Dr.

Shaik Kareem Ahmed 2018

DIELECTRICS MATERILAS

1. Explain different types of Dielectric polarization

Electronic Polarization

The electronic polarization is due to the displacement of

the positively charged nucleus and the negative electrons
of an atom in opposite directions, on application of an
electric field. On applying a field, the electron cloud
around the nucleus readily shifts towards the positive end
of the field. As the nucleus and the center of the electron cloud are separated by a certain
distance, dipole moment is created within each atom. The extent of this shift is
proportional to the field strength. This type of polarization is independent of temperature.

Ionic Polarization

The ionic polarization is due to the displacement of cations

and anions in opposite directions. This occurs in ionic solids.
This polarization is independent of temperature. It does not
occur in covalent crystals.

Orientational Polarization

When an external field is applied to polar dielectrics, they tend

to align themselves in the direction of external applied field. The
polarization due to such alignment is called Orientational
polarization. The Orientational polarization is strongly
temperature dependent. With increase of temperature, the
thermal energy tends to randomize the alignment. An expression
for Orientational polarization can be obtained by following the same procedure adopted in
Langevin theory of paramagnetism. Here, instead of magnetic field, electric field is used.

Space- charge Polarization

Space charge polarization occurs due to accumulation of charges

at the electrodes or at the interfaces in multiphase dielectrics. As
shown in figure, the ions diffuse over appreciable distance in
response to the applied field. This gives rise to redistribution of
charges in dielectric medium. The space charge polarization is
not an important factor in most common dielectrics. It is found
in ferrites and semiconductors.

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Dr. Shaik Kareem Ahmed 2018

2. Derive expression for Electronic polarization

The displacement of the positively charged nucleus and the (negative) electrons of an atom
in opposite directions, on application of an electric
field, result in electronic polarization

From above diagram nucleus of charge Ze is

surrounded by an electronic cloud –Ze distributed
in a sphere of radius R. The charge density  is
given by

 Ze  3  Ze 
 
4  R 3 
--------- (1)
4 / 3R 3

When an external field of intensity E is applied, the nucleus and the electrons experience Lorentz
forces of magnitude ZeE in opposite directions. Hence the nucleus and electron cloud are pulled
apart. When they are separated a coulomb force develops between them, which tend to oppose
the displacement. When these forces are equal and opposite, equilibrium is reached. Let x be the
displacement Since nucleus is much heavier than the electron cloud it is assumed that only the
electron cloud is displaced when external field is applied.

Lorentz force = -ZeE

1  Charge enclosed in the sphere of radius x 

Coulomb force = Ze   
4 0  x2 

The charge enclosed in the sphere after applying the field is given by = density X Volume

4
  x 3   (substitue equ  value form equatio 1)
3
4   3  Ze  
  x3   3 
3  4  R  
Zex 3
 3
R

Ze   Zex 3  Z 2e2 x
Hence Coulomb force is  
4 0 x 2  R 3  4 0 R 3

Under equilibrium conditions, these two forces are equal and opposite. Therefore,

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Dr. Shaik Kareem Ahmed 2018

1 𝑍2𝑒 2𝑥
𝑍𝑒𝐸 =
4𝜋𝜖0 𝑅 3

1 𝑍𝑒𝑥 4𝜋𝜖0 𝑅3 𝐸
𝐸=
4𝜋𝜖0 𝑅 3
or 𝑥= 𝑍𝑒
Thus the displacement of the electron cloud is proportional to the applied field. Thus the two
electric charges +Ze and –Ze are separated by a distance x under the action of the applied field thus
constituting induced dipoles. Induced dipole moment is given by

4𝜋𝜖0 𝑅3 𝐸
𝜇𝑒 = 𝑐ℎ𝑎𝑟𝑔𝑒 X displacement = Ze X 𝑥 = 𝑍𝑒
𝑍𝑒

= 4𝜋𝜖0 𝑅 3 𝐸 ----- (3)

But from the definition of electronic Polarizability 𝜇𝑒 = 𝛼𝑒 𝐸 ----- (4)

Comparing (3) and (4) we get 𝜶𝒆 = 𝟒𝝅𝝐𝟎 𝑹𝟑

Thus electronic Polarizability is directly proportional to the volume of the atom.

3. Explain frequency and temperature dependence of dielectric

polarization

Frequency dependence of the dielectric Polarizations:

On application of an alternating field across the material, the polarization process occurs
as a function of time. Electronic polarization is extremely rapid and is complete at any
instant of time even when the frequency of the voltage is very high in the optical range.
Thus it occurs at all frequencies. But ionic polarization is slower and the ions do not
respond at all when the voltage is corresponds to optical frequencies. That is, the electric
field here is changing too rapidly for the ions to reorient themselves in response to the
field. Therefore, ionic
polarization does not occur at
optical frequencies where as it
occurs at infrared frequencies.
The Orientational polarization is
slower than the ionic polarization
and occurs only at microwave
frequencies which are smaller
than the infrared frequencies.
Space-charge polarization is
slowest process and occurs at

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Dr. Shaik Kareem Ahmed 2018

power frequencies (50-60 per sec).

Thus at low frequencies, the value of total polarization is very high and at high frequencies
(optical frequencies) the value of total polarization is very small. Above 1015 Hz, None of
the polarization mechanisms are able to switch rapidly enough to remain in step with the
field. The material no longer possess the ability to polarize, and the dielectric constant
drops to 1, the same as that of vacuum.

Temperature dependence of the dielectric Polarizations:

Usually Orientational polarization depends strongly on temperature whereas the
electronic and the ionic polarizabilities are practically independent of temperatures for
normal temperatures. Normal temperatures oppose the permanent dipoles to align in the
field direction. But higher temperatures facilitates the movement of ions and molecules so
that a given polarization process which is not possible at higher frequencies at normal
temperature can occur at higher frequencies at high temperatures.

4. Determine dielectric constant by Schering bridge method

Principle: It is based on the measurement of the capacitance of the capacitor without the
dielectric (C1) and capacitance of the capacitor with dielectric material (C1’ )

A circuit diagram of a general Schering bridge is shown in Figure.

C1=capacitor whose capacitance is to be measured.

R1= a series resistance representing the loss in the capacitor C1
C2=Standard capacitor
R3=Non-inductive variable resistance
R4=Non-inductive Resistance
C4=Variable capacitor
D= A.C. Null detector
HFO=High Frequency Oscillator

(i) First without inserting dielectric inside C1, the bridge is balanced by varying C4 and
R3. When current flowing through the detector becomes zero,

1 1
𝑗𝜔𝐶1 + 𝑅1 𝑗𝜔𝐶2
=
𝑅3 𝑅4
1 + 𝑗𝜔𝐶4 𝑅4

1 𝑅3 (1 + 𝑗𝜔𝐶4 𝑅4 )
[(𝑅1 + ] 𝑅4 =
𝑗𝜔𝐶1 𝑗𝜔𝐶2

𝑅4 𝑅3 𝑅3 𝑅4 𝐶4
𝑅1 𝑅4 + = +
𝑗𝜔𝐶1 𝑗𝜔𝐶2 𝐶2

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Dr. Shaik Kareem Ahmed 2018

Equating the real and imaginary parts, we get

𝑅3 𝐶4 𝑅4 𝐶2
𝑅1 = and 𝐶1 =
𝐶2 𝑅3

Since R4 and C2 are fixed, the dial of R3 is calibrated to read the capacitance C1 directly.

(ii) The dielectric specimen should be in the size of C1 (in its area) and inserted
between the plates C1. Now once again the bridge is balanced. Now the dial
reading in R3 will give the value of new capacitance C1’
𝑪 𝑪′
Then the dielectric constant can be calculated using the formula𝜺𝒓 = 𝑪 = 𝑪𝟏
𝟎 𝟏

5. Discuss ferroelectricity in dielectrics

Ferroelectricity refers to the creation of enormous value
of induced dipole moment in a weak electric field as well
as existence of electric polarization even in the absence
of applied electric field. Ferroelectricity is a result of
dielectric hysteresis.

When a ferroelectric material is subjected to electric

field, the polarization P versus electric field E describes a
closed loop called as hysteresis loop as shown figure. Let
initially, the material has polarization equal to zero. When the electric field is applied, the
polarization increases along the path OA. After the point A, the polarization will not
increase even if E is increased. This polarization is called saturation polarization P s.

When E is reduced gradually such that E=0, the curve traces the path AB. It is observed
that certain amount of polarization called remnant polarization P r is still present. This is
the polarization that exists in the absence of external electric field. Therefore this is called
spontaneous polarization.

In order to reduce the polarization to zero, a field in reverse direction must be applied. This
is denoted by Ec called as coercive field. Further increase of field brings the material to
saturation state. When the field is brought to zero and increased in the positive direction,
a curve FGA is traced. Now, the hysteresis cycle is completed. The area bounded within the
curve represents the loss of electrical energy per cycle.

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Dr. Shaik Kareem Ahmed 2018

6. Write a short notes on Barium titanate

The structural changes in Barium titanate (BaTiO3)

crystal due to lattice variation give rise to
Ferroelectricity. Above Curie temperature (approx.
120oC), BaTiO3 has a cubic crystal structure
withBarium ions are at the corners the titanium
ions exactly at the body centre, and Oxygen ions are
at the face centres. At those temperatures, there is
no spontaneous dipole moment.

When the crystal is cooled below 120oC, one axis (axis C) stretches and the other axes
shrink and turn into a tetragonal crystal structure. In this case, polarization happens as a
result of the unit shift of axially elongated Ti- ion crystal. This polarization occurs without
applying an external electric field or pressure, and is known as "spontaneous polarization."
This characteristic is called “ferroelctricity”. The displacements of titanium ions create
electric dipoles and all the dipoles of the adjacent unit cells get aligned in the same c-
direction. Similarly at 5oC spontaneous polarization direction corresponds to the face
diagonal direction and at -80oC the direction corresponds to a body diagonal. At those
temperatures there is an enormous value for dielectric constant.

7. Write Applications of ferroelectric materials

 Capacitors
 Non-volatile memory
 Piezoelectrics for ultrasound imaging and actuators
 Electro-optic materials for data storage applications
 Thermistors
 Switches known as transchargers or transpolarizers
 Oscillators and filters
 Light deflectors, modulators and displays

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Dr. Shaik Kareem Ahmed 2018

QUESTIONS FROM PREVIOUS EXAMINATIONS

1. Explain the phenomenon of Ferro-electricity and discuss how dielectric constant of

Barium titanate changes as its temperature is decreased. [June 2011, 7 marks]
2. Write few applications of ferroelectrics. [June 2011, 3 marks]
3. What are dielectrics? Explain various electrical polarization mechanisms. [Jan 2012, 6
marks]
4. Draw the crystal structure of Barium titanate above 393 K and explain how its structure
and polarization changes with decreasing temperature. [Jan 2012, 3 marks]
5. Derive the expression for electronic Polarizability in case of dielectrics. [June 2012, 5
marks]
6. Explain the concept of spontaneous polarization in Ferro-electrics. [June 2012, 3 marks]
7. Explain the experimental method of Schering Bridge for determination of dielectric
constant. [Jan 2013, 5 marks][April/May-2007,5marks]
8. What are dielectrics? Explain electronic polarization in detail. [Dec-2007& 2008,
3marks]

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Dr. Shaik Kareem Ahmed 2018

UNIT-IV Thin Films

1. Explain Thin film preparation by Thermal evaporation techniques

Thin film: A thin film is a layer of material on a substrate ranging from fractions of a
nanometer to several micrometers (100 to 1000nm) in thickness.
When bulk material is heated to a high temperature, it vaporizes and the condensation of
the vapor onto a cold substrate yields thin films.
(a) Simple Thermal Evaporation: Thermal
evaporation technique requires vacuum up to
10-5 torr. Fix the boat with material which is to
be evaporated between two electrodes and
arrange and fix the substrates to substrate
holder over the boat at the distance of 30 to
40 cm from the boat. Then place the bell jar on
these and create the vacuum up to 10-5 torr.
After achieving the required vacuum, switch
on the electrodes and heat the boat slowly.
Material in the boat starts to evaporate and
condense on the substrate resulting thin film formation on substrate as shown in figure.

(b) Simultaneous Evaporation: This is

similar to the above method with little
modification. Here two or three sets of
electrodes are required and each set is used to
evaporate particular material. After setting
the voltages to each set of electrodes, simply
switch on the dimmerstats of all sets
simultaneously as shown in figure till the
material in each boat is evaporated. Materials
from different boats evaporate
simultaneously and film formation takes place.
(c) Sequential Evaporation: This is similar to the above method with little
modification in the operation. In this method materials get evaporated one after the other
sequentially for a few seconds and continue this process until the entire material in each
boat gets evaporated.
(d) Laser Evaporation: Most intensive laser
beam may be used to heat and vaporize
materials by focusing the beam onto surface of
the material to be evaporated as shown in figure.
(here boat is not connected to power supply) and
film formation takes place on substrates. These
films can be heated and annealed to get
uniformity.

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Dr. Shaik Kareem Ahmed 2018

(e) Electron Beam Evaporation:In general in thin film

preparation, little contamination in film may take place due
to heating boat. In turn the properties of the film will be
different from expected. In order to avoid this electron
bombardment heating technique were developed in which
material is heated by focusing high intense electron beam
onto material and gets evaporated as shown in figure.

2. Explain applications of Thin Films

Field Examples

Optics Antireflection coating; on lenses or solar cells,

Reflection coatings for mirrors.
Coatings to produce decorations (color, luster,
Interference filters.
CD's, DVD's and upcoming D's.

Chemistry Diffusion barriers.

Protection against corrosion / oxidation.
Sensors for liquid / gaseous chemicals.

Mechanics "Hard" layers (e.g. on drill bits).

Adhesion providers.
Friction reduction.

Magnetics "Hard" discs.

Video / Audio tape.
"SQUIDS"

Electricity Insulating / conducting films; e.g. for resistors, capacitors.

(without Piezoelectric devices
semiconductors)

Semiconductor high-speed transistors, solar cells, solid-state lighting, sensors, information

Technology storage devices, etc.

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Dr. Shaik Kareem Ahmed 2018

3. Explain construction and working

of Solar

It is a p-n junction diode, which converts light

energy into electrical energy. This effect is
called photovoltaic effect and the device is
called photovoltaic cell or solar cell.

Construction: It consists of
heavily doped P-N junction, the top layer forming the N-region usually made very thin to
allow the solar radiation to fall onto the junction. To avoid the electron hole
recombination before reaching their end point, prepare a comb shaped grid structure on
the upper part. The gap between successive vertical lines should be less than the mean
free path of the particle generated between them. An anti reflecting coating on the top is
made to prevent light losses due to reflection from the surface of the solar cell. To get the
desired voltage, several solar cells are connected in series and to get desired current,
several solar cells are connected in parallel. After completion of above all, finally the cell is
encapsulated in a plastic material.

Working:When a solar cell is exposed to solar radiation a photon has energy less than the
band gap Eg makes no contribution to the cell output. A photon having energy greater
than Eg contributes an energy Eg to the cell output and energy greater Eg is wasted as heat.
The absorbed energy of photon excites valence electron to the conduction band leaving
holes in the valence band. So electrons are collected on N-side and holes are collected on
P-type of a P-N solar cell. An electric field within the photovoltaic cell acts to force the
electrons in a certain direction. A metal grid on either side of the solar cell allows the
electrons to collect and, if connected to an external circuit, a current will flow.

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Dr. Shaik Kareem Ahmed 2018

I-V Characteristics:To draw I-V characteristics of solar cell, complete the circuit as shown
in figure.Switch on the light on cell and the maximum voltage measured between the two
ends of the cell is called open circuit voltage (VOC). If the minimum load is connected to
the cell, the charge carriers moves in the circuit
creating the maximum current called short circuit
current(ISC).
Now increase the potentiometer, voltage increases
but current decreases. Note down these readings
upto maximum value of voltage where the current will
be minimum. Repeat the experiment for two or three
light intensities and draw the graph as shown.
Now select a point on each graph such that if the
perpendiculars are drawn on X-axis and Y-axis from this point, then the maximum area
formed by the rectangle. That indicates the maximum power extracting. Then note down
Vm on X-axis and Im on Y-axis.

Fill factor(FF):It is defined as the reliable and maximum extracting power of the cell and is
𝐼 𝑉
given by 𝐹𝐹 = 𝐼𝑚𝑉𝑚
𝑠𝑐 𝑜𝑐

𝑃𝑜𝑤𝑒𝑟 𝑜𝑢𝑡𝑝𝑢𝑡 𝑝𝑒𝑟 𝑢𝑛𝑖𝑡 𝑎𝑟𝑒𝑎

Efficiency 𝜼 = × 100
𝑃𝑜𝑤𝑒𝑟 𝑖𝑛𝑝𝑢𝑡 𝑝𝑒𝑟 𝑢𝑛𝑖𝑡 𝑎𝑟𝑒𝑎

QUESTIONS FROM PREVIOUS EXAMINATIONS

1. Write notes on solar-cells. [June 2011, 5 marks]
2. Distinguish between bulk, thin film and nano-scale materials. [Jan 2012, 3 marks]
3. Explain the thermal evaporation method of depositing thin films. [Jan 2012, 7 marks]
4. Explain in detail thermal evaporation technique to prepare a thin film [June 2012, 7 marks]
5. What is thin film and explain the thermal evaporation method for preparation of thin film? [Jan
2013, 6 marks]
6. Distinction between bulk, thin films and nano materials (June-2013, 3)
7. Describe the working of a thin film solar cell. (Dec-2013, 5)

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Dr. Shaik Kareem Ahmed 2018

Unit IV Experimental Techniques

1. Explain priciple of X-ray Fluorescence

X-ray fluorescence is a non-destructive method for elemental analysis of solids and liquids. The
process of emission of characteristic X-rays is called X-ray fluorescence.

In X-ray fluorescence the following steps are involved

1. In most cases, the innermost K and L shells are involved.

2. An electron in the K shell is ejected from the atom by an external excitation x-ray, creating a
vacancy.
3. An electron from the L or M shell "jumps in" to fill the vacancy. In the process, it emits a
characteristic x-ray (𝐾𝛼/𝛽/ 𝛾or 𝐿𝛼/𝛽/ 𝛾) unique to this element and in turn, produces a vacancy
in the L or M shell.
4. When a vacancy is created in the L shell by either the primary excitation x-ray or by the previous
event, an electron from the M or N shell "jumps in" to occupy the vacancy. In this process, it
emits a characteristic x-ray unique to this element and in turn, produces a vacancy in the M or
N shell.

A typical X-ray spectrum from an irradiated sample will display

multiple peaks of different intensities from which elements present
in the sample can be identified. The key part here is that the energy
levels of atoms are very specific to each element.
2. Explain RAMAN effect
Raman scattering or the Raman is the inelastic scattering of a photon by molecules
which are excited to higher vibrational or rotational energy levels. It was discovered
by C. V. Raman and K. S. Krishnan
When photons are scattered from an atom or molecule, most photons are elastically
scattered (Rayleigh scattering), such that the scattered photons have the same energy
(frequency and wavelength) as the incident photons. A small fraction of the scattered
photons (approximately 1 in 10 million) are scattered by an excitation, with the
scattered photons having a frequency different from, and usually lower than, that of
the incident photons. In a gas, Raman scattering can occur with a change in energy of

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Dr. Shaik Kareem Ahmed 2018

a molecule due to a transition to another (usually higher) energy level. Chemists are
primarily concerned with the transitional Raman effect.
According to quantum theory, the Raman effect may be regarded as the outcome of
the collision between the light photons and molecules of the substance.
Applications
1. Raman spectroscopy is commonly used in chemistry, since vibration information is
specific to the chemical bonds and symmetry of molecules. Therefore, it provides
a fingerprint by which the molecule can be identified.
2. Raman gas analyzers have many practical applications. For instance, they are used
in medicine for real-time monitoring of anesthetic and respiratory gas mixtures
during surgery.
3. Raman spectroscopy has also been used to confirm the prediction of existence of
low-frequency phonons in proteins and DNA greatly stimulating the studies of low-
frequency collective motion in proteins and DNA and their biological functions
4. Raman scattering by an anisotropic crystal gives information on the crystal
orientation. The polarization of the Raman scattered light with respect to the
crystal and the polarization of the laser light can be used to find the orientation of
the crystal, if the crystal structure known.
3. Explain principle of Electron microscope (SEM) with neat diagram
Accelerated electrons in an SEM carry significant amounts of kinetic energy, and this
energy is dissipated as a variety of signals produced by electron-sample interactions
when the incident electrons are decelerated in the solid sample.
These signals include secondary electrons, backscattered electrons, diffracted
backscattered electrons, photons (characteristic X-rays that are used for elemental
analysis and continuum X-rays), visible light, and heat. Secondary electrons and
backscattered electrons are commonly used for imaging samples: secondary electrons
are most valuable for showing morphology and topography on samples and
backscattered electrons are most valuable for illustrating contrasts in composition in
multiphase samples (i.e. for rapid phase discrimination).
X-ray generation is produced by inelastic collisions of the incident electrons with
electrons in discrete orbital (shells) of atoms in the sample. As the excited electrons
return to lower energy states, they yield X-rays that are of a fixed wavelength (that is
related to the difference in energy levels of electrons in different shells for a given
element). Thus, characteristic X-rays are produced for each element in a mineral that
is "excited" by the electron beam.
SEM analysis is considered to be "non-destructive"; that is, xrays generated by
electron interactions do not lead to volume loss of the sample, so it is possible to
analyze the same materials repeatedly.

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Dr. Shaik Kareem Ahmed 2018

Applications
1. The SEM is routinely used to generate high-
resolution images of shapes of objectss and to
show spatial variations in chemical
compositions:
2. Acquiring elemental maps or spot chemical
analyses using EDS
3. Discrimination of phases based on mean
atomic number (commonly related to relative
density) using Back scattered elections
4. Compositional maps based on differences in
trace element "activitors" (typically transition
metal and Rare Earth elements) using CL.
5. The SEM is also widely used to identify phases
based on qualitative chemical analysis and/or
crystalline structure. Precise measurement of very small features and objects
down to 50 nm in size is also accomplished using the SEM. Backscattered electron
images (BSE) can be used for rapid discrimination of phases in multiphase samples.
SEMs equipped with diffracted backscattered electron detectors (EBSD) can be
used to examine micro fabric and crystallographic orientation in many materials.

4. Explain principle of AFM with neat diagram

The atomic force microscope (AFM) was
invented by Binning et al. in 1986. The AFM
measures the forces acting between a fine tip
and a sample. The tip is attached to the free end
of a cantilever and is brought very close to a
surface.
Attractive or repulsive forces resulting from
interactions between the tip and the surface will
cause a positive or negative bending of the
cantilever. The bending is detected by means of
a laser beam, which is reflected from the back
side of the cantilever. Figure shows the basic
concept of AFM. The working principle of AFM is Hooks law.
Contact mode imaging: cantilever’s tip is brought in contact with the surface of the
sample. The force between the tip and the sample causes the cantilever to deflect in
accordance with Hooke's Law.The amount of deflection is measured by reflecting light
from a laser diode off the back of the beam, and onto an array of position-sensitive photo
detectors.

Non-contact imaging employs a small piezo element mounted under the cantilever to
make it oscillate at its resonance frequency. When this oscillating cantilever is brought

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Dr. Shaik Kareem Ahmed 2018

down to within 10-100 nm from the sample surface, the oscillation gets modified
by interaction forces (Van der Waals, electrostatic, magnetic, or capillary forces) between
the tip and the sample.

The advantages of AFM over electron microscopy include the following: 1) it generates
true, 3-dimensional surface images; 2) it does not require special sample treatments that
can result in the sample's destruction or alteration; and 3) it does not require a vacuum
environment in order to operate (it can operate in both air and liquid). On the other hand,
itsdisadvantages include the following: 1) the image size that it provides is much smaller
than what electron microscopes can create; and 2) it is slow in scanning an image, unlike
an electron microscope which does it in almost real-time.

Questions from previous papers

1. Explain the basic principle used in atomic force microscopes. [Jan 2012, 2 marks]
2. Explain the principle of X-ray fluorescence. [Jan 2013, 2 marks]
3. Explain the construction & working of SEM . [Jun11, 4 m] (June-13, 6m)
4. What is the principle of X-ray fluorescence and mention its applications
(Dec-13, 5)&(June-13, 5)

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Dr. Shaik Kareem Ahmed 2018

UNIT-V Nanomaterials

1. What are Nano materials

Nano means 10-9. A nano meter (nm) is one thousand millionth of a meter (i.e.,10-9m). Atoms are
extremely small and the diameter of a single atom can vary from 0.1 to 0.5 nm depending on the
type of the elementThe materials which have at least one external dimension in the size range from
approximately 1nm to 100 nm are called nanomaterials.

If one dimension of the material is reduced to nano range while the other two dimensions remain
large, then the material or structure is called quantum well. Quantum well is also called nanolayers.

If two dimensions are reduced to nano size while the third dimension remains large, then the
resulting structure is called quantum wire. A quantum wire is a one dimensional nanostructure.

If all the three dimensions lie between ‘1’ to ‘100’ nm they are considered as zero dimensional
nano structures. These are also called as nano particles or nano powders.

A number of physical phenomena become noticeably pronounced as the size of the system
decreases. For example, opaque substances become transparent (Copper); inert materials become
catalysts (Platinum & gold); stable materials turn combustible (Aluminum); solids turn into liquids
at room temperature (Gold); insulators become conductors (Silicon).

2. Explain Properties of Nano materials

As the size of the nanoparticle is very very less, these materials exhibit peculiar physical,
electrical, magnetic, mechanical and chemical properties. Some of them are discussed
below.

1. Electrical properties
(a) The energy bands in these materials will be very narrow
(b) In nano-ceramics the electrical conductivity increases with reduction in particle size
where as in metals electrical conductivity decreases.
(c) Electrical conductivity of Nano materials depends on surface scattering, quantized
conditions and discrete energy band gaps.
(d) When the dimensions of solids become comparable to mean free path, the
scattering probability decreases and hence electrical properties change.
(e) Energy of the particle inside the potential is given by E = n2h2 / 8 m a2

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Dr. Shaik Kareem Ahmed 2018

For a = 1 cm, the separation between energy levels order of 10-14 eV, then energy
levels are continuous
For a = 100 nm, the separation between energy levels order of 10-4 eV, then energy
levels are discrete.
(f) The important point here is that, with decreasing the diameter of wire, the
number of electron wave modes contributing to the electrical conductivity is
becoming increasingly.
2. Optical properties.
(a) The optical properties of nano materials depends on size, shape, surface
characteristics.
(b) Depending on size of particles different colors are seen.
(c) Decreasing the size of Nano structured material increases the energy
difference between allowed energy levels.
(d) Nano crystals absorb light then re emit light in different color, the size of the
Nano crystal determined the color.
(e) As size is small, quantum effects play, which limit the energies at which
electrons and holes can exist in the particles.
(f) Bulk gold particles appears yellow in color, Nano sized gold particles appears
red in color.
(g) The particles are so small that electrons are not free to move about as in bulk
gold because this moment restricted, the particles react differently with light.

3. Magnetic properties
(a) In nanomaterials a large number of atoms will be present at the surface. These
atoms will have less co-ordination number and hence possess local magnetic
moment within them.
(b) The nanomaterials show variation in their magnetic property, when they change
from bulk state to nano-particle state. Some of the examples are listed in table
S.No Material Bulk state Nano-Phase state

1 Iron, Ni, Cobalt Ferro-magnetic Super para-magnetic

2 Sodium, Potassium Para-magnetic Ferro-magnetic

3 Chromium Anti-ferromagnetic Frustrated para-magnetic

4. Mechanical properties
(a) The hardness of Nano-phase materials varies from material to material. This may
be due to the phase transformation, stress relief, density and grain boundaries.
(b) They exhibit super plastic behavior.
(c) If the grains in Nano size scale, the interface area within the material greatly
increases, which enhance its strength.

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(d) Hardness, elastic modulus, fracture toughness, scratch resistance modified due to
Nano size.
(e) 2 to 7 times higher hardness and strength of Nano crystalline pure metals (10 nm
grain size) than those of large grain size metals.
(f) Super plastic behavior in brittle ceramics with nanoscale grain size at low
temperature.
(g) The Nano materials has less defects compare to bulk materials, which increase
the mechanical strength.

3. Explain surface to volume ratio

Increase in surface area to volume ratio:

Nanomaterials have a relatively larger surface area when compared to the larger form of
the material of same volume or mass.
4
Let us consider a sphere, its surface area=4πr2 ; Its volume =3 𝜋𝑟 3
3
Surface area to volume ratio = 𝑟
Thus, when the radius of the sphere decreases, its surface area to volume ratio increases.
Let us consider another example: Cube

Thus we find that when the given volume is divided into small pieces, the surface area
increases. Hence as material size decreases, a greater proportion of atoms are found
at the surface compared to those inside. This makes materials more chemically
reactive. This also effects strength and electrical properties.

4. What is Quantum confinement

Metals in general are characterized by their electronic bonding system differing from non-metals
and semiconductors. When dimensions are decreased to a certain extent, this special behaviour of
metals no longer possible. The electrons are trapped in a too small volume and they behave very
differently and consequently change their physical and chemical properties.

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In small nano-crystals the electronic energy levels are not continuous as in the bulk but discrete,
because of the confinement of the electronic wave-function to the physical dimensions of the
particles. This phenomenon is called quantum confinement.

5. Explain different types preparation techniques of nano materials.

There are two approaches to the synthesis of nanomaterials and the fabrication of nanostructures;
top-down and bottom-up.

Top down approach involves the breaking down of the bulk material into nano sized structures or
particles. An example of such a technique is high-energy ball milling.

The alternative approach, which has the potential of creating less waste and hence the more
economical, is the ‘bottom- up’. 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 of these techniques are
still under development or are just beginning to be used for commercial
production of nano powders

Ball Milling Method:

Ball milling is a method of production of nano materials. This method
is preferred mainly in the preparation of metal oxide nano crystals.
Ball milling consist of a hollow cylindrical shell rotating about its axis.
The axis of shell may be horizontal or at some angle. It is partially filled
with balls. These balls are grinding materials, made up of chrome steel,
stainless steel or rubber. The inner surface of the hollow cylinder is lined with a resistant material
such as manganese, steel or rubber. In this method, small balls are allowed to rotate inside a drum
and are made to fall on a solid with high gravitational force, which crushes the solid into nano
crystals.

The ball mill used to for grinding materials such as coal, pigment etc. Grinding can be carried out
either wet or dry but the former is performed at low speed. For system with multiple components,
ball milling has been shown to be effective in increasing solid state chemical reactivity.
Additionally, ball milling has been shown effectivle8 production of amorphous materials.

Advantages

The cost of installation, power required and grinding medium is low, it is suitable for both batch
and continuous operation, similarly it is used for open as well as closed circuit grinding and is
applicable for materials of all degree of hardness

Disadvantages

Bulky size, running a strong vibration and noise, there must be a solid foundation, low efficiently,
energy consumption is relatively large, grater friction loss.

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Dr. Shaik Kareem Ahmed 2018

Sol-Gel method:

Sol-Gel is a chemical process used to make

ceramic and glass materials in the form of
thin films, fibers or nano powders. Sol-Gel
process involves the formation of a
colloidal suspension (Sol)and gelation of
the sol to form nano-powders in a
continuous liquid phase (Gel).

A sol is a dispersion of the solid particles (20

to 100nm) in a liquid. The gel is a state
where both liquid and solid are dispersed in
each other, which presents solid
networking containing liquid components.
The transformation to a gel is often
achieved by changing the PH or the concentration of the solution. The following four steps are
involved in sol-gel method

1. The desired colloidal particles are dispersed in a liquid to form a sol.

2. The deposition of the sol solution on the substrates by spraying, dipping or spinning.
3. The particles in the sol are polymerized through the removal of the stabilizing components and
produce a gel.
4. The final heat treatments pyrolyze the remaining organic or inorganic components and form
an amorphous or crystalline nano particles coating on the substrate.

The chemical deposition method (CVD)

In this method nanoparticles are deposited from the gaseous phase. Initially material is heated to
form a gas and then allowed to deposit on a solid surface under vacuum condition. In deposition
by chemical reaction a new product is formed which is different from material used. This process
forms nano powders of oxides and carbides of metals.

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6. What are carbon nano tubes? Explain properties and applications.

Carbon nanotubes are large molecules of pure carbon that are long and thin and shaped
like tubes, about 1-3 nanometers (1 nm = 1 billionth of a meter) in diameter, and
hundreds to thousands of nanometers long.
Properties
 Extremely small
 Strong and flexible structure.
 Unique electrical properties
 Efficient heat conductors long tube.
Carbon nanotubes classified into two types 1) single walled nanotubes. 2) Multi walled
nanotubes.
Single walled carbon nanotubes (buckytubes) having a single atomic layer thick
sheet of graphene rolled into a seamless cylinder. Most SWNT have a diameter close
to 3 nm with tube length 104 times longer. Multiwalled nanotubes (MWNT) consist
of multiple layers of graphite. MWNT can have 0D-20nm . 1D-3nm length can be 104
times longer. As individual molecules, nanotubes are 100 times stronger-than-steel
and one-sixth its weight. Some carbon nanotubes can be extremely efficient
conductors of electricity and heat; depending on their configuration, some act as
semiconductors.

Applications

1. Bucky tubes have extraordinary electrical conductivity, heat conductivity and

mechanical properties. They are probably the best electron field-emitter possible.
They are polymers of pure carbon and can be reacted and manipulated using the
tremendously rich chemistry of carbon. This provides opportunity to modify the
structure and to optimize solubility and dispersion.
2. CNT have the intrinsic characteristics desired in material used as electrodes in
batteries and capacitors, two technologies of rapidly increasing importance.
Buckytubes have a tremendously high surface area (~1000 m2/g), good electrical

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conductivity, and very importantly, their linear geometry makes their surface highly
accessible to the electrolyte.
3. Carbon nanotubes can perform as a catalyst in a fuel cell, avoiding the use of
expensive platinum on which most catalysts are based. Researchers have found that
incorporating nitrogen and iron atoms into the carbon lattice of nanotubes results
in nanotubes with catalytic properties.
4. Nanotubes bound to an antibody that is produced by chickens have been shown to
be useful in lab tests to destroy breast cancer tumors. The antibody-carrying
nanotubes are attracted to proteins produced by one type of breast cancer cell. Once
attached to these cells, the nanotubes absorb light from an infrared
laser, incinerating the nanotubes and the attached tumor.
5. An inexpensive nanotube-based sensor can detect bacteria in drinking water.
Antibodies sensitive to a particular bacteria are bound to the nanotubes, which are
then deposited onto a paper strip. When the bacteria is present it attaches to the
antibodies, changing the spacing between the nanotubes and the resistance of
the paper strip containing the nanotubes.

6. Carbon nanotubes used to direct electrons to illuminate pixels, resulting in a

lightweight, millimeter thick "nanoemissive" display panel. Printable
electronic devices using nanotube "ink" in inkjet printers Transparent, flexible
electronic devices using arrays of nanotubes.

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