Nanomaterials and its Application

What is Nano?
‘Nano’ is derived word from the Greek word i.e., Nanos which means Dwarf .It is more correct
and near meaning is “Small”.
On length scale, a unit of length is define as nanometer. It is one of very small value of size i.e.,
billionth part of part of 1 meter or 10 core equal length division of 1 meter. 1 part of 10 core
1
division has length 10−9 meter or 109 part of 1 meter. So we have
1𝑚 = 109 𝑛𝑚
10−9
1𝑛𝑚 = 10−9 𝑚 = 10 𝑚 = 10 × 10−10 𝑚 = 10Å
10
The nanometer is practically defined in term of size of atoms.
In term of Hydrogen atoms, 1 nanometer is approximately equal to length of 10 hydrogen atoms
are aligned in a line.

The atomic radius of H atom is 𝑟𝐻−𝑎𝑡𝑜𝑚 = 0.529 Å

𝑑𝐻−𝑎𝑡𝑜𝑚 = 2 × 𝑟𝐻−𝑎𝑡𝑜𝑚 = 1.058 × 10−10 𝑚
So,
1𝑛𝑚 = 10 × 𝑑𝐻−𝑎𝑡𝑜𝑚 = 1.058 × 10−9 𝑚
In term of Si- atoms, 1 nanometer is approximately equal to length of 05 Si- atoms are aligned in
a line.

The atomic radius of Si- atoms is 𝑟𝑆𝑖−𝑎𝑡𝑜𝑚 = 1.11 Å

𝑑𝑆𝑖−𝑎𝑡𝑜𝑚 = 2 × 𝑟𝑆𝑖−𝑎𝑡𝑜𝑚 = 2.22 × 10−10 𝑚
So,
1𝑛𝑚 = 5 × 𝑑𝑆𝑖−𝑎𝑡𝑜𝑚 = 1.11 × 10−9 𝑚
An objects existing in our observable world have to divide broadly into two type on basis of size
of objects or collection types on basis of size of objects or collection of particles.

Microscopic World: The size of particle or system of particle are in range i.e.
, 0 < 𝑠𝑖𝑧𝑒 ≤ 10−6 𝑚 . The physical properties is described by quantum mechanics. Such particle
can’t see by naked eyes but its existence is understand by its effect.
The Microscopic World is further divided into two sub group i.e., Atomic Scale world and Nano
world
Atomic Scale world: The size of particle and group of particles of it is in range 0 < 𝑠𝑖𝑧𝑒 ≤
10−9 𝑚
Nano Scale world: The size of particle and group of particles of it is in range 10−9 𝑚 < 𝑠𝑖𝑧𝑒 <
10−6 𝑚 or the practical range of Nano scale world is 1𝑛𝑚 𝑡𝑜 100𝑛𝑚
Macroscopic World: The size of particle or system of particle are in range i.e.
, 𝑠𝑖𝑧𝑒 > 10−6 𝑚 . The physical properties is described by Classical mechanics. Such particle can
be seen by naked eyes.

The Microscopic World is further divided into two sub group i.e., Classical and Astronomical
world.

Nanoscience: This is a branch of scientific study of material whose dimension is in scale of 1nm
to 100nm.This branch of science in which one can study the properties i.e., physical, chemical,
mechanical, electrical, magnetic, optical etc. of material and it helps to understand the drastic
change in their properties at nanoscale dimension.
Nano Technology: It is technology through which we develop, design and produce the useful and
beneficial products/device/structure at nano level by manipulating and controlling the facts of
variation of properties on reduction of size of material upto nanoscale.
It is an outcome of Nanoscience.
Example of Nanoscience and Nanotechnology:
1. The leaf of lotus plant is naturally coated by nano thin film which keep clean the lotus plant
leaf, has self-cleaning and water repellent properties through nano film. The knowing the
self-cleaning and water repellent properties is Science. But using this fact to produce some
application is nanotechnology.
2. The DNA is also best example of nano- objects. The size of DNA is 2.5 nm to 3.5 nm.
3. The wings of butterfly have natural coated thin film which are responsible for strength to
the wings and appearance of colour.
Note: As per size of particle we have system as decreasing size
Bulk System (3D system)
Macroscopic particle
Microscopic Particle
Nanoscale System
Cluster: It is a collection of atoms that are between individuals atom or molecule and bulk material.
The collection of atoms are in range from 3 𝑡𝑜 3𝑋107 atoms.
Atonic scale system
Magic Number configuration: It is number of collection o atoms enable to closed shell formation
and geometrical stable configuration. It can be used to useful system. e.g., Au 55 (Gold) is cluster
in which gold has 55 atoms in collection of gold atoms.
History Nano Science:
A. Lycurgus cup:
Nanoparticles and structures have been used unknowingly by humans in fourth century AD, by
the Roman, which demonstrated one of the most interesting examples of nanotechnology in the
ancient world. The Lycurgus cup, from the British Museum collection, represents one of the most
outstanding achievements in ancient glass industry.
It is the oldest famous example of dichroic glass. Dichroic glass describes two different types of
glass, which change color in certain lighting conditions. This means that the Cup have two different
colors: the glass appears green in direct light, and red-purple when light shines through the glass.
In 1990, the scientists analyzed the cup using a transmission electron microscopy (TEM) to explain
the phenomenon of dichroism.
1. The observed dichroism (two colors) is due to the presence of nanoparticles with 50–100
nm in diameter.
2. X-ray analysis showed that these nanoparticles are silver-gold (Ag-Au) alloy, with a ratio
of Ag: Au of about 7:3, containing in addition about 10% copper (Cu) dispersed in a glass.
3. The Au nanoparticles produce a red color as result of light absorption (~520 nm).
4. The red-purple color is due to the absorption by the bigger particles while the green color
is attributed to the light scattering by colloidal dispersions of Ag nanoparticles with a size
> 40 nm.
5. The Lycurgus cup is recognized as one of the oldest synthetic Nanomaterials

Fig: The Lycurgus cup. The glass appears green in reflected light and red-purple in transmitted
light.

B. Stained glass windows of Church:

A similar effect is seen in late medieval church windows, shining a luminous red and yellow colors
due to the fusion of Au and Ag nanoparticles into the glass. An example of the effect of these
nanoparticles with different sizes to the stained glass windows.
Fig: Effect of nanoparticles on the colors of the stained glass window
After analyzing the reason, it has been found that the cause for appearing different color in stained
window glass are
1. Due to doping of spherical shaped Gold nano particle of different size, stained glass appears
in different colors.

Size Shape Colour reflected

25 nm Sphere Red
50nm Sphere Green
100nm Sphere Orange

2. Due to doping of spherical shaped Silver nano particle of different size, stained glass
appears in different colors.
Size Shape Colour reflected
40 nm Sphere Blue
100nm Sphere Yellow
100nm Prism Red

C: Different Historical Event

During the 9th–17th centuries, glowing, glittering “luster” ceramic glazes used in the Islamic
world, and later in Europe contained Ag or copper (Cu) or other nanoparticles . The Italians also
employed nanoparticles in creating Renaissance pottery during 16th century. They were influenced
by Ottoman techniques: during the 13th–18th centuries, to produce “Damascus” saber blades,
cementite nanowires and carbon nanotubes were used to provide strength, resilience, and the
ability to hold a keen edge. These colors and material properties were produced intentionally for
hundreds of years. Medieval artists and forgers, however, did not know the cause of these
surprising effects.
D. Colloidal gold

In 1857, Michael Faraday studied the preparation and properties of colloidal suspensions of
“Ruby” gold. Colloidal gold is a sol or colloidal suspension of nanoparticles of gold in a fluid,
usually water.[1] The colloid is usually either wine-red coloured (for spherical particles less than
100 nm) or blue/purple (for larger spherical particles or nanorods). Their unique optical and
electronic properties make them some of the most interesting nanoparticles. Faraday demonstrated
how gold nanoparticles produce different-colored solutions under certain lighting conditions.

Nanoparticle System:
It is collection of atoms having dimension of 1nm. Such systems are called Nanoparticle
Systems.
Nanomaterial:
Nanomaterials are materials with at least one external dimension that measures 100 nanometers
(nm) or less or with internal structures measuring 100 nm or less. The Nanomaterials that have the
same composition as known materials in bulk form may have different properties.
Materials reduced to the nanoscale can suddenly show very different properties compared to what
they show on a bulk/ macroscale. The best example properties shown at nanoscale
 The Copper (Cu) are Opaque substances at bulk level but it becomes transparent at
nanolevel
 The Platinum (Pt) is an inert material at bulk level but it becomes catalysts at nanolevel.
 The Aluminum (Al) is a stable material at bulk level but it turns combustible at nanolevel.
 The Gold (Au) is a Solid at bulk level but it turns into liquids at nanolevel.
 The silicon (Si) is a Semiconductor at bulk level but it may turn into insulator or conductor
at nanolevel
Classification of nano materials:
Nanomaterials are classified into different types on the base of size of dimension and on the base
of occurrence.
A. On the base of size of dimension: There are three types of nanomaterial on the bases of
reduction of size of dimension of nanomaterial.
Zero Dimensional Nanomaterials (0D):
Zero-dimensional (0-D) structures include materials with all dimensions at nanoscale of 1
to 100 nm. Most of these materials are spherical in shape; however, cubes and polygonal
shapes with nano-dimensions are also found under this class. Such material are also called
Quantum Dot.
For example, nanoparticles, nanospheres etc.
One-dimensional Nanomaterials (1D):
One –Dimensional (1D) structures are those that exhibit at least two dimensions in the
nanoscale of 1 to 100 nm and one of dimension in bulk range i.e.,(≥ 1𝜇𝑚) .
Some examples of 1D Nanomaterials include, nanorods, nanotubes, nanowires, nanobelts,
nanoribbons, nanofibers, nanotips etc.
Two-dimensional Nanomaterials (2D): Two –Dimensional (2D) structures are those that
exhibit at least one dimensions in the nanoscale of 1 to 100 nm and two dimension are in
bulk range i.e. (≥ 1𝜇𝑚) .
Some examples of 2D Nanomaterials are thin films, nanoplates, nanosheets, nanoflowers,
quantum wells etc.
Three-dimensional Nanomaterials (3D): The 3D structures are actually microscale
porous materials with pore diameters in the nanometer range (1 to 100 nm).
For example, zeolite, mesoporous materials etc.

B. On the bases of Occurrence: There are three types of nanomaterial on the bases of
Occurrence.
 Natural Nanomaterials: The material is found in nature in sale of nanoscale 1nm to
100nm. Nature is full of example of Nanomaterials which are naturally present in nature.
E.g., smoke, volcano dust, bacteria, virus, Nao film coated on leaf of lotus plant etc.
Incidental Nanomaterial: Such nanomaterial are formed and resulted unintendedly by
product of human activity. Such as diesel exhaust, coal combustion and welding fumes
grinding dust etc.

Engineered Nanomaterials:
These Nanomaterials are created intentionally. Such a material are created using controlled
method and manipulation at nanoscale e.g., carbon nanotube, fullerene, 2D graphene etc.

C. On the bases of structural configuration

Carbon Based Materials: These Nanomaterials are composed mostly of carbon network,
most commonly taking the form of a hollow spheres, ellipsoids, or tubes. In these material
carbon are mostly bound by van der Waals interaction. Spherical and ellipsoidal carbon
Nanomaterials are referred to as fullerenes, while cylindrical ones are called nanotubes.
These particles have many potential applications, including improved films and coatings,
stronger and lighter materials, and applications in electronics.
Metal Based Materials: These Nanomaterials include quantum dots, nanogold, nanosilver
and metal oxides, such as titanium dioxide. A quantum dot is a closely packed
semiconductor crystal comprised of hundreds or thousands of atoms, and whose size is on
the order of a few nanometers to a few hundred nanometers. Changing the size of quantum
dots changes their optical properties.
Dendrimers: Dendrimers are repetitively branched molecules. The name comes from the
Greek word ‘Dendron’ (tree). These Nanomaterials are nanosized polymers built from
branched units. The surface of a dendrimer has numerous chain ends, which can perform
specific chemical functions. These Nanomaterials are nanosized polymers built from
branched units. The surface of a dendrimer has numerous chain ends, which can be tailored
to perform specific chemical functions. This property could also be useful for catalysis.
Also, because three-dimensional dendrimers contain interior cavities into which other
molecules could be placed, they may be useful for drug delivery. Dendrimers are used in
molecular recognition, nanosensing, light harvesting, and opto-electrochemical devices.
Composites: Composites combine nanoparticles with other nanoparticles or with larger, bulk-type
materials. Nanoparticles, such as nanosized clays, are already being added to products ranging
from auto parts to packaging materials, to enhance mechanical, thermal, barrier, and flame-
retardant properties.
Nano Effect:
The nano effect in nanomaterial details about the properties which countered during reduction of
size of material upto nanoscale. The properties of material changed drastically. This is caused due
to quantum effect which become dominate at nanoscale. This huge change in properties of
nanomaterial has great interest.
e.g. if material at bulk level shows some parametric value of some quantities of properties and due
to it , the physical quantities have certain a set of application but nanoscale same material shows
different set of parametric value of same properties of same quantities. So nano counterpart is
ready to use for newer applications. It is caused due to nano effect.
Why does Nano effect appear in Nanomaterials?
Various macroscopically measured properties of bulk material i.e., electrical conductivity,
magnetic, mechanical properties etc., are based on phenomena based that occur at an altogether
different size range. The some properties of matter even at bulk level, occurs at grain boundary
level, atonic level, plane of atoms, group of atoms or molecules. Due to control over properties
some material “X”. It can stand for upto 1100 ℃ at bulk scale. But in some application we need
material must stand upto 3000K. Due to Nano effect, same material can stand for required
temperature. We don’t need to search new material “Y”. This increases in production cost. We
need new technique, new assembly line etc.

Why do we study properties of Nano material?

It is because a material transforms from bulk to nanoscale, all the physical properties change
drastically due to nanoeffect so we need to know systematically them. By Knowing correct
information of properties of nano materials, one make use of it to develop fruitful device and
technology.
e.g., Bulk Gold Id Yellow but nanogold particles become red. It is example of Nanoscience.
The screen of LED TV is made of quantum Dots. Each pic cell of screen is made off materials
which are in form of Quantum Dots.
Note:
1. According R P Feynman, any devices or material can be made atom by atom. This idea
evolved the nanotechnology
2. The technique involved in preparation, cartelization and use of properties of nano materials
in different application are collectively known as Nanotechnology.
Understanding of origin Properties of materials at Bulk and Nanolevel:
The origin of any properties has root cause at microscopic origin. So the resultant value of that
properties is average value of it over all grain boundaries etc. The dependence and value of
properties may be different grain level than bulk level.
It is noted that different properties of material may depend o atomic structure of a material i.e.,
geometric structure. It also size dependent. But it must has some trend from atomic level to bulk
level.
Example: A sample i.e., dog shaped of any material which is being tested for measuring its
mechanical property i.e., stress-strain. The plot of stress-strain curve provides the many
mechanical properties i.e., Bulk modulus, young’s modulus etc.

1. The mechanical properties of sample occur at very small level not at bulk level. That small
level can be grain size, atoms, plane of atoms, group of atoms, cluster etc.
2. For many mechanical properties, we have to apply load on sample, the plane of atoms of nano
dimension or grain may slip/twist/deform with each other. Such may cause origin of
mechanical properties.
3. Due to these facts, some mechanical properties originated and affected by plane to plan or
atom to atom.
4. The origin of mechanical properties are not happening at bulk level. It is occurring at very
much atomic dimension (microscopic level).
So, the properties i.e. optical, electrical, mechanical, chemical, magnetic, etc., are originated
at microscopic level not at bulk level. At Bulk level the value of these properties are basically
cumulative average of value/dependence of that properties at microscopic level i.e., electronic
level, atomic level, plane of atoms, group or cluster of atoms etc.
Important Points:
1. If we manipulate the material at or near to atomic level or nano size of grain of material
on which phenomena is actually happening. For certain property, it occurring at electronic
 level/atomic level/ plane of atoms/group of atoms/cluster etc. and size is reduced to
electronic level/atomic level/ plane of atoms/group of atoms/cluster etc. The value of such
properties has very much different and drastic vale than bulk level.
2. If phenomena is happening at 100toms level so the size of same is reduced to 100 atoms
levels the properties are drastically change.
Therefore, the material at nanoscale shoes total newer properties which are very much
different than bulk so it can be used for new application.
On reduction of size of material upto nanoscale i.e., desire characteristic size of material on
which properties originated, we get a newer control of manipulating the properties which
change drastically and has potential for newer application.
A best example to study the tensile strength of material. It occurs at atomic plane level. If the
size of material is reduced to few order of atomic plane (off course upto certain nanoscale).
Certainly the tensile strength change drastically and such set sudden change in value of tensile
vale of material opened the door for newer application and power to technology. Actually we
are rearranging and controlling the size upto characteristic length on which phenomena are
occurring to result the properties. Now, we have fine control over their properties of same
material. So Nanomaterials become more interesting and useful for newer application.
Note:
In older days, if we requires material for new application, we always need new material
because that application requires different specification. To match new specification for
application, we need new material. But in nano age, the same material is used by controlling
the properties and specification matched to application by reducing the size of material at
nanoscale. E.g., in one application we requires a material (X) which stands with 800 C. The
material (X) can’t be used in other application in which material stands with 1100 C. In older
day one needs to search new material(Y). But in nano age, we can tailor the X material by
controlling size of material upto desire characteristic length.
Size dependent properties of Nanomaterials:
The properties of nanomaterial are changing drastically at nanoscale. This change is very
useful to develop new application. The main cause of change in properties of nanomaterial
can be understand on the bases of following facts:
1. Surface to Volume ratio
2. Large fraction of surface atoms
3. Change in energy band gap
4. Quantum confinement
5. Reduced imperfections
Surface area to Volume ratio:
Surface area to volume ratio in nanoparticles have a significant effect on the
Nanoparticles properties. Firstly, nanoparticles have a relative larger Surface
Area when compared to the same volume of the material. It is a ratio between
Surface are of system and volume of system.
In general a mathematically, it is given as
𝑆𝑢𝑟𝑓𝑎𝑐𝑒 𝐴𝑟𝑒𝑎
𝑆𝑉𝑅 =
𝑉𝑜𝑙𝑢𝑚𝑒
What happens to the surface area and volume when sizes of objects become
Small?
Surface area is the measure of how much exposed area a solid object has, expressed in square
units. One of the main features of materials at the nanoscale is the increase in their surface
area. Actually, what is important is the ratio of surface area to volume. This ratio is called the
Surface Area to Volume Ratio and is abbreviated as SVR. This ratio is the amount of surface
are per unit volume of an object. SVR is measured in units of inverse distance. We will
calculate the values of SVR for different geometrical objects and investigate. what happens to
this ratio as sizes become small?
Sphere:
For example, let us consider a sphere of radius r:
 The surface area of sphere is given SA
𝑆𝐴 = 4𝜋𝑟 2
The volume of sphere is V
4 3
𝑉= 𝜋𝑟
3
𝑆𝑢𝑟𝑓𝑎𝑐𝑒 𝐴𝑟𝑒𝑎 4𝜋𝑟 2 3
𝑆𝑉𝑅 = = =
𝑉𝑜𝑙𝑢𝑚𝑒 4 3 𝑟
𝜋𝑟
3

It is clear from the formula SVR = 3/r that when r becomes very small, SVR becomes very
large. As r approaches zero, the value of SVR approaches infinity. Thus for an infinitesimally
small sphere, the value of SVR becomes infinitely large It means that the surface area to
volume ration increases with the decrease in radius of the sphere and vice versa. It can also be
conclude here that when given volume is divided into smaller piece, the surface area increases.
Therefore as particle size decreases, a greater portion of the atoms are found at the surface
compared to those inside.
For example, a particle of size 3 nm has 50% of its atoms on its surface, at 10 nm 20% of its
atoms and at 30 nm has 5% of its atoms on its surface. Therefore nanoparticles have a much
greater surface area per unit volume compared with the larger particles. It leads to
nanoparticles more chemically reactive. As growth and catalytic chemical reaction occurs at
surfaces, therefore a given mass of nanomaterial will be much more reactive than the same
mass of material made up of large particles. It is also found that materials which are inert in
their bulk form are reactive when produced in their nanoscale form. It can improve their
properties.
Cube:
Assume the cube to have a side of length 𝑠
𝑆𝑢𝑟𝑓𝑎𝑐𝑒 𝑎𝑟𝑒𝑎 𝑆𝐴 𝑜𝑓 𝑐𝑢𝑏𝑒 = 6𝑠 2
𝑉𝑜𝑙𝑢𝑚𝑒(𝑉) 𝑜𝑓 𝑐𝑢𝑏𝑒 = 𝑠 3

𝑆𝑢𝑟𝑓𝑎𝑐𝑒 𝐴𝑟𝑒𝑎 6𝑠 2 6
𝑆𝑉𝑅 = = 3 =
𝑉𝑜𝑙𝑢𝑚𝑒 𝑠 𝑠
Cylinder:
The cylinder structure are found in CNT, wire and fibrous nanomaterial etc.

Assume the cylinder to have 𝑎 𝑟𝑎𝑑𝑖𝑢𝑠 = 𝑟 𝑎𝑛𝑑 𝑎 ℎ𝑒𝑖𝑔ℎ𝑡 = ℎ

𝑆𝑢𝑟𝑓𝑎𝑐𝑒 𝑎𝑟𝑒𝑎 𝑜𝑓 𝑐𝑦𝑙𝑖𝑛𝑑𝑒𝑟 = 2𝜋𝑟 2 + 2𝜋𝑟ℎ
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑐𝑦𝑙𝑖𝑛𝑑𝑒𝑟 = 𝜋𝑟 2 ℎ
𝑆𝑢𝑟𝑓𝑎𝑐𝑒 𝐴𝑟𝑒𝑎 2𝜋𝑟 2 + 2𝜋𝑟ℎ
𝑆𝑉𝑅 = =
𝑉𝑜𝑙𝑢𝑚𝑒 𝜋𝑟 2 ℎ
2 2
𝑆𝑉𝑅 = +
ℎ 𝑟
As SVR is inversely proportional to r and h. As r reduces the SVR increases very rapidly.

The larger the surface area of material, provides the more free surfaces to act. On more free
surface area, more number of loosely bound atoms or atom like system which actively take
part in the process. This process helps us to understand the phenomena like chemical
reactivity, melting and mechanical process.
Large fraction of surface atoms:
The surface of a sphere scales with the square of its radius r, but its volume scales
With 𝑟 3 . The total number of atoms 𝑁 in this sphere scales linearly with volume. The fraction
of atoms at the surface is called dispersion F, and it scales with surface area divided by volume,
i.e. with the inverse radius or diameter, and thus also with 𝑁 −1/3 . Basically the same relation
holds for long cylinders of radius 𝑟 and for thin plates of thickness𝑑. The size dependence of
dispersion is illustrated for cubes of n atoms along an edge and a total of 𝑁 = 𝑛3 atoms,
where the number of atoms at the surface is 6𝑛 corrected for double counts at the 12 edges
and for reinstalling the 8 corners. For large N the edge and corner corrections become
negligible, leading to the 𝑁 −1/3 scaling:
6𝑛2 − 12𝑛 + 8 6 12 8 6 12 8
𝐹= 3
= − 2+ 3= 1− 2+
𝑛 𝑛 𝑛 𝑛 𝑁
𝑁3 𝑁3
6 2 8 6
𝐹= 1 [1 − 1 + 2] ≅ 1
𝑁3 𝑁3 𝑁3
𝑁3
All properties which depend on the dispersion of a particle lead to a straight line when plotted
1
against 𝑟 −1 , 𝑑 −1 𝑜𝑟𝑁 3 .
Atoms at the surface have fewer direct neighbours than atoms in bulk. Therefore, particles
with a large fraction of atoms at the surface have low coordination number. In a small isolated
nanoparticle, a large proportion of the total number of atoms will be present either at or near
the free surface. Similarly in nanocrystalline materials, where a large portion of atoms will be
either at or near grain boundaries. Such structural differences in reduced-dimensional systems
would be expected to lead to very different properties from the bulk. The major difference
between the nano materials compared to bulk is big fraction of total number of atoms on
surface.
In reality, however, the atoms in the interior of the cluster are more highly coordinated, form
more bonds and are therefore more stable than those at the cluster surface. For cubic crystals
the corner atoms are the least saturated ones, followed by the edge, the in-plane surface and
then the atoms in the interior. For this reason, the corner atoms normally exhibit the highest
affinity to form bonds to adsorbate molecules, followed by the edge and the in-plane surface
atoms, a fact that is of utmost importance for the catalytic activity. A further consequence of
the lower stabilisation of atoms or molecules at the surface is the lower melting point of
surface layers.
Nanoparticles have a substantial fraction of their atoms on the surface. This high surface area
to volume ratio is an important factor in many of the physical properties of nanoparticles, such
as their melting point and vapor pressure, and also in their reactivity. Heterogeneous
catalysts, for example, are often based on nanoparticles because the catalytically reactive
atoms are those that are on the surface of the particle.
Change in energy band gap:
As we know that material having different optical and electrical properties which are directly
related to band gap between valance band and conduction band. The energy gap is also known
as forbidden region energy. If that forbidden amount of energy is given any how to charge
carrier (an electron/ a hole). The charge carrier i.e., electron of valance band jump to
conduction band. So the electron may start conduct or show optical properties. A suitable
energy (by optical energy or electrical) is given to atom like system. The energy is being
absorbed and absorption take place and it Excited atom like system emits the energy as EMR
as emission.
What will happen the formation of band in material (meta/semiconductors/insulators) is
quantum mechanical process. In solids atom like systems are closely placed and packed
densely in material to have regular manner of arrangement with maintain periodicity or
irregular manner of arrangement with maintain non periodicity. It well established that atom
like systems are quantum mechanical system and have the discrete energy pattern. Which can
be obtained by solving Schrodinger wave equation under various interaction. As isolated atom
like system do not intact each other until unless such system bring in cols proximity in space
to form a bound system. Due to closely packed system, the collection of atoms interact via
many inactions so the energy level of such systems also intact and does not remain unaffected.
So such collection of energy levels get split into more number of sub energy levels due to
Pauli Exclusion Principle and interaction between them. Therefore, the energy pattern are
rearranged due to the rearrangement of electronic configuration of system. It results and forms
bunch of dense split energy levels with least spacing and energy level almost become
continuous in band.
The group or bunch of permissible sub splinted energy levels are called Energy band. The
redistribution of energy level results a different types of band pattern. In which different bands
are formed with some order of forbidden energy i.e., energy gap.
1. Valance Band
The band of energies occupied by the valance electrons is called as valance band.
The electrons in the outermost orbit of an atom are known as valance electrons. In a normal
atom, the valance band possesses electrons of higher energy. This band may be completely or
partially filled. Electrons can be moved from the valance band to the conduction band by the
application of external energy.
2. Forbidden Band or Energy Gap
The gap between the valance band and the conduction band on the energy level diagram is
known as the forbidden band or energy gap.
Electrons are never found in this gap. Electrons may jump back and forth from the bottom
valance band to the top conduction band, but they never come to rest in the forbidden gap.
3. Conduction Band
The band of energies occupied by conduction electrons is known as the conduction band.
This is the uppermost band, and all electrons in the conduction band are free electrons. The
conduction band is empty for insulators and partially filled for conductors.

Explain formation of energy bands in solid sodium (Na):

 For an isolated sodium atom (atomic number 11) the electronic configuration is given
as1𝑠 2 , 2𝑠 2 , 2𝑝6 , 3𝑠1. The outermost level 3s is half filled in sodium.
 The energy levels are filled according to Pauli’s exclusion principle.
 Consider two sodium atoms close enough so that outer 3s electrons can be considered
equally to be part of any atom.
 The 3s electrons from both the sodium atoms need to be accommodated in the same
level. v. This is made possible by splitting the 3 s level into two sub-levels so that the
Pauli’s exclusion principle is not violated. Figure given below shows the splitting of
the 3 s level into two sub levels.
 When solid sodium is formed, the atoms come close to each other such that distance
between them remains of the order of 2 – 3 Å. Therefore, the electrons from different
atoms interact with each other and also with the neighbouring atomic cores.
 The interaction between the outer most electrons is more due to overlap while the inner
most electrons remain mostly unaffected. Each of these energy levels is split into a
large number of sub levels, of the order of Avogadro’s number due to number of atoms
in solid sodium is of the order of this number.
 The separation between the sublevels is so small that the energy levels appear almost
continuous. This continuum of energy levels is called an energy band. The bands are
called 1 s band, 2s band, 2p band and so on. Figure shows these bands in sodium metal.
Energy bands in solid Diamond:

What will happen to energy band as reduction of size of material upto nanoscale?
On reducing the size of material upto nanoscale, material has few number of atom like systems
which are having least interaction so the number of energy level in band become less and
spacing between energy level become large. The energy level spacing increases with
decreasing dimension. The energy level are
Energy band structure in metal:
On decreasing the size of metal upto nanoscale, the metal loses it conductivity and become
insulators. The DOS (the number of energy levels per unit interval of energy) is reduced and
spacing between energy level increasing. So energy levels in band become quantized. In that
way the meat system become insulator.

Energy band structure in Semiconductor:

On decreasing the size of Semiconductor upto nanoscale, the Semiconductor become

insulators. The DOS (the number of energy levels per unit interval of energy) is reduced and
spacing between energy level increasing. So energy levels in band become quantized. In that
way the metal system become insulator.
The band gap is very low value in semiconductor and DOS in bulk for both CB and VB are
high. On reduction of size upto nanoscale DOS of both CB and VB also decreases and band
gap increases. The electrical conductivity also decreases. It means the more energy is required
to send electron from valance band to conduction band. The Semiconductors GaAs at bulk
level is 1.014eV but at nanoscale the energy band gap of GaAs is 1.5eV.
To understand more clearly, the nature of semiconductor to insulator on reduction of size of
material

What is the relationship between band gap and size of nano particles?

One treats the electronic properties of a single semiconducting nanoparticle (quantum dot, for
example) as that of a particle in a box. This yields the discretization of energy levels, and presence
of degeneracy, depending upon the number of dimensions that are subject to quantum confinement.
For instance, a quantum dot is considered to be quantum-confined in all the three dimensions,
whereas a quantum wire would have confinement in two of the three dimensions.

The relationship between the band gap and the particle size is given by the Effective mass
approximation:

ℎ2 𝜋 2 1 1 18𝑒 2
𝐸 = 𝐸𝑔 (𝐵𝑢𝑙𝑘) + ( + ) − + 𝑠𝑚𝑎𝑙𝑙 𝑡𝑒𝑟𝑚
2𝑅 2 𝑚𝑒 𝑚ℎ 4𝜋𝑅𝜖0

Here, 𝐸 is the band gap of the semiconducting nanoparticle, 𝐸𝑔 is the band gap of the bulk
semiconducting phase, 𝑚𝑒 and 𝑚ℎ are the effective masses for electrons and holes in that
semiconducting phase, and 𝑅 is the radius of the nanoparticle (assuming spherical symmetry as an
approximation). ℎ is the well-known Planck's constant, and 𝜖0 is the permitivitty of free space.
Question: Using ZnO as an example (𝑬𝒈 = 3.3 eV, 𝒎𝒆 and 𝒎𝒉 = are 0.28 𝒎𝟎 and
0.49m0 , 𝝐𝟎 (for ZnO) = 9.1), the particle size turns out to be 4.6 nm. Calculate the Energy of
nano particle ZnO.

Quantum confinement:
The quantum confinement is a quantum size effect. As the size reduction of material upto
nanoscale (upto characteristic length), the confinement of carrier are confined in spatial region.
The carriers have restriction on it motion because the non-availability of enough space to move
freely in physical space. So the motion of carriers are bound in region of space as size is reduced
upto nanoscale. The quantum effect become more effective and carriers are considered as wave
which associated with particle so we may consider the wave nature of carriers but same carries
behaves as particle in bulk form. The confinement is Quantum effect.
Broadly quantum confinement is an effect where the dimension of a typical material is comparable
to the de Broglie wavelength of electrons involved. At such low dimensions the electrons present
in the material behave more or less similar to the electrons present in atoms. In other words,
electrons occupy discrete energy levels rather than a continuum of energy levels in a band. The
following are a few characteristic length scales that are commonly considered to observe quantum
confinement

1. Semiconductors: in semiconductors, Excitons are formed.ie. Bound entity of electron

and holes i.e., electron- hole pair in conduction band and valence band .At nanoscale,
the bound pair are formed and become spatially confined in their respective position.
The characteristic length of confinement is equal to order of radius of Exciton radius i.e.
electron-hole pair radius
2. Metals: In case of metal, the characteristic length of confinement of electron is mean
free path of electrons i.e., order of de-Broglie wavelength associated to Fermi electron
in metal at nanoscale.
3. Ferromagnetic materials: In case ferromagnetic material at nanoscale, the characteristic
length for confinement is typical size of a domain. It results super magnetic properties
at nanoscale.
4. Superconductors: The Coherence length of Cooper pairs is characteristic length.
5. Another good example of confinement is ‘quark confinement’ which results from a
harmonic oscillator potentials operating between quarks. A confinement of quantum
particles can result from a confining potential and differs from classical world that the
particle has a finite probability of escaping the confining potential.

Example of Confinement in Semiconductors:

Semiconductor quantum dots are also known as semiconductor nanocrystals or nanoparticles.

A semiconductor nanocrystal (SNC) or quantum dot (QD) is a semiconductor whose Excitons
are confined in all three spatial dimensions. As a result, they have properties that are between
bulk semiconductors and those of discrete molecules. Size effects are observed in
semiconductor crystals measuring 10-100 nm, whereas quantum size effects are usually the
characteristics of nanocrystallites measuring less than 10 nm.
The physico chemical properties of nanocrystalline particles different from those of bulk
materials for two specific reasons.
 First, the high surface to volume ratio that results in many atoms at the surface in the
crystalline lattice.
 And secondly, the electronic bands are spilt up in to discrete energy levels as the result
three dimensional confinement of the charge carriers occurs.
This leads to quantum confinement of charge results in the increase bandgap with decreasing
particles size.
The band gap, 𝐸𝑔 , increases in magnitude as the semiconductor particle radius decrease in
size to the point where it becomes comparable or smaller than the Exciton radius. These
properties have led to the applications in a wide range of fields i.e., semiconducting quantum
well and super lattice devices, nonlinear optical materials, photocatalysis and imaging
systems. It’s very clear that Quantum confinement effect based semiconductor nanocrystals
were produced tremendous optical and electrical properties than of the bulk materials which
are due to the reduced behavior of characteristic length which is called as Exciton Bohr
diameter. This peculiar characteristic length is usually in the range of few nanometers when
the material reveals size dependent of optical and electrical properties.

One of the most important consequences of the spatial confinement effect is an increase in energy
of the band-to-band excitation peaks (blue shift) as the radius R of a microcrystallite
semiconductor is reduced in relation with the Bohr radius. However due to significant spatial
confinement effect there is an increase in energy of band-to-band excitation peaks which is called
blue shift. In terms, microcrystallite of Radius (R) ranges in semiconductor having less relation
with than of the Bohr Radius. Some of minor difference would have happen between the theoretical
and experimental of confine effect it is due to electron electron-hole interaction energy, in coulomb
term and the confinement energy of the electron and hole in the kinetic energy.
Weak confinement regime
To observe this regime, the radius R of a crystallite should be greater than the bulk Exciton
Bohr radius𝑎𝐵 . In this region of weak confinement, the dominant energy is the Coulomb term
and they already occur in size quantization of the Exciton motion. The Exciton energy states
1
are shifted to higher energies by confinement and shifts in energy ∆E is proportional to𝑅2.
The shift ‘∆𝐸’ of the exciton ground state is given approximately by
ℏ2 𝜋 2
∆𝐸 ≈
2𝑀𝑅 2
Where, 𝑀 is the mass of the Exciton, and it is given by𝑀 = 𝑚𝑒∗  𝑚ℎ∗ , with𝑚𝑒∗ 𝑎𝑛𝑑 𝑚ℎ∗
being the effective masses of the electron and hole respectively.
Moderate confinement regime
Quantum confinement taking another point of view, especially II-VI semiconductor region the
Bohr radius equal 𝑎𝐵 to the material radius (𝑅) which is called moderate confinement regime and
also following terms condition should satisfy 𝑎ℎ < 𝑅 < 𝑎𝑒 for moderate confinement regime
process. The overall process were observed in small QD and its well the well restricted motion of
a photo excited hole.
Strong confinement regime
Finally, the strong confinement regime were confirmed by satisfying the following condition such
that 𝑅 << 𝑎𝐵 , and𝑅 << 𝑎ℎ . Due to these conditions excitations are not formed and separate
size quantization of an electron and hole is the dominant factor. For strong confinement regime
must need two different reason first one is the Coulomb term of electron-hole interaction is small
it’s acted as perturbation and another one is independent behavior of electron and holes when
above condition is apply. Following the optical spectra should then consist of a series lines due to
transition between sub-bands. This factor was confirmed experimentally, and the simple model
gives shift in energy as a function of crystallite size as,
ℏ2 𝜋 2
∆𝐸 ≈
2𝜇𝑅 2

in which the Exciton mass 𝑀 is replaced by reduced Exciton mass µ, where,

1 1 1
= ∗+ ∗
𝜇 𝑚𝑒 𝑚ℎ
The electrons and holes in QDs are treated as independent particles, and for the excited state there
exist a ladder of discrete energy levels as in molecular systems.
Concept of Dimensionality:

The reduction in dimensionality produced by confining electrons (or holes) to a thin semiconductor
layer leads to a dramatic change in their behavior.
 This principle can be developed by further reducing the dimensionality of the electron’s
environment from a two-dimensional quantum well to a one -dimensional quantum wire
and eventually to a zero-dimensional quantum dot.
 The dimensionality refers to the number of degrees of freedom in the electron momentum;
in fact, within a quantum wire, the electron is confined across two directions, rather than
just the one in a quantum well and so therefore reducing the degrees of freedom to one.
 In a quantum dot, the electron is confined in all three dimensions, thus reducing the degrees
of freedom to zero.
 If the number of degrees of freedom are labeled as 𝐷𝑓 and the number of directions of
confinement are labeled as 𝐷𝐶 then clearly:
𝐷𝑓 + 𝐷𝐶 = 3

Nanostructure Directions of Degrees of 𝐷𝑓 + 𝐷𝐶

confinement 𝐷𝐶 freedom 𝐷𝑓
Bulk 0 3 3
1D Quantum well 1 2 3
2DQuantum Wire 2 1 3
3DQuantum Dot 3 0 3

Density of State (DOS) of Nanostructure:

It is as number of energy states for given energy level interval that electrons are allowed to
occupy. The D.O.S is physical measure of how close to gather the allowed energy states to
each other in energy interval.
Density of State (D.O.S.) is a ratio between numbers of energy states exist in energy level
interval.
Let 𝑑𝑁 is number of allowed energy levels exsit in energy interval 𝐸 𝑡𝑜 𝐸 + 𝑑𝐸 so D.O.S.
is defined as
𝑑𝑁
𝐷. 𝑂. 𝑆 = 𝐷(𝐸) =
𝑑𝐸
The density of State per unit volume is given as 𝑔(𝐸)which measure the closeness of
energy levels in is given energy interval per unit volume.
𝑑𝑁
𝑔(𝐸) =
𝑉𝑑𝐸
The density of state are useful concept to understand the physical properties of material
such as emission, absorption, magnetization etc..
The density of state is also dependent on dimension of material. It varies as order of
dimension change and put greater role to understand properties of Nanomaterials. As size
of material changes from bulk to nanoscale. DOS also Changes. In general, the DOS is
given by
𝑑𝑁 𝐷
𝑔(𝐸) = = 𝐶𝐷 𝐸 ( 2 −1)
𝑉𝑑𝐸
𝐷 𝑖𝑠 𝑜𝑟𝑑𝑒𝑟 𝑜𝑓 𝐷𝑖𝑚𝑒𝑛𝑠𝑖𝑜𝑛. 𝐷 = 1,2,3
For D=0, the density of state is given by
𝑑𝑁
𝑔(𝐸) = = 𝛿(𝐸)
𝑉𝑑𝐸
Density of state in One Dimension Nano Material:
In one dimension nanomaterial, one dimension is normal scale (>100nm) and other two
dimension are in nanoscale (<100nm). It seems like quantum wire or nanowire.
The density of state of 1D material is available allowed energy state for electrons to be
occupied in given energy interval 1D material.
𝑑𝑁
𝑔(𝐸) =
𝐿𝑑𝐸
𝐿 𝑖𝑠 𝑠𝑖𝑧𝑒 𝑜𝑓 𝑙𝑒𝑛𝑔𝑡ℎ 𝑜𝑓 1𝐷 𝑛𝑎𝑛𝑜𝑚𝑎𝑟𝑒𝑖𝑎𝑙.
Density of state in two Dimension Nano Material:
In one dimension nanomaterial, two dimension are in normal scale (>100nm) and other
one dimension is in nanoscale (<100nm). It seems like quantum sheet or nanosheet.
The density of state of 2D material is available allowed energy state for electrons to be
occupied in given energy interval 2D material.
𝑑𝑁
𝑔(𝐸) =
𝐴𝑑𝐸
𝐴 𝑖𝑠 𝑎𝑟𝑒𝑎 𝑜𝑓 2𝐷 𝑛𝑎𝑛𝑜𝑚𝑎𝑟𝑒𝑖𝑎𝑙
Density of state in three Dimension Bulk Material:
In one dimension nanomaterial, all dimension are in normal scale (>100nm) and no one
dimension is in nanoscale (<100nm). It seems like bulk material.
The density of state of 3D material is available allowed energy state for electrons to be
occupied in given energy interval 3D material.
𝑑𝑁
𝑔(𝐸) =
𝑉𝑑𝐸
𝑉 𝑖𝑠 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑚𝑎𝑡𝑒𝑟𝑖𝑎𝑙
Production and Synthesis of Nanomaterials:
There are mainly two approach to synthesize the nanomaterial at nanoscale:
i. Top –down approach
ii. Bottom up approach
Top –Down Approach: In this approach, the bulk material is fragments into small size
particle upto nanoscale.

 It is a physical process.
 In this process, the large scale objects (> 10−6 𝑚) is progressively reduced in
dimension upto 10−6 𝑚 to 10−9 𝑚.
 It consists of ultra-fine micromachining of material using epitaxy, milling,
grinding, cutting etc.
 This method is time taking process and relatively costly
 The best method of top down approach is ball milling method. It is based on
mechanical concept. In this method high kinetic energy is used to grinding the m
bulk material.
Draw Back of Top down Approach
 It does not produces perfect nanomaterial in shape and size.
 The morphology of nanomaterial is not controlled.
 It has no homogeneity.
 It has imperfection.
 The produced nano material in range of 100nm.
Ball Milling Method:
BALL MILLING METHOD is TOP DOWN APPROACH .It is Popular,
simple, inexpensive and extremely scalable material to synthesize all
classes of nanoparticles. It can produce amorphous or nanocrystalline
materials. MECHANICAL ATTRITION MECHANISM is used to obtain
nanocrystalline structures from either single phase powders or amorphous
materials. It consists of the milling drum whish can rotate. It can use either
refractory balls or steel balls, SiC ball or TgC ball of different size or plastic
balls depending on the material to be synthesized. When the balls rotate at
a particular rpm, the necessary energy is transferred to the powder which in
turn reduces the powder of coarse grain-sized structure to ultrafine
nanorange particle.

The energy transferred to the powder from the balls depends on many
factors such as
 Rotational Speed of the balls
 Size of the balls
 Number of the Balls \
 Milling Time
 Ratio of ball to powder mass
 Milling medium /atmosphere
 Cryogenic liquids can be used to increase the brittleness of the
product
 One has to take necessary steps to prevent oxidation during milling
process
 The selection of ball material influences the type of material
obtained.
 The harder material balls, synthesize softer materials Alpha-alumina
and zirconia are widely used ball materials due to their high grinding
resistance values.
ADVANTAGES OF BALL MILLING
Scaling can be achieved upto tonnage quantity of materials for wider
applications
 DISADVANTAGES OF BALL MILLING:
 There may be contaminants inserted from ball and milling additives.
Contamination of the milling media Non-metal oxides require an
inert medium,
 Vacuum or glove box to use powder particles. So the milling process
is restrictive.
 As the process is not so sophisticated, therefore the shape of the
nanomaterial is irregular.
 This method produces crystal defects.
Bottom up Approach: It is used to produce nano system. In this approach the small, i.e., seeds of
atoms of species join together to form nanomaterial through increasing and adding atom to atom,
the nano material evolves from atom to group of atoms to nanoscale materials.

 It is a chemical process.
 In this process, different material are constructed from atoms and molecular
component on their own (It is self-assembly) which do not require any external
agent to assemble them. In this process, material is formed by self-assembly.
 The chemically assembly themselves recognises the molecule or atoms of their own
types.
 This approach starts by collecting atoms to form cluster to Nanomaterials. Or build
complex Nanomaterials.
 It is relatively less costly.
 It is natural process.
 The best examples are Physical vapor Deposition (PVD), Chemical Vapor
Deposition (CVD) and Sole gel method.
Physical vapor Deposition (PVD):
The physical vapor Deposition method is Bottom up Approach. In this method the
nanomaterial is synthesized by vapor deposition of target material. In this process the target
material is evaporated by supplying the huge amount of energy. There are two methods for
providing energy (I) resistive method and (II) sputtering method.
I. Resistive Method: In the resistive method the target material is evaporated by
heating high resistance coils in vacuum chamber. The vacuum is maintained
because the air molecule or other material other than target material can’t be deposit
on cooled substrate. The vaporized particle of target material get deposited on
substrate in for of thin film of nanoscale thick and condense in solid.

II. Sputtering method: In the Sputtering method the target material is evaporated by
bombarding the high kinetic energy electron by electron gun in vacuum chamber.
This electron beam by applying the magnetic field. The vacuum is maintained
because the air molecule or other material other than target material can’t be deposit
on cooled substrate. The vaporized particle of target material get deposited on
substrate in for of thin film of nanoscale thick and condense in solid.
Sol Gel Method for Synthesizing Nanomaterial:
It is a class of Bottom up approach. It is also known as wet chemical technique which widely used
to fabricate nanomaterial of metal oxide. It is chemical synthesis because chemical substance are
involved.
In the Sol Gel approach metal alkoxide covert into nano particle of metal oxide through chemical
reaction.
 Sol which is colloidal suspension built in water.
 Gel is formed
 It is a technique in which sole to gel transition occur.
In this process, a precursor is used as metal alkoxide (M-OR). The precursor is stating material
which undergoes change as
 Step 1:
Metal oxide should be dissolved in water. The water is practically act as catalyst in this
synthesis. It is not easier to dissolve it in water. So we need to add alcohol, the powder of
metal alkoxide is completely and easily dissolved. After complete dissolve of metal
alkoxide in alcohol, we add water which acts as catalyst and it is homogenous solution of
metal oxide (precursor), water (Catalyst and alcohol (solvent).

Homogenous solution is mixture of metal alkoxide, alcohol and water. In this homogenous
solution the solute is completely dissolved in solvent.
 Step 2: Hydrolysis is: the homogenous solution is continuously starrier. So dissolved metal
alkoxide reacts with water molecule and undergo Hydrolysis. Due to chemical reaction
between metal alkoxide, it forms Sol which consist of metal hydroxide with water which
is not soluble in water and prepare a heterogeneous solution. It makes a colloidal solution
suspension of molecule of metal hydroxide.
 Note: The difference between Solution and Sol is that nearly 100%solute is solvable
in solvent.in case of solution. In case of solute i.e. metal hydroxide is not 100% solvable
in water.
 Step 3: The prepared Sol in step 2 is kept undisturbed for long tine (for 2 or more
days).This process is called Aging. Due to aging effect Sol converts into Gel because some
of water molecule evaporated. It is called condensation. This gel is homogenous and it
forms metal oxide of metal oxygen bond. At this stage the polymerization of Meat oxide
is done and it start forming Nanosized metal oxide. So the network of metal oxide is
formed.
 Step 4: (Extraction of nanomaterial) there are three way to get nanomaterial from the
network of metal oxide formed in step 3. Any how we dry the water and alcohol from gel.
According to drying, there are different types of morphology of nanomaterial.
a. Drying through Thermal Evaporation: The metal oxide nanoparticle network with
changing Morphology is obtained in this drying method. The formed nonmaterial
is called XEROGEL.
b. Calcination: The nano metal oxide powder is obtained in this drying method in
which heat is provided in presence of Oxygen at 800 o C so the imparted alcohol
in side ano is evaporated and we get NANO POWDER.
c. The morphology of nanomaterial is unchanged. As heat at stage of formation. It
provides 100% highly pure Metal oxide nanomaterial i.e, it is called AEROGEL In
this process the gel is undergoes the super critical condition in which the
temperature is kept above critical point of material.
Note: Most preferred methods are Thermal evaporation and calcination over super critical
method. Because super critical method is costly method.
Example the Sol Gel method is used to prepare the 𝑇𝑖 𝑂2 nanomaterial which is semiconductor
material. It has wide range of application from Solar cell to Cosmetic.
 The precursor is Titanium tetraisopropoxide.
 It is dissolved in ethanol in which isopropoxide is completely dissolved.
 Add distilled water in ratio of 𝑇𝑖: 𝐻2 𝑂 as 1: 4.
 Add 𝐻𝐶𝑙 𝑜𝑟 𝐻𝑁𝑂3 to adjust the pH and restrain the hydrolysis process of solution.
 Then solution is stirred for 30 min in order to get Sol (a suspension of particle as colloidal
solution.
 The Sol is kept for aging for 24 hour duration. .During aging Sol transformed into Gel. It
is due to poly condensation formation of inorganic network.
 After this Drying process is done to get nanomaterial of 𝑇𝑖 𝑂2
Chemical Vapor Deposition (CVD)

Chemical Vapor Deposition (CVD) refers to the formation of a non-volatile solid film of nano
dimension on a substrate from the reaction of vapor phase chemical reactants containing the right
constituents. A reaction chamber is used for this process, into which the reactant gases are
introduced to decompose and react with the substrate to form the film of nano dimension. Chemical
vapor deposition is used in a multitude of semiconductor wafer fabrication processes, including
the production of amorphous and polycrystalline thin films (such as polycrystalline silicon),
deposition of 𝑆𝑖𝑂2 and silicon nitride, and growing of single-crystal silicon epitaxial layers. It is
widely used to develop and grow the Nanomaterial in power forms and rods i.e., carbon nanotube.
The CVD to develop the nanomaterial requires the mainly two major components
1. Precursor: The metalorganic compound is used as starting martial which kept as vapor
forms.
2. Carrier Gas: It is normal inert or noble gas which continuous flowed along with mixture of
metalorganic vapor at control rate.

A basic CVD process consists of the following steps:

 A predefined mix of reactant gases and diluents inert gases are introduced at a specified
flow rate into the reaction chamber;
  The gas species move to the substrate;
 The reactants get adsorbed on the surface of the substrate;
 The reactants undergo chemical reactions with the substrate to form the film; and
 The gaseous by- products of the reactions are desorbed and evacuated from the reaction
chamber.
During the process of chemical vapor deposition, the reactant gases not only react with the
substrate material at the wafer surface (or very close to it), but also in gas phase in the reactor's
atmosphere. Reactions that take place at the substrate surface are known as heterogeneous
reactions, and are selectively occurring on the heated surface of the wafer where they create good-
quality films of nano dimension.

Reactions that take place in the gas phase are known as homogeneous reactions. Homogeneous
reactions form gas phase aggregates of the depositing material, which adhere to the surface poorly
and at the same time form low-density films with lots of defects. In short, heterogeneous reactions
are much more desirable than homogeneous reactions during chemical vapor deposition.

A typical CVD system consists of the following parts:

 Sources of and feed lines for gases;

 Mass flow controllers for metering the gases into the system;
 A reaction chamber or reactor;
 A system for heating up the wafer on which the film is to be deposited; and
 Temperature sensors.
Block Diagram:

In this technique, the precursor vapor is passed through a hot walled reactor. The precursor
decomposes and nano particles nucleate in the gas phase. The nano particles are carried by the gas
stream and collected on a cold finger. The size of the nano particles is determined by the particle
residence time, temperature of the chamber, precursor composition and pressure.
Step of formation of Nanomaterial in CVD:
Step 1: The noble gas as carries gas from chamber is send through control valve V1 in camber of
precursor where precursor is kept in vapor form. In this chamber the mixture of metalorganic vapor
and carrier gas is kept.
Step 2: This mixture is send to hot furnace in a control manner through valve V2 and V3.Because
of high temperature in Furnace, the metalorganic compound start intact and aggregate as group of
atom i.e. Cluster of atom of spices of which nanomaterial is to be formed.
Step 3: In the furnace, these clusters further bind and forms nanomaterial due to continuous flow
these nanomaterial is sent to subtract chamber in which substrate is kept at very low temperature
to keep it cool with use the liquid nitrogen.. This subtract is called cooled finger .It is rotating so
the formed nanomaterial continuous bind to finger. After homogenous deposition of nanomaterial.
Step 4: The deposited nanomaterial on cooled finger is collected in powder collector by using
scupper.
Advantages:
 Low power input
 Low temperature range, i.e., liquid mitogen is required.
 Relatively purr nanomaterial are formed.
 Synthesis of doped and coated Nanomaterials are formed
 The flow of vapor precursor is controlled the yield of nano particle through variation of
temperature and flow of carrier gas and precursor.
Carbon Nanomaterial:

The carbon materials are made network of carbon which are normal one atom thick. It is material
in nanoscale. The carbon has fore It is allotropes of carbon i.e., fullerene and graphene.
The carbon Nanomaterials are
1. Bucky Ball or Fullerene i.e., 𝑪𝟔𝟎 Molecule
2. Graphene
3. Carbon Nanotube

Fullerene is an allotrope of carbon wherein its molecules consist of carbon atoms that are
connected by single and double bonds. This results in the formation of a closed or partially closed
cage-like structure (a mesh consisting of fused rings) that further contain several atoms. The
fullerene molecule in this form can either have a hollow sphere, be it an ellipsoid, a tube, or it can
also have many other different shapes and sizes. When the carbon molecules are arranged in a
cylindrical form they usually form a tube-like structure known as carbon nanotubes.
𝑪𝟔𝟎 Molecule:
It is allotropes of carbon. It chemically known as 𝐶60 Molecule which is a hallow cluster of 60
atoms of carbon shaped like football. It is one of member of Fullerene group. It is spherical hallow
structure.
 The carbon atom is bounded to three adjacent carbon atoms just like in case of graphite.
The carbon atom network is arranged in a sphere about nanometer in diameter.
 It is named after R. Buckminster Fuller. It is called Buckminster Fullerene of Bucky Ball.
 It is most roundest molecule, known in the world
i. It has carbon atom network in which mostly 60chemically equivalent vertices are
present. Such vertices are connected and forming 32 faces. Out of which 12 faces
are pentagonal and 20 faces are hexagonal. It is made of pentagons and hexagons
faces. The pentagon faces provide curvature to Bucky Ball.
Note: In all fullerene family 𝑪𝒏 number of pentagon are present. The number of
fullerene family is 12 pentagon faces. The number of hexagon is different and
dependent on number of carbon atoms present in fullerene. The number of hexagon
is given as
𝑛
𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 ℎ𝑎𝑥𝑒𝑔𝑜𝑛 𝑓𝑎𝑐𝑒𝑠 𝑖𝑛 𝑓𝑢𝑙𝑙𝑒𝑟𝑒𝑛𝑒 = ( − 10)
2
𝑛 𝑛+4
𝑇𝑜𝑡𝑎𝑙 𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑓𝑎𝑐𝑒𝑠 𝑖𝑛 𝑓𝑢𝑙𝑙𝑒𝑟𝑒𝑛𝑒 = ( − 10) + 12 = ( )
2 2
Example for 𝑪𝟔𝟎 Molecule, the number of carbon atom in this network 𝑛 = 60

𝑛 60
𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 ℎ𝑎𝑥𝑒𝑔𝑜𝑛 𝑓𝑎𝑐𝑒𝑠 𝑖𝑛 𝑪𝟔𝟎 𝑓𝑢𝑙𝑙𝑒𝑟𝑒𝑛𝑒 = ( − 10) = ( − 10) = 20
2 2
𝑛+4 60 + 4
𝑇𝑜𝑡𝑎𝑙 𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑓𝑎𝑐𝑒𝑠 𝑖𝑛 𝑓𝑢𝑙𝑙𝑒𝑟𝑒𝑛𝑒 = ( )=( ) = 32
2 2
Example for 𝑪𝟖𝟎 Molecule, the number of carbon atom in this network 𝑛 = 60

𝑛 80
𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 ℎ𝑎𝑥𝑒𝑔𝑜𝑛 𝑓𝑎𝑐𝑒𝑠 𝑖𝑛 𝑪𝟖𝟎 𝑓𝑢𝑙𝑙𝑒𝑟𝑒𝑛𝑒 = ( − 10) = ( − 10) = 30
2 2
𝑛+4 80 + 4
𝑇𝑜𝑡𝑎𝑙 𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑓𝑎𝑐𝑒𝑠 𝑖𝑛 𝑓𝑢𝑙𝑙𝑒𝑟𝑒𝑛𝑒 = ( )=( ) = 42
2 2
Question: Find the Number of hexagonal faces and Total faces of fullerene𝑪𝟐𝟎, 𝑪𝟑𝟐 , 𝑪𝟖𝟎 , 𝑪𝟕𝟖 and
𝑪𝟗𝟎 ?
 It has 𝑠𝑝2 hybridization which leads single and double bond.
 The side of each polygon is made of C-C bond, the bond length 0.142 nm
 It is electron deficiency due to which it interact with species of electron rich.
 The Co0 has Face centered (FCC) structure. It has 8- 𝑪𝟔𝟎 molecule at corner and 6- 𝑪𝟔𝟎
molecule at center of faces of Cube.
  The vender-walls (region 𝜋 of electrons) diameter and molecule to molecule diameter of
𝑪𝟔𝟎 is 1.1 nm to 0.71 nm respectively.
 The diameter of 𝑪𝟔𝟎 molecule is 0.72 nm and the lattice constant is 0.246 nm

Structure of Fullerene

Fullerenes in their natural form tend to be highly symmetrical. Their structure is quite similar to
that of graphite and is made up of a sheet of connected hexagonal rings (cage structure). However,
they have pentagonal and sometimes heptagonal rings which do not allow the sheet to become
planar. They are often referred to as buckyballs and buckytubes depending on their shape.
Cylindrical fullerenes are referred to as nanotubes.

Model of the C60 fullerene (buckminsterfullerene)

In any case, there is an infinite number of fullerenes that can exist. Fullerenes can be
𝐶60 , 𝐶70 , 𝐶80 , 𝑎𝑛𝑑 𝐶90 existing in various forms. This depends largely on the number of carbon
atoms present in the molecule. Nonetheless, their structure is primarily based on pentagonal and
hexagonal rings that are constructed as per the rules for making icosahedra.

Types of Fullerene

Fullerenes exist in two major families depending on some distinct properties and applications. The
two families include the closed buckyballs and the open-ended cylindrical carbon nanotubes.
However, there are also hybrid structures that can exist between these two classes. They can be
carbon nanobuds which are basically nanotubes capped by hemispherical meshes or larger “buck
buds”.
Bucky ball Clusters

These fullerenes are basically unsaturated versions of dodecahedra. These are also some of the
smallest members of the fullerene group. Its structural formula is C20.

Buckminsterfullerene

Buckminster-fullerene is the smallest fullerene molecule. It contains pentagonal and hexagonal

rings and no two pentagons will share an edge. Buckminster-fullerene exists in C60 form is the most
common in terms of natural occurrence. The structure of buckminsterfullerene is a truncated
icosahedron similar to that of a football.

Linked Ball and Chain Dimer: In this type of fullerene, two Bucky balls are mainly linked by a
carbon chain. There are also other fullerenes such as heterofullerenes, which have heteroatoms
substituting carbons in a cage or tube-shaped structures. Then there is metallofullerene whose
molecule is composed of a metal atom trapped inside a fullerene cage.

Carbon Nanotubes

This type of fullerene has cylindrical or hollow tubes of very small dimensions; they are mostly a
few nanometers wide. However, they can also be micrometre to several millimetres in length.
Talking about some of the properties of carbon nanotubes, they can be both closed and open-ended.
As a result of their unique molecular structure, they have some unique macroscopic properties.
Some of them include high tensile strength and electrical conductivity, high ductility and heat
conductivity including relative chemical inactivity. Another form that we find is the megatubes.
These are slightly bigger in diameter than nanotubes and are generally found with walls of different
thicknesses.