge.
• Because of the Coulomb attraction between hole and electron, a bound pair,
called an exciton, is formed that can move through lattice.
• Separation between hole and electron is many lattice parameters.
• Existence of exciton has a strong influence on the electronic properties of the
semiconductor and its optical absorption.
 Semiconducting nanoparticle-optical properties

• When nanoparticle becomes smaller than or comparable to the radius of orbit of

the electron-hole pair, there are two situations, called the weak-confinement and
strong-confinement regimes.
• In weak regime, particle radius is larger than radius of electron-hole pair, however
range of motion of the exciton is limited, which causes a blue shift of the
absorption spectrum.
• When the radius of the particle is smaller than the orbital radius of the electron-
hole pair, the motion of the electron and the hole become independent, and the
exciton does not exist.
• The hole and electron have their own set of energy levels.
• There is also a blue shift, and the emergence of a new set of absorption lines.
 Semiconducting nanoparticle-optical properties
• Lowest energy absorption region,
absorption edge, is shifted to higher
energy as the particle size decreases.
• Since the absorption edge is due to
the band gap, the band gap increases
as particle size decreases.
• Intensity of absorption increases as
particle size is reduced.
• Higher energy peaks are associated
with the exciton, and they shift to Optical absorption spectrum of CdSe for two
higher energies with the decrease in nanoparticles having sizes 20A and 40A,
particle size. respectively. [D. M. Mittleman, Phys. Rev. B49,
14435 (1994).]

As the particle size is reduced, hole and electron are forced closer
together, and separation between the energy levels changes.
Nanoparticles: Synthesis
Approaches – Physical and Chemical
Physical
Bottom up - Controlling aggregation
Vaporize metals or oxides
Resistive heating from crucible
Electron beam heating
Laser pulses
Top down – Deformation of coarser materials
High energy ball-mill
High-energy shear process
Very useful in generating commercial quantities of material
suffers from the disadvantage of contamination
Nanoparticles: Synthesis
Thin film deposition techniques can be put as follows:
1. Physical Methods (Bottom up)
Physical Vapor Deposition (using different heating techniques)
• Resistive heating
• Laser heating
• Electron beam heating
• Induction heating
2. Chemical Methods
• Screen printing
• Chemical Vapour deposition (CVD)
• Solution Growth or electroless deposition.
• Electrochemical deposition.
Top-Down Approach: Mechanical Milling (Ball milling)
• Mechanical Milling (Ball milling): A Top-Down Approach for
synthesis of Nanomaterials and Nanocomposites
• A simple, low cost and in high yield method of synthesis of
nanoparticles has been a great challenge.

• High energy ball milling, has been widely exploited for synthesis of
various nanomaterials, nanograins, nanoalloy, and nanocomposites
materials.
 Ball milling

• In high-energy ball milling, plastic deformation, cold-welding and

fracture are predominant factors.
• Deformation leads to a change in particle shape
• Cold-welding leads to an increase in particle size
• Fracture leads to decrease in particle size
• Resulting in formation of fine dispersed alloying particles in the
grain-refined soft matrix
 Ball milling
• More economical process for large scale production .
• Reduces particle size and blends into new phases.
• Balls impact upon powder changes with different ball sizes.
• Kinetics of mechanical milling depends on energy transferred to the
powder from balls during milling.
• Energy transfer is governed by type of mill, powder, milling speed,
size and size distribution of balls, dry or wet milling, temperature
and duration of milling.
 Ball milling

• Size and size distribution of balls should be optimized.

• Temperature during milling depends on kinetic energy of balls and
material characteristics of powder and milling media (process
control agent).
• Temperature of powder influences diffusivity and defect
concentration in powder influencing phase transformations induced
by milling.
 Cluster Beam Evaporation
• Solid metal material is heated by
electron bombardment.
• During deposition, temperature of
crucible is kept as high as Melting point
of solid material.
• Chamber is evacuated with high vacuum
(10-6 torr) to minimize impurities and
increase mean free path for getting good
quality film.
• Substrate temperature: Either Room or
liquid nitrogen temperature (low as
─196oC).

• Classical nucleation theory predicts that size of nanostructures formed by cluster

beam evaporation would be much smaller than those by conventional thermal
vacuum evaporation technique.
Laser induced evaporation of atoms from surface of a metal.
Laser evaporation

• A high intensity laser beam is incident on a metal rod, causing

evaporation of atoms from the surface of metal.
• Atoms are then swept away by a burst of helium and passed
through an orifice into a vacuum where the expansion of the gas
causes cooling and formation of clusters of the metal atoms.
• These clusters are then ionized by UV radiation and passed into a
mass spectrometer that measures their mass : charge ratio.
 RF Plasma
• Starting metal is contained in a pestle in an
evacuated chamber.

• Metal is heated above its evaporation

point using high voltage RF coils wrapped
around evacuated system in the vicinity of
pestle.

• Helium gas is then allowed to enter the

system, forming a high temperature
plasma in the region of the coils.

• Metal vapor nucleates on He gas atoms and diffuses up to a colder collector rod
where nanoparticles are formed.

• The particles are generally passivated by the introduction of some gas such as
oxygen.

• In the case of aluminum nanoparticles, oxygen forms a layer of aluminum oxide

about the particle.
Thermolysis

Synthesis of metal nanoparticles by thermally decomposing solids

consisting of metal cations and molecular anions, or metal organic
solids called thermolysis.
 Thermolysis

• Material is placed in an evacuated

quartz tube and heated to 400°C.
• At about 370°C LiN3 decomposes,
releasing N2 gas
• Indicates increased pressure on
vacuum gauge.
• In a few minutes pressure drops back to its original low value,
indicating removal of N2.
• Remaining Li atoms coalesce to form small colloidal metal particles.
• Particles less than 5 nm can be made by this method.
• Passivation achieved by introducing an appropriate gas.
• Ex., small Li particles made by decomposing lithium azide, LiN3.
Pulsed Laser Method
• Metal nitrate solution and a
reducing agent are flowed
through a blender like device.
• Solid disk in blender rotates in
solution.
• Solid disk is subjected to pulses
from a laser beam creating hot
spots on surface of disk.
• Metal nitrate and reducing agent react at these hot spots, resulting
in formation of small metal particles.
• Metal particles are then separated from solution using a centrifuge.
• Particle size is controlled by energy of laser and rotation speed of
disk.
• This method is capable of a high rate of production of 2-3 g/min.
 Nanoparticles: Synthesis
Chemical
Chemistry plays vital role in developing new materials with novel and
technologically important properties.
Advantage
Versatility in designing and synthesizing new materials that can be
refined into final product.
Good chemical homogeneity
Chemical synthesis offers mixing at molecular level.
Molecular chemistry can be designed to prepare new materials by
Understanding how matter is assembled on atomic and
molecular level
Consequent effects on desired macroscopic properties.
 Nanoparticles: Synthesis
Chemical: Advantages
Basic understanding of principles of
Crystal chemistry
Thermodynamics
Phase equilibrium
Reaction kinetics

Important to take advantage of many benefits

that chemical processing has to offer.
 Nanoparticles: Synthesis
Chemical: Disadvantages
In some preparations
Chemistry is complex and hazardous.
Contamination can result from
Byproducts being generated or
Side reactions in chemical process.
Should be minimized or avoided to obtain desirable
properties in final product.
Agglomeration major concern any stage in synthetic process
Can dramatically alter the properties of the materials.
Example
Agglomeration frequently makes it more difficult to
consolidate nanoparticles to a fully dense compact.
Although many chemical processes are scalable for economical
production, it is not always straightforward for all systems
Nanoparticles: Synthesis
Chemical
 Nanoparticles: Synthesis
Chemical: Solution Chemistry
Used sometimes to prepare precursor
Subsequently converted to nanophase particles by
Non-liquid phase chemical reactions.
Precipitation from solution is common technique for synthesis of fine
particles.
Generally, involves reactions in aqueous or nonaqueous solutions
containing soluble or suspended salts.
Solution becomes supersaturated with product
Precipitate formed by either homogeneous or heterogeneous
nucleation.
Formation of stable material with or without presence of foreign
species by
Heterogeneous or
Homogeneous nucleation.
 Nanoparticles: Synthesis
Chemical: Solution Chemistry

Growth of nuclei after formation usually proceeds by diffusion

Growth rate of particles determined by
Concentration gradients
Reaction temperatures
For instance
Prepare un-agglomerated particles with very narrow size distribution
All nuclei must form at nearly same time
Subsequent growth must occur without further nucleation or
agglomeration of particles.
Nanoparticles: Synthesis
Chemical: Solution Chemistry
Importance of reaction kinetics
Particle size and particle size distribution
Physical properties such as
Crystallinity
Crystal structure
Degree of dispersion
Additional factors
Concentration of reactants
Reaction temperature
pH
Order of addition of reactants to solution
Nanoparticles: Synthesis
Chemical: Solution Chemistry
Multi-element materials often made by coprecipitation of batched
ions
It is not always easy to coprecipitate all desired ions
simultaneously
Different species may only precipitate at different pH.
Control of chemical homogeneity and stoichiometry requires very
careful control of reaction conditions.
Problem of agglomeration may be avoided by
Spray drying
Freeze drying.
Nanoparticles: Electronic Structure
• When atoms form a lattice, discrete energy levels of atoms are
smudged out into energy bands.
• Density of states refers to number of energy levels in a given
interval of energy.
• For a metal, top band is not totally filled.
• In semiconductor top occupied band, called the valence band, is
filled.
• Small energy separation, band gap, between it and next higher
unfilled band.
 Nanoparticles: Electronic Structure

• Electronic, optical and magnetic properties become size-and shape-

dependent at nano range.
• Optical behaviour is very sensitive to quantum effects otherwise
called ‘quantum confinement’.
• Significance of quantum mechanical effects depends on
temperature and distance between neighbouring energy levels or
bands.
• Has to be large compared to thermal energy, kBT, in order to
avoid a smear-out of effect by thermal fluctuations.
Nanoparticles: Electronic Structure

• Density of states in conduction band containing electrons, changes

dramatically with reduction in size.
• Continuous density of states in the band is replaced by a set of
discrete energy levels.
• May have energy level spacings larger than thermal energy kT, and a
gap opens up.
Nanoparticles: Electronic Structure
Nanoparticles: Electronic Structure
• Spacing of electronic levels and bandgap increases with decreasing
particle size.
• Because electron-hole pairs are now much closer together and
Coulombic interaction between them can no longer be
neglected giving an overall higher kinetic energy.
• Increase in bandgap can be observed experimentally by blue-shift in
the absorption spectrum or sometimes even visually by colour of
samples.
• A larger bandgap means more energy is required to excite an
electron from valance band to conduction band.
• hence light of a higher frequency and lower wavelength would
be absorbed.
 Nanoparticles: Quantum Wells, Wires and Dots

• Word quantum is associated with three types of nanostructures

• changes in properties arise from quantum-mechanical nature of physics in the
domain of the ultrasmall.

• If one dimension is reduced to nano-range while other two

dimensions remain large, then structure known as a quantum well.
• If two dimensions are so reduced and one remains large, structure is
referred to as a quantum wire.
• Size reduction in all three dimensions is called quantum dot.
 Nanoparticles: Quantum Wells, Wires and Dots

• Dimensionality effects that occur when one, two, or all three

dimensions becomes small.
• How electronic properties are altered by these changes?
 Nanoparticles: Quantum Confinement

• Particle behaves as if it was free when confining dimension is large

compared to wavelength of particle.
• During this state, bandgap remains at its original energy due to a
continuous energy state.
• As confining dimension decreases typically in nanoscale, energy
spectrum becomes discrete.
• As a result, bandgap becomes size-dependent.
• As size of particles decreases, electrons and electron holes come
closer, and energy required to activate them increases,
• Results in a blueshift in light emission.
Nanoparticles: Carbon nanotubes (CNT)

• Cylindrical molecules consist of rolled-up sheets of single-layer

carbon atoms (graphene).
• CNT can be
• single-walled with a diameter of less than 1 nm or

• multi-walled, consisting of several concentrically interlinked nanotubes, with

diameters 100 nm.

• Their length can reach several m or even mm.

• Ultra-high strength, low-weight materials that possess highly
conductive electrical and thermal properties
Carbon nanotubes (CNT): Synthesis

Carbon nanotubes can be made by laser evaporation, carbon arc

methods, and chemical vapor deposition.
Carbon nanotubes (CNT): Synthesis- laser evaporation
• Quartz tube containing argon gas and a graphite target are heated
to 1200°C.
• A water-cooled copper collector is placed in the same tube but
outside furnace.
• Graphite target contains small amounts of cobalt and nickel that
act as nucleation sites for the formation of carbon nano tubes.
• An intense pulsed laser beam is incident on the target, evaporating
carbon from the graphite.
• Argon then sweeps the carbon atoms from high temperature zone
to colder copper collector on which they condense into nanotubes.
• Tubes 10-20 nm in diameter and 100 m long can be made by this
method.
Carbon nanotubes (CNT): Synthesis-Carbon Arc
• A potential of 20-25 V is applied across carbon electrodes of 5-20 m
diameter and separated by 1 mm at 500 torr pressure of flowing
helium.
• Carbon atoms are ejected from positive electrode and form
nanotubes on the negative electrode.
• As the tubes form, length of positive electrode decreases, and a
carbon deposit forms on negative electrode.
• To produce single-walled nanotubes, a small amount of cobalt,
nickel, or iron is incorporated as a catalyst in the central region of the
positive electrode.
• If no catalysts are used, the tubes are nested or multiwalled types
(MWNT), which are nanotubes within nanotubes.
• Carbon arc method can produce SWCNT of diameters 1-5 nm with a
length of 1 m.
Carbon nanotubes (CNT)- Synthesis- CVD

• CVD involves decomposing a hydrocarbon gas such as methane (CH4)

at 1100°C.
• As the gas decomposes, carbon atoms condense on a cooler
substrate that may contain catalysts such as iron.
• CVD produces tubes with open ends, which does not occur when
other methods are used.
• CVD allows continuous fabrication and may be the most favorable
method for scaleup and production.
Carbon nanotubes (CNT)- Synthesis- CVD

• A metal catalyst combined with carbon-containing reaction gases

(hydrogen or carbon monoxide) to form carbon nanotubes on
catalyst inside a high-temperature furnace.
• First, small secondary catalyst particles of size of a CNT diameter
develop on which nanotubes start growing.
• Catalyst particle is either at top or at bottom of emerging nanotube.
• Growth will stop if catalyst particle is deactivated through
development of a carbon envelope.
Carbon nanotubes (CNT)
• As the metal catalyst is necessary for the growth of SWNTs,
mechanism must involve the role of the Co or Ni atoms.
• As per “scootter mechanism”
• atoms of metal catalyst attach to the dangling bonds at the
open end of the tubes,
• these atoms scoot around the rim of the tube, absorbing carbon
atoms as they arrive.
Carbon nanotubes (CNT)- Synthesis- CVD
• Generally when nanotubes are synthesized, result is a mix of
different kinds, some metallic and some semiconducting.
• Separation was accomplished by depositing bundles of nanotubes,
some of which are metallic and some semiconducting, on a silicon
wafer.
• Metal electrodes were then deposited over the bundle.
• Using the silicon wafer as an electrode, a small bias voltage was
applied that prevents the semiconducting tubes from conducting,
effectively making them insulators.
• A high voltage is then applied across the metal electrodes, thereby
sending a high current through the metallic tubes but not the
insulating tubes.
• This causes the metallic tubes to vaporize, leaving behind only
semiconducting tubes.
 Carbon nanotubes (CNT)

Illustration of some possible structures of carbon nanotubes, depending on how

graphite sheets are rolled: (a) armchair structure; (b) zigzag structure; (c) chiral
structure.
 Carbon nanotubes (CNT)

• Rolling-up direction (rolling-up

or chiral vector) of graphene layers
determines electrical properties of
nanotubes.
• Chirality describes angle of nanotube's
hexagonal carbon-atom lattice.
• MWCNTs are always conducting and achieve at least same level of
conductivity as metals.
• SWCNTs' conductivity depends on their chiral vector:
• They can behave like a metal and be electrically conducting; display
the properties of a semi-conductor; or be non-conducting.
• Ex, a slight change in pitch of the helicity can transform the tube from
a metal into a large-gap semiconductor.
 Nanoparticles: Carbon nanotubes properties

• Carbon nanotubes have the most interesting property that they are
metallic or semiconducting, depending on the diameter and chirality
of the tube.

• Chirality refers to how tubes are rolled with respect to direction of

the T vector

Graphitic sheet showing the basis vectors a, and a2 of the two-dimensional unit cell, the axis
vector T about which the sheet is rolled.
 Nanoparticles: Carbon nanotubes properties

• High mechanical tensile strength 400 times that of steel.

• Light-weight –density is one sixth of that of steel.

• Thermal conductivity is better than that of diamond.

• Very high aspect ratio greater than 1000,

• in relation to their length they are extremely thin;

• A tip-surface area near the theoretical limit

• Smaller the tip-surface area, more concentrated the electric field,

and the greater field enhancement factor.
 Nanoparticles: Carbon nanotubes properties

• Highly chemically stable and resist virtually any chemical impact

unless they are simultaneously exposed to high temperatures and
oxygen
• Extremely resistant to corrosion;
• Hollow interior can be filled with various nanomaterials, separating
and shielding them from the surrounding environment
• Extremely useful for nanomedicine applications like drug
delivery.
Nanoparticles: Carbon nanotubes synthesis

• Three main methods currently available for the production of

CNTs: Arc discharge, Laser ablation of graphite, and chemical
vapor deposition (CVD).
• In first two processes, graphite is combusted electrically or by
means of a laser, and CNTs developing in gaseous phase are
separated.
• All three methods require use of metals (e.g. iron, cobalt, nickel)
as catalysts.
 Nanotechnology applications
Field Emission and Shielding
• When a small electric field is applied parallel to the axis of a
nanotube, electrons are emitted at a very high rate from the ends of
the tube. This is called field emission.
• Samsung in Korea is developing a flat-panel display using the
electron emission of carbon nanotubes.
• A thin film of nanotubes is placed over control electronics with a
phosphor-coated glass plate on top.
• A Japanese company is using this electron emission effect to make
vacuum tube lamps that are as bright as conventional light bulbs,
and longer-lived and more efficient.
 Nanotechnology applications
Field Emission and Shielding

• High electrical conductivity of carbon nanotubes means that they

will be poor transmitters of electromagnetic energy.
• A plastic composite of carbon nanotubes could provide lightweight
shielding material for electromagnetic radiation.
• This is a matter of much concern to the military, which is developing
a highly digitized battlefield for command, control, and
communication.
• The computers and electronic devices that are a part of this system
need to be protected from weapons that emit electromagnetic
pulses.
 Nanotechnology applications
Field Emission and Shielding

• High electrical conductivity of carbon nanotubes means that they

will be poor transmitters of electromagnetic energy.
• A plastic composite of carbon nanotubes could provide lightweight
shielding material for electromagnetic radiation.
• This is a matter of much concern to the military, which is developing
a highly digitized battlefield for command, control, and
communication.
• The computers and electronic devices that are a part of this system
need to be protected from weapons that emit electromagnetic
pulses.
 Nanotechnology Medical applications
• Nanomaterials show very high efficiency in destroying cancer cells
and are already undergoing clinical trials.
• Allow cancer cells to be targeted specifically and enable detailed
imaging of tissues, making planning further therapy much easier.
• Nanostructures may be used in both preventing and increasing the
stability of atherosclerotic lesions.
• Other potential applications of nanotechnology in medicine include:
1. nano adjuvants with immune modulatory properties used to deliver vaccine
antigens;
2. the nano-knife, an almost non-invasive method of destroying cancer cells with
high voltage electricity;
3. carbon nanotubes, for repairing damaged tissues and might be used to
regenerate nerves in the future.
 Nanotechnology Medical applications

• Doctors have used nanotechnology to treat cancer for more than a

decade.
• Two approved treatments -- Abraxane and Doxil -- help
chemotherapy drugs work better.
• Abraxane is a nanoparticle made from protein albumin attached to
the chemo drug docetaxel.
• It stops cancer cells from dividing.
• Abraxane treats breast and pancreatic cancers that have spread, and
non-small-cell lung cancer.
• Doxil is the chemo drug doxorubicin wrapped inside a liposome, a
fatty sac.
• It disrupts cancer genes so the cancer cells can't divide.
• Doxil treats ovarian cancers, multiple myeloma, and
Kaposi's sarcoma.