Nanomaterials

The era of Nanoscience and nanotechnology was inaugurated on 29 th December

1959, by Nobel laureate Richard Feynman, a physicist at Caltech, gave a talk called
"There's Plenty of Room at the Bottom. Till that date the progress in Nanoscience is
persistent. Many exciting things uncovered during last three decades, one of which is as
the size decreases, the quantum mechanical properties (microscopic level) become
distinct and surface to volume ratio increases drastically. This changes the elastic,
mechanical, optical, thermal etc. properties of the material. For example, opaque
substances become transparent (copper), insoluble material becomes soluble (gold). To
understand how it is possible let us start our discussion with the quantum mechanical
view point as quantum mechanics is the only mechanics with the help of which the
properties at microscopic level (atomic level) can easily be comprehensible.

1.1 Quantum mechanics and its Importance in nanoscience

Before 1900 all physical phenomena were believed to be explained in terms of

Newtonian mechanics (1687) that explained the motion of mechanical objects on both
celestial and terrestrial scales. Application of this theory to the motion of molecules
resulted in the kinetic theory of gases. J.J. Thomson's discovery of the electron (1897)
involved demonstrating that its behavior is described by Newton's equations of motion.
The wave nature of light had been suggested by the diffraction experiments of Young
(1803). It became more obviously so by Maxwell's discovery in 1864 of the connection
between optical, magnetic and electrical phenomena. Taking all this into account it is not
surprising that at the end of the nineteenth century many physicists thought that all
interesting questions had been asked and that finding the right answers would be merely a
matter of time. But, there were three critical experiments in the pre-quantum era which
could NOT be explained by a straightforward application of classical physics: Black-
body radiation (Planck, 1900), photoelectric effect (Einstein, 1905) and Optical line
spectra (Bohr’s atom model, 1913). Moreover, the dual nature of the electron (de Broglie,
1923) could not be explained by the classical mechanics.
Today the combined work of Plank, Einstein and Bohr is known as the Old
Quantum Theory which was able to explain the derivation of the Balmer formula,
quantum numbers and selection rules for energy states in an atom and the Pauli Exclusion
Principle. The old quantum theory relied heavily on the Newtonian mechanics, but sought
to supplement it with supplementary conditions.
Although this quantum theory in it’s original form was not complete until the mid
1920: two distinct and independent theories of a new quantum theory were presented i.e.
Matrix mechanics (W. Heisenberg, 1925) and Wave mechanics (E. Schrödinger, 1926).
Soon after their discovery these two formulations were shown to be equivalent, forming
the basis of today’s quantum theory. Sometime later, it was clear that classical mechanics
turn out to be just an approximate version of quantum mechanics. . Let us now discuss
the quantum mechanics with its essential fundamentals and the applications.
1.1.1 Wave function
According to wave-particle duality, there is the wave associated with the moving
particle called de Broglie wave. Classically, the square of the wave amplitude of
electromagnetic radiation gives radiation intensity. In the same manner, quantum
mechanically, we can make a similar interpretation for de Broglie waves corresponding
to any particle. Hence, if we consider an electron moving somewhere in the space and if
2
ψ is its wave function then   *  P represents the density of electrons or
probability density of an electron for finding it at a given place at a given instant of time.
Here,  * represents the complex conjugate of the wavefunction.
1.1.2 Normalization condition
Let V be a volume inside which an electron is known to be present but its location
is unknown. Then probability of finding the electron in a certain volume element dV of V
2 2
is  dV . Here,  is called the probability function. Since the electron must be inside
2
the volume somewhere, the integration of  over the entire volume V must be unity i.e.
the probability of finding the electron in that particular region is 100%. . Therefore,
2
 dV  1 (1.1)

Or more simply,
2
  dx dy dz  1 (1.2)
This condition is called the normalization condition and the wave function Ψ
satisfying this condition is called a normalized wavefunction.
1.1.3 Eigen values and Eigen functions
The state of the system is completely characterized by a wave function. If the
wavefunction ψ is changed, then the system changes its state. To be an acceptable
wavefunction, the following criteria must be satisfied by the wavefunction and is known
as eigen function,
1. Ψ is single valued everywhere,
2. Ψ and its first derivative with respect to its variables are continuous everywhere.
3. Ψ is finite everywhere: If the space co-ordinates x,y,z extend from  to   then
also   x, y, z  must remain finite for all vales of x,y,z.

(a) (b) (c)

Fig.1.1. The functions which are not single valued (a), not continuous (b), not finite (c).
 Thus, the wave functions possess above criteria are known as eigen functions and
the energy values which evaluated by solving Schrödinger equation are known as energy
eigen values corresponding to eigen function.
1.1.4 Expectation values
Suppose, a particle has a dynamic state in the space and its associated
wavefunction is Ψ (x, t). By observing the position of the particle at certain particular
instant of time, the finite probability of finding the particle at that instant of time t, at any
2
x co-ordinate in the interval x to x   x is obtained by P  x, t  dx   dx . Repeating the
procedure number of times on the same particle having same wavefunction Ψ (x, t)
always at the same instant of time t, we can have an average of the observed values of
position of the particle at time t. This average value is called expectation value of the x-
coordinate of the particle at the instant t and can be represented as

 x    *  x  x  x  dx

This relation suggests the position of the large number of particles determined by the
same wavefunction Ψ (x, t) at the particular of time.
Similar procedure can be adopted to obtain the expectation value  S ( x)  which is a
function of position x (like potential energy U(x)) of a particle described by a
wavefunction Ψ. Hence,

 S ( x)    * ( x) S ( x) ( x) dx


1.1.5 Schrödinger’s Equations

There are two types of Schrodinger equations: time dependent and time independent. Let
us derive both of them.
Time dependent form
Suppose, the wavefunction Ψ which characterize the de Broglie wave is given by
 i ( t  x )
  Ae v (1.3)
this can be re write as
2 i ( ft  x )
 (1.4)
  Ae
where,   2 f and v  f  are to be used.
Let, E be the total energy and p be the momentum of particle. Then E= hf and   h .
p
On substituting above values in equation (1.4), we have,
  Ae
 2 i h  Et  px  (1.5)

Above eq. (1.5) represents wave equivalent of a free particle of total energy E and
momentum p moving in +x-direction. Differentiating above eq. (1.5) twice with respect
to x, we get
 2 4 2 p 2
   (1.6)
x 2 h2
Differentiating eq. (1.5) with respect to t, we get,
 2 iE
  (1.7)
t h
Now, the total energy of a particle moving with small speed compared to c is given by the
2
sum of kinetic energy p and the potential energy V. Then
2m
p2
E V (1.8)
2m
Multiplying above equation by Ψ on both sides,
p2
E    V (1.9)
2m

Now, from eq. (1.7),

h 
E   (1.10)
2 i t
and from eq. (1.6)
h 2  2
p 2   (1.11)
4 2 x 2
Substituting above eq. (1.10) and (1.11) in eq. (1.9) we have,
h  h 2  2
  2  V (1.12)
2 i t 8 m x 2

ih  h 2  2
or  2  V (1.13)
2 t 8 m x 2
Above eq. (1.13) is called time-dependent form of Schrödinger equation in one
dimension.

In three dimensions, the above equation is written as follows,

ih  h 2   2  2  2 
  2  2  2  2   V (1.14)
2 t 8 m  x y z 

Time Independent Form (Steady state form)

When the potential energy of the particle is found to be independent of the time
and varies with the position of the particle only then Schrödinger’s equation may be
simplified by eliminating all reference to t. Hence, the one dimensional wavefunction Ψ
of unrestricted particle is given by
 2 i h  Et  px   2 iE h t
e
2 ip h  x   2 iE h t
  Ae  Ae 0 e (1.15)
where,  0  Ae 2 ip h  x . This means that, Ψ is the product of position dependent function
Ψ0 and time dependent function e 2 iE ht . Differentiating above eq. (1.15) with respect to
t, we get,
   2 iE    2 iE h t
   0 e (1.16)
t  h 
Differentiating eq (1.15) twice with respect to x,

 2  2 0  2 iE h t
 e (1.17)
x 2 x 2

Now, substituting these values in time dependent form of Schrödinger’s equation (1.11),
we get,
h2  2 0  2 iE h t
E 0 e 
 2 iE h t
 V 0 e 
 2 iE h t
 2 e
8 m x 2
Dividing above equation by e 2 iE ht , we have,

h2  2 0
E 0    V 0
8 2 m x 2
 2 0 8 2 m
or,  2 ( E  V ) 0  0 (1.18)
x 2 h
Above eq. (1.18) is the time independent form or steady state form of Schrödinger’s
equation in one dimension. The three dimensional form is given as

8 2 m
 2 0  ( E  V ) 0  0 (1.19)
h2
1.1.6 Physical Interpretation of Schrödinger Equation:
Above eq. (1.19) is used to find the allowed energy levels of quantum mechanical
systems such as atoms or transistors. The associated wavefunction gives the probability
of finding the particle at a certain position. The solution to this equation is a wave that
describes the quantum aspects of a system. Schrödinger’s equation shows the entire wave
like properties of matter and was one of greatest achievements of 20th century science. It
is used in materials science to deal with problems about the atomic structure of matter. It
is an extremely powerful mathematical tool and the whole basis of wave mechanics. The
Schrödinger equation is the name of the basic non-relativistic wave equation used in one
version of quantum mechanics to describe the behavior of a particle in a field of force.
There is the time dependant equation used for describing progressive waves, applicable to
the motion of free particles. Moreover, the time independent form of this equation used
for describing standing waves. Schrödinger’s time-independent equation can be solved
analytically for a number of simple systems. The time-dependant equation is of the first
order in time but of the second order with respect to the co-ordinates, hence it is not
consistent with relativity. The solutions for bound systems give three quantum numbers,
corresponding to three co-ordinates, and an approximate relativistic correction is possible
by including fourth spin quantum number.

1.1.7 Operators
 As discussed in the article 1.1.4, the expectation value is obtained for any function
which is a function of position. But it is found that the same procedure can not followed
for finding the expectation value of momentum. The reason is Heisenberg’s uncertainty
principle. If we specify x, so that x  0 , we can not have a corresponding momentum p,
because,  x  p    . Similarly, the expectation value of <E> for energy can not be
2
specify as  E  t    . So to solve such kind of problem, we should adopt another
2
way to find the expectation values.
Consider the eq. (1.5), the free particle wave function and differentiating it with
respect to x and t.
 2 i
 p (1.20)
x h

 2 i
 E (1.21)
t h
Above set of equations can be rewrite as follows
h  
p    i   (1.22)
2 i x x
ih  
E    i  (1.23)
2 t t

From the above set of equations we can say that, the momentum operator is

p̂  i (1.24)
x
and the total energy operator is

Ê  i  (1.25)
t

We can write above equation (1.25) in terms of kinetic and potential energies, i.e.

2
ˆ  Uˆ  pˆ  U
Eˆ  KE (1.26)
2m
where,
2
ˆ  pˆ  1        
2 2 2
KE   (1.27)
2m 2m  i x  2m x 2

is the kinetic energy operator. Therefore, substituting eq.(1.25) and eq.(1.27) in eq.
(1.26) we have,
 2  2
i   U (1.28)
t 2m x 2
Multiplying above eq. (1.28) by Ψ, we have Schrödinger equation.
  2  2
i     U (1.29)
t 2 m x 2
1.1.8 Particle in a box
For the understanding of microscopic properties (e.g. position, momentum) of the
particles like electrons in the atomic structure, we can compare the electron with a
particle which is trapped in the box of finite dimensions. Consider a particle which
bounces back and forth between the walls of a box of width L as shown in the Fig. 1.2.
Suppose that the walls of the box are infinitely hard so that the particle does not loose
energy each time it strikes a wall. Moreover, suppose that particle is moving with
sufficiently low velocity so that the relativistic case can be ignorable. Such particle
behaves like a standing wave in a string stretched between the walls of the box. Further,
the potential energy U of the particle is infinite on both sides of box and is constant inside
the box as shown in the Fig. 1.3. The possible de Broglie wavelengths of the particle in
this case are determined by the width L of the box as shown in the Fig. 1.4. Particle does
not acquire enough energy so that it can go outside the box and so the probability of
finding the particle outside is zero. Hence, its wave function   0 for x  0 and x  L .
So to find the value of wavefunction  within the box i.e. within x=0 and x=L we can
start with the Schrödinger equation within the box. The Schrödinger equation within the
box is
 2 2m
 E  0 (1.30)
x 2  2

The solution of above Schrödinger equation is

 2mE   2 mE 
  A sin   x  B cos   x (1.31)
     
which can be verified by substituting above eq (1.31) in to (1.10). Here, A and B are
constants. Here, in above eq. (1.31),   0 when x=0 and x=L. The second term here can
not describe the particle because cosine (0) =1 and hence it can not vanish at x=0.
Therefore, we can say that, B=0. Here,   0 when x=0 but   0 when x=L only when
2mE
L  n n=1,2,1,4 …. (1.32)

This suggests that the energy of the particle can have only certain values known as
eigenvalues. The energy levels of the particle are found by solving the eq. (1.12) which
gives,
 n 2 2  2
En  n=1, 2, 1 …. (1.33)
2mL2
Here, the integer n that specifies an energy level En is called quantum number. Above eq.
(1.33) gives following important conclusions:
(i) A particle trapped in a box can occupy only certain specific energies which are depend
on the mass of the particle and the nature of its trapping. (ii) It can not acquire zero
energy. If it has zero energy means its velocity is zero and hence its de Broglie
wavelength   h will become infinite but there is no way to reconcile an infinite
mv
wavelength with a trapped particle. Hence, the trapped particle can not acquire zero
kinetic energy.
The wavefunctions of a particle in a box whose energies are En are given with the help of
eq. (1.31) by taking B=0.
 2 mEn 
 n  A sin  x (1.34)
  
 
Substituting eq.(1.31) in eq.(1.34) we have,
n x
 n  A sin (1.35)
L
Above eq.(1.35) gives the eigenfunctions of the trapped particle in the box of width L for
different quantum number n. Now, the probability density of particle can be derived by
2
taking the integral of  n over all space which in turn gives

2 L
 n  A2    1 (1.36)
  2 
Substituting the value of A from eq.(1.36) into eq. (1.35) we get,
n x
 n  2 L sin (1.37)
L
2
which gives the normalized wave function of the particle. In every case,  n  0 at x=0
and x=L i.e. at the boundaries of the box.

1.2 Nanophysics
Feynman suggested that it may eventually be possible to precisely manipulate
atoms and molecules. At such microscopic level, the principles of classical mechanics are
failed to explain the properties and behavior of systems. So, one has to consider the
concepts of quantum mechanics.
It is well understood and accepted universally now that for the solutions of the
problems at the macroscopic level, the principles of classical mechanics are applicable.
But, at microscopic level of atoms, these principles are observed to be fail and the
principles of quantum mechanics must be used for solutions. In fact, quantum mechanics
is valid at all length scales. It is possible to describe the characteristics of macroscopic
objects also with quantum mechanics. Classical mechanics and quantum mechanics give
the same predictions for macroscopic objects so we usually use the simpler classical
mechanics to describe large objects. Nanometer scale objects lie near the boundary
between classical mechanics and quantum mechanics and sometimes it is necessary to
use quantum mechanics to describe phenomena on the scale of nanometers. Therefore,
after having a brief discussion on quantum mechanics, let us now see the different aspects
of nanophysics in detail which essentially is the mathematical way to understand the
science at micro level.

1.2.1 Nanoscale systems

Nanoscale systems simply means about the tiny systems with dimensions at
nanometer level (i.e. 10-9m). The technology that relies on Nanoscale systems is known
as nanotechnology. However, the nanotechnology is simply not miniaturizing materials,
and devices at the nanometer scale. At nano-meter length scales new physical properties
emerge in these materials and new techniques are required to make them. Size constraints
often produce qualitatively new behavior in nano-materials. This means that when the
materials (and hence the devices) are manufactured at nanoscale level, all the
corrosponding parameters and properties (e.g. electrical, optical, magnetic, etc.) are
changed with respect to their bulk form. Now let us see the world of nanoscale devices in
detail.
1.3 Nanomaterials
The materials made up of nanoparticles are termed as nanomaterials. The
materials that we are utilizing in our day to day life are in their bulk form. The properties
and hence their behavior under different circumstances are of certain type. But, when the
same material is grown up atom by atom very systematically in a crystal grow machine
by proper method, then all the associated properties as well the behavior are noticed to be
changed dramatically with respect to their corresponding bulk form. One of the main
causes behind this may be the rearrangement of the atoms or molecules. The
combinations of atoms or molecules held together under different circumstances are
known as clusters. In this sense, clusters are artificial molecules that differ from the
molecules that are occurred naturally. Clusters consist of a countable number of atoms
ranging from 50 to 1000.
1.3.1 Importance of nanomaterials:
These materials have created a high interest in recent years by virtue of their unusual
mechanical, electrical, optical and magnetic properties. Some examples are given below:
(i) Nanophase ceramics are of particular interest because they are more ductile at elevated
temperatures as compared to the coarse-grained ceramics.
(ii) Nanostructured semiconductors are known to show various non-linear optical
properties. Semiconductor Q-particles also show quantum confinement effects which
may lead to special properties, like the luminescence in silicon powders and silicon
germanium quantum dots as infrared optoelectronic devices. Nanostructured
semiconductors are used as window layers in solar cells.
(iii) Nanosized metallic powders have been used for the production of gas tight materials,
dense parts and porous coatings. Cold welding properties combined with the ductility
make them suitable for metal-metal bonding especially in the electronic industry.
(iv) Single nanosized magnetic particles are mono-domains and one expects that also in
magnetic nanophase materials the grains correspond with domains, while boundaries on
the contrary to disordered walls. Very small particles have special atomic structures with
discrete electronic states, which give rise to special properties in addition to the
superparamagnetism behavior. Magnetic nanocomposites have been used for mechanical
force transfer (ferrofluids), for high density information storage and magnetic
refrigeration.
(v) Nanostructured metal clusters and colloids have a special impact in catalytic
applications. They may serve as precursors for new type of heterogeneous catalysts
(Cortex-catalysts) and have been shown to offer substantial advantages concerning
activity, selectivity and lifetime in chemical transformations and electro- catalysis (fuel
cells).
(vi)Nanostructured metal-oxide thin films are receiving a growing attention for the
realization of gas sensors (NOx, CO, CO2, CH4 and aromatic hydrocarbons) with
enhanced sensitivity and selectivity. Nanostructured metal-oxide (MnO2) finds
application for rechargeable batteries for cars or consumer goods. Nanocrystalline silicon
films for highly transparent contacts in thin film solar cell and nano-structured titanium
oxide porous films for its high transmission and significant surface area enhancement
leading to strong absorption in dye sensitized solar cells.
(vii) Polymer based composites with a high content of inorganic particles leading to a
high dielectric constant are interesting materials for photonic band gap structure.

1.4 Methods for synthesis of nanomaterials

In broad way, there are two approaches for synthesis of nanomaterials: (i) top
down approach in which we start with the bulk (larger) sample and with the help of
various experimental techniques, the size of the sample is allowed to reduce until the
desired size obtained. Following techniques are employed under top down approach:
(a) High energy ball milling, (b) laser ablation (c) Sputtering (d) electron beam
evaporation (e) photolithography. The approach is bottom up approach for the synthesis
of nanomaterials in which the materials are assembled atom by atom to form the clusters
of certain particular size. Following techniques are employed under bottom up approach:
(a) chemical vapor deposition, (b) sol gel method, (c) electro-deposition. Let us now see
some important methods for synthesis of nanomaterials.
1.4.1 Top down approach:
A top-down approach is the breaking down of a system to gain its compositional
sub-systems (Fig. 1.5). A key advantage of the top-down approach is that the parts are
both patterned and built in place, so that no assembly step is needed.

(1) High energy ball milling (Mechanical alloying):

 This process was developed by Benjamin and his coworkers at the International
Nickel Company in the late of 1960. In this process a powder mixture placed in the ball
mill is subjected to high-energy collision from the balls. It was found that this method
could successfully produce fine, uniform dispersions of oxide particles (Al2O3, Y2O3,
ThO2) in nickel-base super alloys that could not be made by more conventional powder
metallurgy methods.
Traditionally, a ball mill consists of stainless cylinder and some crushing agents
(e.g. iron balls or silicon carbide balls). After
filling up the samples in the powder form, the
milling chamber is allowed to rotate. The
crushing agents (i.e. balls) continuously move up
and down due to centrifugal and gravitational
forces and impart high amount of energy by
colliding with material powder particles. The
impact energy of the milling balls in the normal
direction attains a value of up to 40 times higher
than that due to gravitational acceleration.
The fig. 1.6 shows the motions of the balls
and the powder. Since the rotation directions of
the bowl and turn disc are opposite, the
centrifugal forces are alternately synchronized.
Fig. 1.6 High energy ball milling: Thus, friction resulted from the hardened milling
Motion of balls and powder. balls and the powder mixture being ground
alternately rolling on the inner wall of the bowl
and striking the opposite wall. The synthesis of
nanostructured metal oxides for gas detection is one of the most promising applications of
high-energy ball milling.
(2) Laser Ablation:
In general, ablation is removal of material with the help of the incident laser light.
In most metals and glasses (or crystals) the removal is by vaporization of the material due to
heat. When the material removal is by vaporization, it will form the plume which is plasma-
like substance consisting of molecular fragments, neutral particles, free electrons and ions,
and chemical reaction products (Fig. 1.7). The plume is responsible for optical absorption
and scattering of the incident beam and can condense on the surrounding work material and
the beam delivery optics. Normally, the ablation site is cleared by a pressurized inert gas,
such as nitrogen or argon.
For high energy deposition in a small volume for rapid and complete ablation, the selection
of a wavelength with a minimum absorption depth is necessary. Moreover, pulse duration
must be short to maximize peak power and to minimize thermal conduction to the
surrounding work material. The pulse repetition rate must be optimum for more efficient
ablation. If the rate is too low, all of the energy which was not used for ablation will leave the
ablation zone allowing cooling.
(3) Sputtering:
Sputtering is a technique to deposit thin (nano) films of a material onto a substrate. In
this technique, at first, the target material (cathode) and the substrate (anode) are placed in a
vacuum chamber. Then a sputtering gas which in general a chemically inert and heavy gas
(e.g. Argon) is allowed inserting in the chamber. A high voltage is applied between them so
that ions are generated by the collision of neutral atoms of inert gas with high energy
electrons. Hence, plasma is created by ionizing a sputtering gas (Fig. 1.8). The ions of
sputtering gas bombard the target and sputters off the material to be deposited. The energies
required for sputtering are much higher than lattice bonding energies, therefore sputtering
collisions are considered as elastic collisions.

1.4.2 Bottom up approach:

A bottom-up approach is the piecing together of microscopic systems to give rise
to grander macroscopic systems. Following methods follow the bottom up approach:

(1) Chemical vapor deposition:

 Chemical vapor deposition is the process of depositing solid materials (thin films)
at high or ambient temperature as a result of chemical reactions. This deposition forms
ordered crystal grown from vapor. In this technique, the Precursor gases (the gas
materials to be deposited from the gaseous state during process) are delivered into the
reaction chamber at approximately ambient temperatures. As they pass over or come into
contact with a heated substrate, they react or decompose forming a solid phase and are
deposited onto the substrate. The substrate temperature is critical and can influence what
reactions will take place. The various types of CVD Processes are: (1) Atmospheric
Pressure Chemical Vapor Deposition (APCVD) (2) Low Pressure Chemical Vapor
Deposition (LPCVD) (3) Metal-Organic Chemical Vapor Deposition (MOCVD)(4)
Plasma Enhanced Chemical Vapor Deposition (PECVD)(5) Laser Chemical Vapor
Deposition (LCVD) (5) Photochemical Vapor Deposition (PCVD),(6) Chemical Vapor
Infiltration (CVI),(7) Chemical Beam Epitaxy (CBE).
Advantages:
(1) CVD gives uniform thickness of coating of three dimensional structures.
(2) CVD processes have a greater flexibility of using a wide range of chemical precursors
such as halides, hydrides, organo-metallic compounds and so forth which enable the
deposition of a large spectrum of materials, including metals, non-metallic elements,
carbides, nitrides, oxides, sulphides, as well as polymers.
(3) The CVD technique requires relatively low deposition temperatures. This effectively
enables the desired materials to be deposited in-situ at low energies through vapor phase
reactions. This enables the deposition of refractory materials at a temperature much lower
than their melting temperatures.
(4) CVD also has the ability to control the crystal structure, stoichiometry, surface
morphology and orientation of the CVD manufactured products by tailor-making through
controlling the deposition parameters.
(5) The deposition rate can be adjusted readily. Low deposition rate is favored for the
growth of epitaxial thin film for microelectronic applications. However, for the
deposition of thick protective coatings, a high deposition rate is preferred and it can be
greater than tens of micrometers per hour. The deposition rate using CVD technique is
high and thick coatings can be readily obtained (in some cases centimeters in thickness).
(6) CVD equipment does not normally require ultra-high vacuum working environments
and the equipment generally can be adapted to many process variations. This great
flexibility is advantageous such that it allows many changes in composition during the
deposition, and the co-deposition of elements or compounds into multiple layers or mixed
layers.
Disadvantages:
(1) A major disadvantage is that CVD requires chemical precursors as the essential
reactants, which can often present safety and health hazards as they can be at times
extremely toxic, corrosive, flammable and explosive. CVD precursors can be highly toxic
even at low concentration (e.g. Ni(CO4)), explosive such as B 2H6, or corrosive (e.g.
SiCl4).
(2) CVD requires numerous test runs to determine and reach suitable growth parameters,
especially for single-crystal growth.
(2) Sol Gel method:

Sol is a stable colloidal dispersion of small particles in a liquid (solvent). The

particles may be amorphous or crystalline. Whereas a gel is a state where both liquid and
solid are dispersed in each other, which presents a solid network containing liquid
components. In a colloidal gel, the network is built from agglomeration of colloidal
particles. Generally, the sol particles may interact by van der Waals forces or hydrogen
bonds. A gel may also be formed from linking polymer chains. In most gel systems used
for materials synthesis, the interactions are of a covalent nature and the gel process is
irreversible.

Fig. 1.9 Sol Gel method

Advantages:
(1) This method produces thin bond-coating to provide excellent adhesion between the
metallic substrate and the top coat.
(2) This method produces thick coating to provide corrosion protection performance.
(3) This method can easily shape materials into complex geometries in a gel state.
(4) Produces high purity products.
(5) This method has low temperature sintering capability, usually 200-600°C.
(6) This method prevents the problems with co-precipitation, which may be
inhomogeneous.
(7) This method provides a simple, economic and effective method to produce high
quality coatings.
(8) Sol-gel synthesis may be used to prepare materials with a variety of shapes, such as
porous structures, thin fibers, dense powders and thin films.
1.5 Characterization of nanomaterials:
The stage after the growth (or synthesis) is to check whether the material is really
composed of desired nanoparticles or nanostructures. Various characterization methods
are available nowadays like x-ray diffraction (XRD), scanning electron microscopy
(SEM), tunneling electron microscopy (TEM), atomic force microscopy (AFM),
Reflection high-energy electron diffraction (RHEED), low energy electron diffraction
(LEED) etc. for characterization of nanomaterials. Let us now discuss about an important
characterization method of nanomaterials.

1.5.1 Scanning electron microscopy (SEM)

Scanning electron microscope (SEM) is a microscope that uses electrons instead of light
to form an image. The SEM is an instrument that produces a largely magnified image by
using electrons instead of light to form an image. An electron gun produces beam of
electrons at the top of the microscope. The electron beam follows a vertical path through
the microscope, which is held within a vacuum. As shown in fig. (1.10), the beam travels
through electromagnetic fields and lenses, which focus the beam down toward the
sample. Once the beam hits the sample, electrons and X-rays are ejected from the sample.
Detectors collect these X-rays, backscattered electrons, and secondary electrons and
convert them into a signal that is sent to a screen similar to a television screen and
produces the final image.
 Before the sample is inserted for an SEM, all water must be removed from the
sample because the water would vaporize in the vacuum. The scanning electron
microscope has many advantages over traditional microscopes. The SEM has a large
depth of field, which allows more of a specimen to be in focus at one time. The SEM also
has much higher resolution, so closely spaced specimens can be magnified at much
higher levels. Because the SEM utilizes electromagnets rather than lenses, the degree of
magnification enhanced to a very high level.

1.5.2 Transmission Electron Microscope (TEM)

Transmission Electron Microscopy (TEM) is a straight forward method which

decide the size and shape of the nanostructured materials and give structural information.
The first TEM was built by Max Knoll and Ernst Ruska in 1931. In the TEM method, an
electron beam is passed through thin section of the specimen and will get a two-
dimensional cross-section of the specimen and it can be magnified between 500 to
500,000 times .In the SEM, in contrast, view the surface structure of the specimen and
provide 3-D impression and Specimens can be enlarged approximately between 10 and
100,000 times.

Principle
In TEM, a beam of electrons is accelerated to 100KeV through an ultra-thin
specimen by means of a condenser system and enter in to the sample. An image is formed
from the interaction of the electrons that transmitted through the specimen, then this
obtained image is magnified and focused on a fluorescent screen, on a layer of
photographic film, or to be detected by a sensor such as a CCD camera. The greatest
advantage of TEM is high magnification ranging from 50 to 106 and its capability to
produce both image and diffraction information from a single sample. Unlike SEM, no
scanning required for the high resolution. These highly energetic incident electrons
interact with the atoms in the sample and produce characteristic radiation and particles
which provide information for materials characterization. This information is achieved
from both deflected and non-deflected transmitted electrons, backscattered and secondary
electrons, and emitted photons.
The high magnification or resolution of TEM is given by,
L=

Where m and q are the electron mass and charge, h is the Plank’s constant and V is the
potential difference through which the electrons are accelerated. When electrons are
accelerated up to high energy levels and focused on a material, they can scatter or back
scatter elastically or in elastically or outcome many interactions. Some of them are used
in Transmission electron microscopy (TEM). The quantum mechanical behavior of
electron took into consideration in the development of TEM.
 The interaction of electron with the object was obtained due to the inherent nature
of electron which is a quantum mechanical object. A single column of atoms, electrons
have both wave and particle nature and the De Broglie wavelength of electrons are
smaller than that of light and so they have higher resolution capability. In both physical
and biological sciences, TEM forms a major analysis method in a range in scientific
fields.

Advantages
The main application of TEM is in material science as well as pollution,
nanotechnology, semiconductor research and cancer research. TEM are most powerful
microscopes which give maximum potential magnification of 1 nanometer and produce
two dimensional images with high resolution. A Transmission electron microscope
(TEM) uses energetic electrons to give crystallographic, morphologic and compositional
information of samples. In both physical and biological sciences, it forms a major
analysis method. Due to the thickness, composition and absorption of electrons in the
material. TEM contrast at smaller magnification, But at higher magnifications require
expert analysis of detected images and complex wave interactions which modulate the
intensity of the image. TEM also find application in chemical identity to observe
modulations.
1.5.3 X ray Diffractoemeter (XRD)

X-rays were discovered in 1895 by Wilhelm Conrad Roentgen (1845-1923) who

was a Professor at Wurzburg University in Germany. Working with a cathode-ray tube in
his laboratory, Roentgen observed a fluorescent glow of crystals on a table near his tube.
The tube was made up of a glass envelope (bulb) with positive and negative electrodes
encapsulated in it. The air in the tube was evacuated, and when a high voltage was
applied, the tube produced a fluorescent glow. Roentgen shielded the tube with heavy
black paper, and discovered a green colored fluorescent light generated by a material
located a few feet away from the tube. He concluded that a new type of ray was being
emitted from the tube. This ray was capable of passing through the heavy paper covering
and exciting the phosphorescent materials in the room. He found that the new ray could
pass through most substances casting shadows of solid objects. Roentgen also discovered
that the ray could pass through the tissue of humans, but not bones and metal objects. It is
interesting that the first use of X-rays were for an industrial (not medical) application, as
Roentgen produced a radiograph of a set of weights in a box to show his colleagues.
X-rays are produce when fast moving electrons strike a target of suitable material.
To produce the x-rays, one requires electron source, electron accelerating system and a
target of suitable materials having high atomic weight. The method by which x rays were
produced in Roentgen's first experiments is basically the one still used today.
The wavelength of x rays is ranging from 0.01 nm to 1 nm. So, these rays can
easily penetrate the object of moderate thickness via diffraction. Hence, it is easy to
determine the internal structure of the materials via diffraction pattern of x rays. Such
study is possible because of the fact that the intensities of diffracted beams and their
directions are related to the atomic arrangement in the crystals. Therefore, intensities and
directions of diffracted beams help to determine desired information about the crystal.
According to the observations of W.L.Bragg, the directions of diffracted beams can be
treated as the x rays that are reflected like mirror reflection from parallel atomic planes in
the crystal.

Fig. 1.13 Bragg’s diffraction of x rays in crystal

The Bragg condition for diffraction is

2d sin θ = nλ (1.38)
Where, n is the order of diffraction, λ is the wavelength of incident x rays, d is the
interatomic distance and θ is the angle of incidence of x rays. This means that there are
only certain directions θ in which the reflections of given wavelength λ from all parallel
planes add up in the phase to give strong diffracted beam. Moreover, since sin θ ≤ 1,
wavelengths λ≤ 2d are necessary for the occurrence of Bragg diffraction. This is the
reason why x rays are most useful for crystal analysis.
There are mainly three experimental methods of x ray diffraction for the analysis
of the material: Laue method, single crystal method and powder method. Let us discuss
each of them in detaile.
1.5.3.1 Laue method
Experimental arrangement
 In this method, a single crystal specimen is held stationary in continuous X ray
beam. The experimental arrangement is shown in the fig. 1.14. A well collimated x ray
beam with about 0.2 Ǻ to 2 Ǻ wavelength is used in this technique allowed to incident on
the crystal with a pin- hole arrangement as shown in the figure. The dimensions of the
crystal are usually less than 1 mm. A flat photographic plate is placed to receive either
transmitted diffracted or reflected diffracted beam from the crystal.
The diffraction pattern consists of series of spots which is the mirror image of the
crystal. The Laue pattern is very convenient for checking the orientation of crystals. By
this method, the shape of the unit cell can be determined from the symmetry of the
pattern.
Limitations:
This method is not suitable for determining the crystal structure because out of a
continuous range of wavelength, several wavelengths are reflected in different orders of
reflections and they may overlap on a single spot on the photographic plate. Therefore, it
is difficult to measure the reflection intensity of individual spots and hence the missing
reflections.
1.5.3.2 Single crystal method
In this method, a single crystal is rotated about fixed axis in a beam of
monochromatic x rays. Rotation of the crystal makes atomic planes into positions for
Bragg diffraction.

Experimental arrangement
The experimental set up of the method is shown in the Fig. 1.15. Monochromatic
x ray beam is allowed to irradiate a single crystal specimen which is mounted on a
rotating spindle. Crystal is rotated in the direction normal to the incident beam. The
dimensions of the crystal is generally less than 1 mm. A photographic plate is mounted in
a cylindrical holder concentric with a rotating spindle.
Explanation: The incident beam is diffracted from a crystal plane whenever the value of
θ satisfies the Bragg equation. The diffracted beams from all planes parallel to vertical
rotation axis will be in the horizontal plane and those from planes having other
orientations will be in layers above and below the horizontal plane. However, there will
be no diffracted beams from a plane which always contains the incident beam during the
entire rotation and from ones whose spacing is so small that λ>2d. The diffracted spots on
the film form parallel lines. During the entire rotation of the crystal, the diffracted beams
form cone. This cone is basically at right angles to the incident beam. Moreover, the cone
is symmetrically inclined about the rotation axis of the crystal. Since the photographic
film (plate) is cylindrical mounted about the rotation axis, it records the individual
reflections corresponding a layer as spots lying along a horizontal row known as layer
line.
1.5.3.3 Powder method
In this method, the specimen in the powdered form is placed in a monochromatic
beam of x rays (usually Kα radiation). Some of the microcrystals in the powder form
oriented at correct diffraction angle due to which diffracted beam of x rays generate. The
experimental arrangement is shown in the Fig. 1.16. The incident radiation strikes the
finely powdered specimen or finely grained polycrystalline specimen contained in a thin
walled capillary tube. A photographic film strip is wrapped around the inside of a
cylindrical chamber concentric with a sample. The rays are diffracted by those
microcrystals plane that satisfy the Bragg condition i.e. set of planes making Bragg angle
θ with the beam. The various diffracted rays lying along the surface of a cone concentric
with incident beam which is shown in the Fig. 1.16.

1.5.3.4 Low Electron Energy Diffraction (LEED)

During the process of crystal cutting along a certain plane the atoms near the
surface may be disturbed from their equilibrium positions in the bulk. This leads to
changes in the relative positions of the surface and near surface atoms and surface
reconstruction is taking place. Such changes are discovered with LEED. The surface
crystallographic structure can be determined by bombarding the surface with low energy
electrons (approx. 10-200 eV) and observe diffracted electrons as spots on a
phosphorescent screen.
 By this way LEED is the principal technique for the determination of surface
structures. By quantitative analysis of spot positions the information of size, symmetry
and rotational alignment of the unit cell is obtained. Similarly, by qualitative analysis
accurate information of atomic positions is obtained.

Theory
By the principles of wave-particle duality, the beam of electrons are considered as
electron waves incident normally on the sample. These waves will be scattered the
surface atoms.
The de Broglie wavelength of incident electrons is determined by
  h / 2meV
Where, h is Planck’s constant, m is electron mass, e is electronic charge, V is the
acceleration voltage applied. By increasing the value of acceleration voltage (V), the
value of wavelength can be made smaller so that it can become of the order of atomic
spacing to fulfill the condition of Bragg diffraction. Electrons of KE 20-200 eV can be
diffracted by lattice of atomic dimensions. Low energy electrons are strongly back-
scattered by the electrons of the surface atoms. This means that electrons of 20-200 eV
penetrate only ~10-50 Å into surface.
Experimental arrangement
An experimental arrangement of LEED is shown in the Fig. 1.17. A collimated
and monoenergetic beam of electrons with well-defined low energy (typically in the
range 20 - 200 eV) incident normally on the sample surface. The analysis of diffracted
electrons is carried out by modern data acquisition system which usually contains a CCD
camera kept nearby the screen for diffraction pattern visualization and a computer for
data recording and further analysis.

1.6 Properties of nanomaterials:

Nanomaterials have the structural features in between of those of atoms and the
bulk materials. While most microstructured materials have similar properties to the
corresponding bulk materials, the properties of materials with nanometer dimensions are
significantly different from those of atoms and bulks materials. This is mainly due to the
nanometer size of the materials which condense them: (i) large fraction of surface atoms;
(ii) high surface energy; (iii) spatial confinement; (iv) reduced imperfections, which do
not exist in the corresponding bulk materials. Due to their small dimensions,
nanomaterials have extremely large surface area to volume ratio, which makes a large to
be the surface or interfacial atoms, resulting in more surface dependent material
properties. Especially when the sizes of nanomaterials are comparable to length, the
entire material will be affected by the surface properties of nanomaterials. This in turn
may enhance or modify the properties of the bulk materials. For example, metallic
nanoparticles can be used as very active catalysts. Chemical sensors from nanoparticles
and nanowires enhanced the sensitivity and sensor selectivity. The nanometer feature
sizes of nanomaterials also have spatial confinement effect on the materials, which bring
the quantum effects. The energy band structure and charge carrier density in the materials
can be modified quite differently from their bulk and in turn will modify the electronic
and optical properties of the materials. For example, lasers and light emitting diodes
(LED) from both of the quantum dots and quantum wires are very promising in the future
optoelectronics. High density information storage using quantum dot devices is also a fast
developing area. Reduced imperfections are also an important factor in determination of
the properties of the nanomaterials. Nanostructures and Nanomaterials favors of a self-
purification process in that the impurities and intrinsic material defects will move to near
the surface upon thermal annealing. This increased materials perfection affects the
properties of nanomaterials. For example, the chemical stability for certain nanomaterials
may be enhanced, the mechanical properties of nanomaterials will be better than the bulk
materials. The superior mechanical properties of carbon nanotubes are well known. Due
to their nanometer size, nanomaterials are already known to have many novel properties.
Many novel applications of the nanomaterials rose from these novel properties have also
been proposed.

1.6.1 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
nanowires 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. In electrically conducting carbon nanotubes, only one
electron wave mode is observed which transport the electrical current.
1.6.2 Magnetic Properties
Bulk gold and Pt are non-magnetic, but at the nano size they are magnetic.
Surface atoms are not only different to bulk atoms, but they can also be modified by
interaction with other chemical species, that is, by capping the nanoparticles. This
phenomenon opens the possibility to modify the physical properties of the nanoparticles
by capping them with appropriate molecules. Actually, it should be possible that non-
ferromagnetic bulk materials exhibit ferromagnetic-like behavior when prepared in nano
range. One can obtain magnetic nanoparticles of Pd, Pt and the surprising case of Au
(that is diamagnetic in bulk) from non-magnetic bulk materials. In the case of Pt and Pd,
the ferromagnetism arises from the structural changes associated with size effects.
However, gold nanoparticles become ferromagnetic when they are capped with
appropriate molecules: the charge localized at the particle surface gives rise to
ferromagnetic-like behavior. Surface and the core of Au nanoparticles with 2 nm in
diameter show ferromagnetic and paramagnetic character, respectively. The large spin-
orbit coupling of these noble metals can yield to a large anisotropy and therefore exhibit
high ordering temperatures. More surprisingly, permanent magnetism was observed up to
room temperature for thiol-capped Au nanoparticles. For nanoparticles with sizes below 2
nm the localized carriers are in the 5d band. Bulk Au has an extremely low density of
states and becomes diamagnetic, as is also the case for bare Au nanoparticles. This
observation suggested that modification of the d band structure by chemical bonding can
induce ferromagnetic like character in metallic clusters.

1.7 Applications of nanomaterials:

Nanomaterials having wide range of applications in the field of electronics, fuel
cells, batteries, agriculture, food industry, and medicines, etc... It is evident that
nanomaterials split their conventional counterparts because of their superior chemical,
physical, and mechanical properties and of their exceptional formability.

Carbon nanotubes - Microbial fuel cell

Microbial fuel cell is a device in which bacteria consume water-soluble waste
such as sugar, starch and alcohols and produces electricity plus clean water. This
technology will make it possible to generate electricity while treating domestic or
industrial wastewater. Microbial fuel cell can turn different carbohydrates and complex
substrates present in
wastewaters into a source
of electricity. The
efficient electron transfer
between the
microorganism and the
anode of the microbial
fuel cell plays a major
role in the performance
of the fuel cell. The
organic molecules
present in the wastewater
posses a certain amount
of chemical energy,
which is released when
converting them to
simpler molecules like
Fig. 1.18. Schematic representation of microbial fuel cell
CO2. The microbial fuel
cell is thus a device that
converts the chemical
energy present in water-soluble waste into electrical energy by the catalytic reaction of
microorganisms. Carbon nanotubes (CNTs) have chemical stability, good mechanical
properties and high surface area, making them ideal for the design of sensors and provide
very high surface area due to its structural network. Since carbon nanotubes are also
suitable supports for cell growth, electrodes of microbial fuel cells can be built using of
CNT. Due to three-dimensional architectures and enlarged electrode surface area for the
entry of growth medium, bacteria can grow and proliferate and get immobilized. Multi
walled CNT scaffolds could offer self-supported structure with large surface area through
which hydrogen producing bacteria (e.g., E. coli) can eventually grow and proliferate.
Also CNTs and MWCNTs have been reported to be biocompatible for different
eukaryotic cells.

1.8 Disadvantages of Nanomaterials

(i) Instability of the particles - Retaining the active metal nanoparticles is highly
challenging, as the kinetics associated with nanomaterials is rapid. In order to retain
nanosize of particles, they are encapsulated in some other matrix. Nanomaterials are
thermodynamically metastable and lie in the region of high-energy local-minima. Hence
they are prone to attack and undergo transformation. These include poor corrosion
resistance, high solubility, and phase change of nanomaterials. This leads to deterioration
in properties and retaining the structure becomes challenging.
(ii) Fine metal particles act as strong explosives owing to their high surface area coming
in direct contact with oxygen. Their exothermic combustion can easily cause explosion.
(iii) Impurity - Because nanoparticles are highly reactive, they inherently interact with
impurities as well. In addition, encapsulation of nanoparticles becomes necessary when
they are synthesized in a solution (chemical route). The stabilization of nanoparticles
occurs because of a non-reactive species engulfing the reactive nano-entities. Thereby,
these secondary impurities become a part of the synthesized nanoparticles, and synthesis
of pure nanoparticles becomes highly difficult. Formation of oxides, nitrides, etc can also
get aggravated from the impure environment/ surrounding while synthesizing
nanoparticles. Hence retaining high purity in nanoparticles can become a challenge hard
to overcome.
(iv) Biologically harmful - Nanomaterials are usually considered harmful as they
become transparent to the cell-dermis. Toxicity of nanomaterials also appears
predominant owing to their high surface area and enhanced surface activity.
Nanomaterials have shown to cause irritation, and have indicated to be carcinogenic. If
inhaled, their low mass entraps them inside lungs, and in no way they can be expelled out
of body. Their interaction with liver/blood could also prove to be harmful.
(v) Difficulty in synthesis, isolation and application - It is extremely hard to retain the
size of nanoparticles once they are synthesized in a solution. Hence, the nanomaterials
have to be encapsulated in a bigger and stable molecule/material. Hence free
nanoparticles are hard to be utilized in isolation, and they have to be interacted for
intended use via secondary means of exposure. Grain growth is inherently present in
nanomaterials during their processing. The finer grains tend to merge and become bigger
and stable grains at high temperatures and times of processing.
(vi) Recycling and disposal - There are no hard-and-fast safe disposal policies evolved
for nanomaterials. Issues of their toxicity are still under question, and results of exposure
experiments are not available. Hence the uncertainty associated with affects of
nanomaterials is yet to be assessed in order to develop their disposal policies.