Unit-2

Properties of Nano Materials

 SIZE
A meter is about the distance from the tip of your
nose to the end of your hand (1 meter = 3.28 feet).

Millimeter- One thousandth of meter.(10-3m)

Micron: a micron is a millionth of a meter (or) one

thousandth of millimeter (10-6m)

Nanometer:

A nanometer is one thousandth of a micron (10–9m)

(or) a billionth of a meter. ie.,one billion nanometers
in a meter.
• Composites made from particles of nano-size ceramics or metals
smaller than 100 nanometers can suddenly become much stronger
than predicted by existing materials-science models.

• For example, metals with a so-called grain size of around 10

nanometers are as much as seven times harder and tougher than
their ordinary counterparts with grain sizes in the micro meter
range.

• The Nano particles affects many properties such as

Melting point
Boiling point
Band gap
Optical properties
Electrical properties
Magnetic properties
• .Even the structure of materials changes with respect to Size
The properties of materials can be different at the Nanoscale for two
main reasons:
First, Nanomaterials have a relatively larger surface area when
compared to the same mass of material produced in a larger form.

Nano particles can make materials more chemically reactive and affect
their strength or electrical properties.
Second, quantum effects can begin to dominate the behaviour of matter
at the Nanoscale
Nanoscale materials are divided into three category,
1. Zero dimension – length , breadth and heights are confined at single
point. (for example, Nano dots)
2. One dimension – It has only one parameter either length (or) breadth
(or) height ( example:very thin surface coatings)
3. Two dimensions- it has only length and breadth (for example,
nanowires and nanotubes)
4. Three dimensions -it has all parameter of length, breadth and height.
(for example, Nano Particles).
 Melting Point

The melting point decreases dramatically as the particle size

gets below 5 nm

Source: Nanoscale Materials in Chemistry, Wiley, 2001

 Band gap
The band gap is increases with reducing the size of the
particles
 Surface Area
The total surface area (or) the number of surface atom increases
with reducing size of the particles
 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.
– The 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 Due to increase energy level
spacing
• 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.
 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.

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
 Optical Properties

Example: Absorption Spectra of CdSe quantum dots

 Nano gold appears red in
color why ?
• Nanosized gold appears red
in color
– 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
Optical properties are connected with electronic
structure, a change in zone structure leads to a
change in absorption and luminescence spectra.
 Blue shift
Blue shift refers to a shortening of a transmitted signal's
wavelength, and/or an increase in its frequency. The name
comes from the fact that the shorter-wavelength end of the
optical spectrum is the blue end, hence, when visible light is
compacted in wavelength, it is "shifted towards the blue", or
"blue-shifted". Blue shift phenomenon is a quantum size
effect.
Transformation of zone structure of a
solid under reduction of its size from
macro to nano-scale down to a single
atom, showing the increase of the band
gap g ∆E and the blue shift hω = ∆E
for nanoparticles and nanostructured
state of matter.

W is a work function, EF is a Fermi energy, HOMO is the highest occupied molecular

orbital, LUMO is the 36lowest unoccupied molecular orbital
 Electrical Properties
Electrical Properties of Nanoparticles” discuss about
fundamentals of electrical conductivity in nanotubes and
nanorods, carbon nanotubes, photoconductivity of nanorods,
electrical conductivity of nanocomposites. One interesting
method which can be used to demonstrate the steps in
conductance is the mechanical thinning of a nanowire and
measurement of the electrical current at a constant applied
voltage.
The important point here is that, with decreasing diameter of
the wire, the number of electron wave modes contributing to
the electrical conductivity is becoming increasingly smaller by
well-defined quantized steps.
 Electrical Properties
 The effects of size on electrical conductivity of
nanostructures and nanomaterials are complex, since
they are based on distinct mechanisms. These
mechanisms can be generally grouped into categories
 surface scattering including grain boundary scattering
 coulomb charging and tunneling
 widening and discrete of band gap
 change of microstructures.

 In addition, increased perfection, such as reduced

impurity, structural defects and dislocations, would
affect the electrical conductivity of nanostructures and
nanomaterials.
 Surface Scattering
• Electrons have a mean-free-path (MFP) in
solid state materials.
• MFP is the distance between scattering
events as charge carriers move through the
material.
• In metals, the MFP is on the order of 10’s of
nanometers.
• If the dimensions of a nanostructure are
smaller than the electron MFP, then surface
scattering becomes a factor.
 Surface Scattering
• There are two types of surface scattering:
elastic and inelastic.
• Elastic scattering does not affect
conductivity, while inelastic scattering
decreases conductivity.
Elastic Inelastic
Macroscale Material
d > MFP

Nanowire
MFP d < MFP
Coulomb charging and Tunneling
 The principal of quantum
tunneling
Electrons exhibit wave behavior
and their position is presented by a
wave(probability) function.

The wave function represents a

finite probability of finding an
electron on the other side of the
potential barrier.

Since the electron does not posses

enough kinetic energy to overcome
the potential barrier, the only way
the electron can appear on the
other side is by tunneling through
the barrier.
 Widening and Discrete Band gap
In bulk materials, atoms and
molecules possess many discrete
electronic energy levels. The
electronic wave functions of these
atoms/molecules overlap with
each other and give band
structure. With decrease in particle
size the spacing between energy
levels increases and the difference
between energy values of
conduction band and valence band
increases. Fig. 1.6 shows the
changes in the electronic structure
accompanying reduction in size of
semiconductor/insulating
materials
Dielectric Properties
Almost all electronic devices all your
devices like computers or image
processing devices or digital cameras
etc. use dielectric materials.
Everything has integrated circuits or
chips which have many dielectrics
involved. Now, these dielectrics in
today’s world are based on what is
called M L C C’s that is the
multilayer ceramic capacitors and the
main material which is used as a
multilayer ceramic capacitor is
barium titanate. So, they this barium
titanate is acts as a capacitor and is
involved in the fabrication of the chip
or is applied in devices.
 Dielectric Properties
Since a multilayer ceramic capacitor being used in these chips the
thickness of these layers have to be reduced.

Multilayer means several layers of these ceramic capacitor is

involved. Now, if each layer is made up of the barium titanate
material if you use nanoparticles instead of micron sized particles.

Then we are be able to put many such layers in one chip. So, typical
sizes below 100 nanometers will be required in the future for such
M L C C or multi layer ceramic capacitor applications.

So, the dielectric nanoparticles are important because we can pack

these nanoparticles in very dense manner. And they will still have
high surface are, because the particle size is very small.
Because of the polymers have flexibility. So that we can make flexible dielectric films
or embedded flexible dielectric films where the dielectric nanoparticles are embedded
within this polymer film. And such flexible films are of importance in flexible
electronics especially in cell phones in laptops etcetera.
Size of the particle decreases- number of particles on surface area
increases

Surface properties dominate

Decrease the size of the particle for the same area you can put more
number of particles if you have smaller particles, Hence this is very
important property of nanostructured materials.
 Thermal Properties
Heat is transported in materials by two different mechanisms:

 Due to phonons and

 Free electrons.

In metals, the electron mechanism of heat transport is significantly

more efficient than phonon processes.

In the case of nonmetals, phonons are the main mechanism of

thermal transport.

In both metals and nonmetals, as the system length scale is

reduced to the nanoscale, there are quantum confinement and
classical scattering effects.
 Thermal Properties of nanomaterials
The progression of of heat through nanomaterials is slow compared
to other properties such as optical, electrical, mechanical and
magnetic properties as there is a difficulty in the measuring and
controlling the thermal transport at nano dimension.

In the macromaterials, there is a sufficient dimension to measure

thermal properties in different regions but, with nanomaterials, it is
very difficult to define the local temperature due to small
dimensions. Regardless of these difficulties in nanomaterials, recent
advances showed that some nanomaterials show extraordinary
thermal properties than conventional materials. For eg: carbon
nanotubes show very high thermal conductivity and high anisotropy
of heat transport because of its tubular structures. Interfaces also
play a crucial role in explaining thermal properties as they assist in
conduction of heat due to photon and photon scattering.
Also, nanowires show very low thermal conductivity due to the
different behaviour of phonons compared to bulk materials.

In addition to 1D nanowires, other types of nanostructures such as

multi-layers and superlattices also displayed low thermal
conductivity.

Due to this behavior, multi-layers and superlattice nanomaterials

have been using in various applications. The multilayer thin films
are used in engines to improve the efficiency and they behave as
thermal barriers even at higher temperatures.

Low thermal conductivity super-lattice semiconductors have been

selected as good candidates for the production of thermoelectric
power in which they reduce phonon transport as well as electronic
band structure.
Melting Temperature: The large surface to volume ratio of nano materials
has a very unusual effect on their thermal properties, they show lower melting
temperature as compared to the solids. This is explained as follows: when a large
system like a solid is heated, the energy added is completely converted into
potential energy of atoms or molecules (solid is changed to liquid).
In a similar way when a nanomaterial is heated, will tries to avoid the molten
states (Molten is simply an object/ material that has been melted or liquefied by
heat. It's usually objects with high melting point that requires high temperatures
to be liquefied) and converts some of its kinetic energy to potential energy. The
kinetic energy of the nanomaterial decreases and it becomes cooler. Similar
behavior is seen in decrease of melting temperature for gold nanoparticles
 Introduction to Magnetism
Magnetism is virtually universal.

 Coherent magnetic fields have been found at the scale of the

galaxies and cluster of galaxies.
 Earth's magnetic field has a strength of about 1 G and
reverses itself with an average period of about 2 x 105 years.
 Magnetic nanoparticles are found in some rocks and can be
used to determine the earth's magnetic field (strength and
direction) in the past.
 Magnetotactic bacteria have nanometer-sized magnets, which
they use for alignment with the earth's magnetic field.
 Many birds (e.g. the homing pigeon) and other living
creatures have clusters of nanoparticles (~2-4 nm in the
pigeon) in their beak area, which helps them with their
homing ability.
 Magnetic Moment Vector (m or µ). |m| = IA, Units: [Am2] or
equivalently [Joule/Tesla]. Measure of the strength of the magnet.

 Magnetic field strength/Magnetizing force (H). Units: [A/m]

Measure of the strength of the externally applied field.
Magnetization (M) = magnetic moment (m) per unit volume (V).
Units: [A/m] M=m/ V

 M measures the materials response to the applied field H (of

course we know from our experience with permanent magnets that
M can exist even if H is removed). M is the magnetization induced
by the applied external field H.

 σ = magnetic moment per unit mass = m/mass. Units: [Am2/kg]

 Magnetic induction/Magnetic flux density (B) = Magnetic flux

per unit area. Units: [Tesla = Weber/m2 = Vs/m2 = Kg/s2/A]
B is the magnetic flux density inside the material.

 B = µ0 (H + M) (µ0 is the magnetic permeability of vacuum =

H/m = Wb/A/m = mKg/s2A2)
Permeability (µ).Units: [dimensionless]
µ = B/ H

Magnetic susceptibility (χ ). (volume susceptibility) Units:

[dimensionless] χ = M/ H (the symbol χv is also used to
emphasize that the quantity is per unit volume).

χm (mass susceptibility) and χM (molar susceptibility) are also

used. Susceptibility is a better quantity compared to
permeability to get a 'feel' and 'physical picture' of the type
of magnetism involved.
Magnetic nanostructures in bulk
materials
Dependence of magnetic moment on the dimensionality of the
system
Superparamagnetism
Ferromagnetic materials consist of magnetic domains within
which the spins are parallel. When the particle size is reduced
to very small sizes (typically less than 20 nm) the entire particle
becomes a single domain. On further reduction in size (about
less than 5 nm) the spins get thermally disordered in the
absence of magnetic fields. When an external magnetic field is
applied the spins are able to align in the direction of applied
magnetic field, making them behave as super paramagnets (i.e.,
in the absence of external field the particle is paramagnetic and
in the presence of a field all the spins are aligned in parallel,
leading to a large increase in magnetization). This is an
interesting example in which a ferromagnetic material in bulk
behaves like a paramagnet when particle size is made very
small.