MODULE - V

Nanotechnology

Dr. C. R. Kesavulu, Associate Professor, Dept. of Physics

 Nanotechnology
Nanotechnology: Nanoscale, Quantum confinement, Surface to
volume ratio,

Bottom-up fabrication: Sol-gel, precipitation, Combustion methods,

Top-down fabrication: Ball milling, Physical Vapor Deposition

(PVD), Chemical Vapor Deposition (CVD)

Characterization techniques: X-ray diffraction (XRD), and

Transmission Emission Microscopy (TEM), Applications of
Nanomaterials.

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 Nano-Scale
The word “nano” is derived from a Greek word meaning dwarf or
extremely small and means a billionth (10-9) part of a unit.
A nanometer or nm is one thousand millionth of a metre, i.e.,

1 nm = 10-9 m = 10-6 mm = 10 Å.

One nanometer spans 3 to 5 atoms lined up in a row.

For comparison, a single human hair is about 80,000 nm wide and a

red blood cell is approximately 7,000 nm wide. Scientists and
Engineers are nowadays interested in the nanoscale, which may be
taken as 100 nm to 0.2 nm approximately.

Below this lies the atomic scale 0.1nm.Therefore, the nano-world is a

borderland between the quantum world and the macro world.
 Nanotechnology

❑ Nanotechnology is the day-to-day developing subject,

with large number of applications.

❑ Nanotechnology has the potential to create many new

materials and devices with wide-ranging applications, such
as in medicine, electronics, and energy production.

❑ Nanotechnology is the design and development of

techniques, instruments and devices for fabrication,
characterization and application of the nanoparticles.
 Nanotechnology

➢ Many diagnostic instruments like Transmission Electron

Microscope (TEM), Scanning Tunneling Microscope (STM), Atomic
Force Microscopy (AFM) and Magnetic Resonance Imaging (MRI)
have been invented in the Nanotechnology.

➢ Nanoscience is the basic of nanotechnology. The nanoscience relies

more on quantum theory.

➢ Nanoscience can be defined as the study of phenomenon and

manipulation of materials at atomic, molecular and macromolecular
scales, where properties differ significantly from those at larger scale.
 Origin of Nanotechnology

The word nanotechnology is relatively new, the existence of

nanostructure is not new.

In fourth century, AD Roman glass makers fabricated glasses

containing nanosized materials. Similarly gold nanoparticles are
made long ago.

The concept of nanotechnology was first given by Richard

Feynman. In eighteenth century British scientists Thomas
Wedgewood and Sir Humphrey Davy were able to provide
images using nitrate and chloride, but their images were not
permanent.
 Origin of Nanotechnology

In 1960, Richard Feynman presented a visionary and prophetic

lecture at a meeting of American Physical society entitled “there
is plenty of room at the bottom” where he speculated on the
possibility and potent of nanosized materials.

The term nanotechnology was defined by Tokyo Science

University Professor Norio Taniguchi in a 1974 paper as
follows: Nano technology mainly consists of the processing of,
separation, consolidation, and deformation of materials by one
atom or by one molecule.
 Nanomaterials
Nanomaterial means a material whose size is in Nano range, this is an
answer which may be generally thought, but there is an implicit
meaning.
Suppose, consider a gold biscuit of 100 cm3 cut into two pieces, no
properties are changed except its size. Divide it into further small
pieces, then also there would not be any change in properties.

Thus, the macroscopic solid pieces of the materials possess size

independent properties.

It was found that when gold is divided into fine grains of nearly 50
nm, the properties like density, color, hardness, melting point,
resistivity etc are changing.

So, the microscopic pieces possess size dependent properties.

 Nanomaterials
Thus, the size dependency is an essential property of Nanomaterials.

So, Nanomaterial is defined as material having one of its dimensions in

nano range and it possesses size dependent properties. Or

Nanomaterials could be defined as those materials which have

structured components with size less than 100 nm at least in one
dimension.

Generally if one dimension is in nano range, it is called thin films and

quantum well.
If two dimensions are in nano range it is called quantum wire & Q-
tube.
If three dimensions are in nano range it is called quantum dot.
 Application of Nanotechnology

Medicine: Drug delivery systems, Active agents, Contrast

medium, Medical rapid tests, Prostheses and implants,
Antimicrobial agents and coatings, Agents in cancer therapy.

Chemical industry: Fillers for paint systems, Coating systems

based on nanocomposites, Impregnation of papers, Switchable
adhesives, Magnetic fluids.

Engineering: Wear protection for tools and machines (anti

blocking coatings, scratch resistant coatings on plastic parts, etc),
Lubricant-free bearings.
 Application of Nanotechnology
Electronic Industry: Data memory (MRAM, GMRHD), Displays
(OLED, FED), Laser diodes, Glass fibers, Optical switches, Filters
(IR blocking),Conductive antistatic coatings.

Construction: Construction materials, thermal insulation, Flame

retardants, Surface-functionalised building materials for wood, floors,
stone, facades, tiles, roof tiles, etc., Façade coatings, Groove mortar.

Automotive Industry: Light weight construction, Painting (fillers,

base coat, clear coat), Catalysts, Tires (fillers), Sensors, Coatings for
windscreen and car bodies.

Textile/ fabrics/ non-wovens: Surface processed textiles, Smart

clothes.
 Application of Nanotechnology

Energy: Fuel cells, Solar cells, Batteries, Capacitors.

Cosmetics: Sun protection, Lipsticks, Skin creams, Tooth paste.

Food and drinks: Package materials, Storage life sensors, Additives

Clarification of fruit juices.

Household: Ceramic coatings for iron, Odors catalyst, Cleaner for

glass, ceramic, floor, windows

Sports/outdoor: Ski wax, Antifogging of glasses/goggles, Antifouling

coatings for ships/boats, Ring forced tennis rackets and balls.
 Why the properties of Nanoparticles are different

The phenomena due to which properties of nanoparticles are different

are:
(i) Surface area to volume ratio

(ii) Quantum confinement effect

Increase in Surface area to volume ratio:

Nanomaterials have relatively larger surface

When compared to the same volume or mass of the
Material produced in larger form. Consider a sphere of radius ‘r’ .

Its surface area = 4πr2 & Its volume = (4/3) πr3

So, surface area to its volume ratio= (3/r).
 Surface to volume ratio

As ‘r’ decreases surface area to volume ratio increases. So, the properties
of materials will be changing. The material has high surface energy, if it
is small in size or vice versa.

As the surface area to volume ratio increases, the materials possess good
catalytic properties.
Thus, nanoparticles show enhanced stability and broader scope of
applications.

In some cases materials that are inert in their larger form are reactive
when produced in their nano scale form. This affects their strength or
electrical properties.

For example, a particle of size 30 nm has 5% of its atoms on its surface,

at 10 nm 20% of its atoms and at 3 nm 50% of its atoms.
 Quantum confinement
When atoms are isolated the energy levels are discrete (Fig. I).

Nanomaterials represent intermediate stage.

When the dimensions of box or wells in which a particle is represented are of the
order of De-Broglie wavelength of electrons, energy levels of electrons change.
This effect is called quantum confinement effect.
 Quantum confinement
When the material is sufficiently small in size typically 10 nm or less,
organization of energy levels into which electrons can climb or fall
change.
When very large numbers of atoms are closely packed, to form a solid,
the energy levels split and form bands (Fig. II).

Fig. II
 Quantum confinement
Specifically, the phenomenon results from electrons and holes being
squeezed into dimension that approaches a critical quantum
measurement, called the ‘excited Bohr radius ’.

These can affect the optical, electrical and magnetic behavior of

materials, particularly as the structure or particle size approaches the
smaller end of the nano scale.

In small nano crystals or clusters or grains the electronic energy levels

are not continuous as in the bulk and are discrete, because of the
confinement of the electronic wave function to the physical dimensions
of the particles.
Fabrication of Nano-materials/Nano-
particles:

Top-down & Bottom-up approaches

How to prepare the Nano-particle or Nanostructure
1) Ball milling
2) Physical Vapor Deposition
3) Chemical Vapor Deposition

1) Sol-gel
2) Precipitation
3) Combustion methods
 Fabrication of Nano-materials
The two basic approaches used in the fabrication of nanomaterials are:

(i) Bottom-up approach.

(ii) Top-down approach
Bottom-up approach:
In this approach, atoms or molecules or nanoparticles are used as building
blocks for the creation of complex nanostructures.
These processes are highly controlled, complex chemical synthesis
techniques.
In this approach, materials and devices are built from molecular components
which assemble themselves chemically by principles of molecular
recognition.
These seek to arrange smaller components into more complex assemblies.
Nanoscale structures are normally achieved by chemical synthesis of
materials in liquid or gaseous state.
 Fabrication of Nano-materials
Top-down approach:
In this approach, one rely on either division or removal of a bulk material to
produce the desired nanostructure or nanoparticles with the desired properties.
These are inherently much simpler process when compared with bottom-up
approach.

In this approach, nano-objects are constructed from larger entities without

atomic level control.
These seek to create smaller devices by using larger ones to direct their
assembly. The top-down processes of preparing nanoparticles are effectively
examples of solid state processing of materials.
 Top-down Fabrication methods
In this approach, we discuss three methods that are used for the fabrication:

(i) Ball milling

(ii) Physical vapour deposition; (iii) Chemical vapour deposition
Ball Milling:
In ball milling, also called mechanical crushing, small balls (SiC or tungsten balls)
are allowed to rotate around the inside of a drum and then fall on a solid with gravity
force and crush the solid into nanocrystallites..
Ball milling can be used to prepare a wide range of elemental
and oxide powders.
For example, iron with grain sizes of 10-30 nm can be
formed.
Other crystallites, such as iron nitrites, can be made using
ammonia gas.
A variety of inter metallic compounds based in nickel and
aluminum can be formed. Ball milling is preferred method
for preparing metal oxides
 Top-down Fabrication methods
Vapor deposition technique:
Vapor deposition refers to any process in which materials in a vapor
state are condensed through condensation, chemical reaction or
conversion to form a solid material.

These processes are used to form coatings to alter the mechanical,

electrical, thermal, optical, corrosion resistance and wear properties of
the substrates.

Vapor phase deposition techniques can be classified broadly as:

(i) Physical vapour deposition (PVD); and

(ii) Chemical vapour deposition (CVD).

 Top-down Fabrication methods
Physical vapor deposition (PVD) technique:
PVD involves conversion of solid material into gaseous phase by
physical process which is then cooled and re-deposited on a substrate
as per the requirement.
All the reactive PVD hard processes combined have following steps:
A method for depositing the metal.
Combination with an active gas, such as nitrogen, oxygen or methane.
Plasma bombardment of the substrate to ensure a dense, hard coating.
PVD methods differ in the means for producing the metal vapor and
the details of plasma creation.
<

The primary PVD methods are iron plating, ion implantation,

spluttering and laser surface alloying.
 Top-down Fabrication methods
Physical vapor deposition (PVD) technique:
 Top-down Fabrication methods
Thermal evaporation is one of the simplest and most popular synthesis
methods, and it has been very successful and versatile in fabricating
nanobelts and nanowires with various characteristics.

Multi-wall and single-wall carbon

nanotubes have been successfully
fabricated in this system using hydrogen
and methane/acetylene reactants.

Metal catalysts such as Gold, Tin, and

Copper etc., have also been used to
achieve size control alignment.
 Top-down Fabrication methods
Chemical vapor deposition (CVD):

CVD is a widely used method for depositing thin films for a large
variety of materials.

Applications of CVD range from the fabrication of microelectronic

devices to the deposition of protective coatings.
In a typical CVD process, reactant gases at room temperature enter the
reaction chamber.
The gas mixture is heated as it approaches the deposition surface, heated
radiatively or placed upon a heated substrate.

Depending on the process and operating conditions, the reactant gases

may undergo homogenous chemical reactions in the vapor phase before
striking the surface.
 Top-down Fabrication methods
Chemical vapor deposition (CVD):

Input of acetylene (C2H2, purity 99.5 wt%) and electronic grade nitrogen (N2), purity 99.99
wt% through alumina/quartz tubes was localized in the upper (colder) part of the furnace.
Gases were spontaneously premixed at this part, then they flowed through a tubular hot-wall
reactor in which the reaction took place.
 Top-down Fabrication methods
There are a great variety of CVD processes such as:

(i) Atmospheric pressure chemical vapor deposition (APCVD)

(ii) Plasma Assisted (enhanced) chemical vapor deposition
(PACVD,PECVD)
(iii) Low Pressure chemical vapor deposition (LPCVD)
(iv) Photochemical Vapor deposition (PCVD)
(v) Laser Chemical vapor deposition (LCVD)
(vi) Chemical Beam Epitaxy (CBE)
(vii) Chemical vapor Infiltration (CVI)

Chemical vapor deposition (CVD) synthesis is achieved by putting a

carbon source in the gas phase and using an energy source, such as
Plasma or a resistively heated coil, to transfer energy to a gaseous
carbon molecule.
 Bottom-up Fabrication methods

Sol-Gel method:
In solutions, nanosized molecules are dispersed randomly whereas in colloids, the
molecules have diameters in the range of 20µm-100µm and are suspended in the
solvent. So, the colloid appears cloudy.
A colloid that is suspended in a liquid is called a Sol. The gelation of the sol in the
liquid to form a network is called gel. Gel is the suspension that keeps its shape.

Sol-gel formation occurs in different stages.

• Hydrolysis
• Condensation and polymerization of monomers to form particles.
• Agglomeration of particles.
This is followed by the formation of networks which extends throughout the liquid
medium and forms a gel.
Using sol-gel method, silica gels, zirconia and yttrium gels and aluminosilicate gels are
formed. Nanostructured surfaces are formed using the sol-gel method
 Bottom-up Fabrication methods
Important steps are used in sol-gel method:
 Bottom-up Fabrication methods
Sol-gel Method:
 Bottom-up Fabrication methods
Solution Combustion (SC) Method:
 Bottom-up Fabrication methods
Solution Combustion (SC) Method:
This technique is widely used to obtain metal oxide and insulators
nanoparticles.

In this technique, first one should make a solution with solutes and
solvents. Sometimes making solution may require stirring provision.

Then the solution is heated and once the solution reached auto-ignition
temperature, it will start to burn by indication of flames with evolution
of some gases.

After completion of burning process, the remaining ash will give us

the required nanoparticles.
 Bottom-up Fabrication methods
Solution Combustion (SC) Method:
 Bottom-up Fabrication methods
Solution Combustion Synthesis (SCS) :
Select the chemicals such that from which we can get the resultant component.
Ex. Oxidizer: For CuO → Cu (NO3)2 copper nitrate
For ZnO → Zn (NO3)2 Zinc nitrate
Choose the fuel such as containing Carbon and Hydrogen main components.
Ex. Fuel : C2H5NO2 → Glycine

C6H8O6 → Ascorbic Acid

Choose the oxidizer and fuel by calculating the (molecular weight * balancing
constant)

Take the ratio of fuel /oxidizer

By using the electrical balance take the chemical into butter worth paper
 Bottom-up Fabrication methods
Solution Combustion Synthesis (SCS) :
Dissolve the oxidizer into distilled water and mix up with magnetic stirrer.

Add fuel , again stirrer it.

Put the container on electrical heater

After cooling the container, collect the material from the container.

And send for the calcinations

Calcination process normally takes place at temperatures below the melting point of
the product materials.

For CuO, the desired melting temperature is 600oC and calcined sample for at least
half an hour so that carbon will reduce to carbon-dioxide.

Finally CuO nanoparticles are synthesized.

 Bottom-up Fabrication methods
Solution Combustion Synthesis (SCS) :
 Bottom-up Fabrication methods
Chemical Precipitation method/technique :
Precipitation is the process of separating the solid particles from the
solution by physical and/or chemical changes.

This is one of the simplest chemical technique to obtain the

nanoparticles. The principle of this technique is getting the
precipitation of our desired materials after reactions occurred by
mixing solutes and solvents.

In this case, the precipitation of ions may occur slowly. By washing

with some suitable reagents or drying up the precipitation, one can get
the required nanoparticles. It is widely used to synthesis metal oxide
and insulators with broad band gap along with suitable surface.
 Bottom-up Fabrication methods
Chemical Precipitation method/technique :
 Characterization Techniques:

X-Ray Diffraction (XRD)

&
Transmission Electron Microscope (TEM)

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 Characterization Techniques
X-Ray Diffraction (XRD):
Most of the metals and alloys are crystalline in nature. Hence one of the
most useful characterization technique is X-ray diffraction (XRD).
XRD is based on the Bragg’s law 2d sinθ = nλ
The intensity of diffracted X-Rays is
measured as a function of diffracted
angle and the specimen orientation.

This diffracted pattern is used to

identify the specimen’s crystalline
phases and to measure its structural
properties.

The diffraction peaks are accurately

measured with XRD which gives
information about homogenous and
inhomogeneous strains. 42
 Characterization Techniques
X-Ray Diffraction (XRD) Machine:

Fig.: XRD pattern of Nano-particles

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 Characterization Techniques
If there is no inhomogenous strain, the crystalline size D can be estimated
from the peak width with Scherrer’s formula:

D = Kλ / (B cos θB),

Where λ is wavelength, B is the full width of half maximum of diffraction

peaks, θB is diffraction angle and K is Scherrer’s constant of the order of unity
for ordinary crystal.
The XRD is useful for following applications:
Study of d-spacing
Study of mixtures
Study of crystal symmetry
Study of alloys
Stress determination in metals
Determination of particle size
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 Characterization Techniques
Transmission Electron Microscope (TEM):

In TEM, electrons are accelerated from 10 KeV to 1 MeV projected onto

a thin specimen with thickness less than 200 nm. The electron beam is
projected on to the specimen by means of condenser lens system and
penetrates the sample thickness either deflected or undeflected.

The advantages of TEM are its highest magnification up to the order of

micron and its ability to provide both image and diffraction information
from a single sample.

There are two scattering processes experienced by the electrons during

their passage through the specimen. The elastic scattering involves no
energy loss and gives rise to diffraction pattern.
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 Characterization Techniques
Inelastic interactions between primary electrons and secondary electrons
at heterogeneities such as grain boundaries, dislocations, defects, density
variations in the intensity of transmitted electrons.
The high magnification or resolution of TEM is a result of the small
effective electron wavelength which is given by relation λ=
where m and e electron mass and charge, h is Planck’s constant and V is
potential difference through which electrons are accelerated.

The higher the operating voltage of a TEM, greater is the lateral spatial
resolution.

The disadvantage of TEM is its limited depth resolution.

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 Characterization Techniques
Selected Area Diffraction (SAD) offers a unique capability to determine
the crystal structure of individual nanomaterials such as nanocrystals
and nanorods and the crystal structure of different parts of the sample.

SAD patterns are often used to determine the Bravais lattices and lattice
parameters of crystalline materials by the same procedure used in XRD.

TEM can be used to determine the melting point of nanocrystals. An

electron beam is used to heat up the nanocrystals and the melting points
are decided by the disappearance of diffracted pattern.

TEM can be used to measure the mechanical and electrical properties of

individual nano-wires and nano-tubes.

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 Characterization Techniques
TEM gives the following information:
Morphology: The size, shape and arrangement of particles as well as
their relationship to one another on the scale of atomic diameters.

Crystallographic information:
The arrangement of atoms in the
specimen and their degree of
order, detection of atomic-scale
defects a few nanometers in
diameters.
Compositional information:
The elements and compounds the
sample is composed of and their
relative ratios.
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49
 Bottom-up Fabrication methods

Flow Chart
for the
Solution
Combustion
Synthesis