Introduction to Nanotechnology

• In 1959, Prof. Richard Feynman presented an idea of building materials atom

by atom and this idea evolve into a new branch of science called
nanoscience.

• In 1974, Prof. Norio Taniguchi coined the term Nanotechnology to describe

semiconductor processes like thin film deposition and ion beam milling
exhibiting characteristic control on the order of a nanometer.

• The invention of the Scanning Tunneling Microscope (STM) in 1981, followed

by the Atomic Force Microscope (AFM) in 1982 marked the beginning of
nanotechnology, as it enabled scientists to observe atoms for the 1st time.

• Nanotechnology is defined as the technology of manipulating materials at

the atomic and molecular scale to produce innovative functionalities and
exotic properties of the material.
 Introduction to Nanotechnology
• One of the first notable successes in nanotechnology has been in
manipulating the magnetic and electrical properties of atoms to store vast
amounts of data, paving the way for iPods and other storage devices.

• Dr. Fert and Dr. Grunberg discovered even smaller and denser types of
memory storage using spintronics (for which they received Nobel prizes)
where the data is stored by manipulating the spins of electrons.

• Nanoparticles of iron compounds can be used to clean up waste sites and

break down hazardous organic compounds such as PCBs, dry cleaning fluids
and neutralizing poisons such as lead and arsenic.
 Introduction to Nanotechnology
• Study of materials and their properties at the scale of few nanometers is
called nanoscience, and to do so, we required some tools and techniques
used to synthesize and characterize the nanomaterials, as well as the use of
nanomaterial properties in various applications is called nanotechnology.

• The prefix “nano” comes from the Greek word for “dwarf” and it means one
billionth.

• The materials having grain size of the order of nanometer (10-9 m) scale are
known as nanoscale. The dimensions are in the range of 0.1 to 100 nm.
 What is the need for Nanotechnology?
• Nanotechnology offers a variety of new opportunities to tackle a number of
problems and enable research that was not thought to be possible earlier.

• The impact of nanotechnology is being observed in diverse fields as

Electronics, Health care & Medicine, Energy, Agriculture & Food, Materials
science, and many more.

Nanotechnology is revolutionary owing to following primary reasons:

1) Novel properties: Since a material's properties at the nanoscale differ

drastically from the material's macroscale properties, we have novel
properties to exploit in research.

2) Opportunities of Scale: The fact that the scale is so small which allows novel
approaches and applications that weren't thought possible in the past.
 Novel Properties
• Breaking a piece of gold or silver into smaller and smaller pieces, each piece
will still have the same color, melting & boiling points, density, electrical
conductivity, and ability to catalyze chemical reactions as the original.

• However at the nanoscale, both gold and silver exhibits different colors
throughout the nanoscale size range and other different properties except
the size dependent catalytic properties of gold until 5 nm.
 Novel Properties

Material Bulk Nanoscale

Gold Non magnetic Ferromagnetic
Gold Yellow Red/Orange
Graphite Conductor Semiconductor (Armchair)
Graphite Opaque Transparent
Hexagonal Boron nitride Insulator Conductor/Semiconductor
 Opportunities of Scale
• Synthesizing a nanoparticle to target specific cells. e.g. In photothermal
therapy, the nanoparticles embedded within tumors are exposed to tissue-
penetrating near-infrared light, which causes the nanoparticles to produce
enough heat to damage adjacent cancer cells.
Opportunities of Scale
Why materials behave differently at nanoscale?
• At nanoscale, the different properties of the materials changes. There are
two principal factors owing to which the properties of the material changes
and hence the materials behave differently at the nanoscale.

1) Higher Surface to Volume ratio

• Consider a sphere of radius r as shown in figure.

• The surface area of the sphere is 4𝜋𝑟 2 and,

4
• The volume of the sphere is 𝜋𝑟 3
3
4𝜋𝑟 2 3
• The surface area to volume ratio (S/V) will be 4 3
=
𝜋𝑟 𝑟
3
It is evident from the above relation that (S/V) ratio varies inversely with radius
r. This signifies that as the size of particle is small, the S/V ratio will be higher.
Why materials behave differently at nanoscale?
2) Quantum confinement effect: When the diamensions of the material is
equal to the de-Broglie wavelength of electron or mean free path of
electrons, the energy of electron changes. This effect is known as quantum
confinement.

• If only one dimension of any material is constrained to the nanoscale, we

obtain a layered structure known as two-dimensional (2D) material.

• If two dimensions are constrained to the nanoscale, we obtain a

wired/rod/tube shape structure called one-dimensional (1D) material.

• if all three dimensions are limited to the nanoscale, we acquire a sphere-

shaped structure called zero-dimensional (0D) materials.
Schematic of 0D, 1D and 2D
 Synthesis of nanomaterials
• There are two different approaches available to synthesize the nanomaterials
namely Top-down Approach and Bottom-up Approach.

1) Top-down Approach

• It is a physical process wherein a large

scale object is progressively reduced in
dimensions to get nanomaterials.

2) Bottom-up Approach

• It is a chemical process wherein atomic

and molecular component assembles
themselves (atom by atom/ molecule by
molecule) to produce nanomaterials.
 Synthesis of nanomaterials
• There are two different approaches available to synthesize the nanomaterials
namely Top-down Approach and Bottom-up Approach.
Synthesis of nanomaterials
Synthesis of nanomaterials (Physics Methods)
Mechanical Method (High energy ball milling)
• It is one of the simplest ways of making
nanoparticles in the form of powder.

• Many types of mills such as planetary, vibratory,

rod, tumbler etc. are being used for the
preparation of nanoparticles.

• Usually one or more containers are used at a time

to make large quantities of fine particles. Size of
container, of course, depends upon the quantity
of interest.

• In this case we have considered a planetary mill.

Synthesis of nanomaterials (Physics Methods)
Mechanical Method (High energy ball milling)
• Container consist of Hardened steel or tungsten
carbide balls along with powder or flakes (< 50
𝜇𝑚) of a material of interest.

• Usually 2:1 mass ratio of balls to material is

advisable.

• Container is closed with tight lids and can have

two different movements, 1) About its own axis 2)
About particular central axis

• If the container is more than half filled, the

efficiency of milling is reduced.
Synthesis of nanomaterials (Physics Methods)
Mechanical Method (High energy ball milling)
• When the containers starts rotating around the
central axis as well as their own axis at more than
100 rpm speed, the collision between steel balls
and materials takes place.

• The material is also forced to the walls and is

pressed against the walls. Hence, the temperature
rise in the range of 100–1100 ° C . Cryo-cooling is
used sometimes to dissipate the heat generated.

• Heavy milling produce smaller grain size but larger

defects in the particles. The process, however,
may add some impurities from balls.
Synthesis of nanomaterials (Physics Methods)
Mechanical Method (High energy ball milling)
Advantages:

• This technique is simple and does not require any complex set up.

• It is very cheap and easy process.

• It produces nano powder of 2-20 nm in size.

• This technique is effective for synthesizing metal-ceramic composite powder.

• It is possible to produce large quanta of nanoparticles by this method.

Synthesis of nanomaterials (Physics Methods)
Mechanical Method (High energy ball milling)
Disadvantages:

• It is not sophisticated process therefore shape of the nano material is

irregular.

• There is a possibility of contamination from milling media and atmosphere.

• This method produces crystalline defects.

• This process is very restrictive for the production of non-oxide materials.

• The milling should take place in an inert atmosphere

Synthesis of nanomaterials (Physics Methods)
Laser Ablation
• Laser ablation method has been extensively used
for the preparation of nanoparticles and thin Nd:YAG Laser
films.

• It is the process of removing material from a solid

surface by irradiating it with a laser beam.

• In this technique, a highly intense pulsed laser

beam is allowed to strike the target surface. For
instance, Pulsed laser beam Nd:YAG.

• The target is placed in an evacuated chamber at a

pressure of 10-6 Torr.
Synthesis of nanomaterials (Physics Methods)
Laser Ablation
• When a Nd:YAG laser beam strikes the target
surface, it evaporates the target material. Nd:YAG Laser

• This evaporated material forms the ablation

plume. This plume is nothing but the molecular
fragment of target materials (atoms, ions and
molecule) which are going to be removed from
the surface which will result in a situation like
plasma.

• The inert gas carries the plume to the surface of

the substrate on which the nanomaterial is
deposited.
Synthesis of nanomaterials (Physics Methods)
Precautions to be taken care of
• The ablation site should be cleared very often by a
pressurized inert gas, such as nitrogen or argon Nd:YAG Laser
for the sake of cleanliness.

• Pulse duration must be short to maximize peak

power and to minimize thermal conduction to the
surrounding work material

• If the pulse repetition rate is too low, all of the

energy which was not used for ablation will leave
the ablation zone which cooling down the system
Synthesis of nanomaterials (Physics Methods)
Synthesis of nanomaterials (Physics Methods)
Sputtering
• Sputtering is a physical vapor deposition process
used for depositing a thin-film onto a substrate,
by ejecting atoms from target materials and
condensing the ejected atoms onto a substrate in
a high vacuum environment.

• The ejection of atoms from the target materials is

to be done by bombarding the high energetic
ions, typically inert gas ions such as Ar+.

• In this process, the substrate and target material

are first placed on the anode and cathode,
respectively, inside a vacuum chamber.
Synthesis of nanomaterials (Physics Methods)
Sputtering
• Electrically-neutral argon atoms are introduced
into a vacuum chamber at a pressure of 1-10
mTorr.

• A DC voltage is then applied between the target

and substrate which ionizes argon atoms and
creates a plasma, hot gas‐like phase consisting of
ions and electrons in the chamber.

• These argon ions are accelerated towards the

cathode target. Upon collision with the target,
atoms from the target are ejected and travel to
the substrate, where they begin to condense.
Synthesis of nanomaterials (Physics Methods)
Sputtering
• As atoms accumulate on the substrate, they
interact at the molecular level, forming a strongly
bonded atomic layer.

• By controlling the sputtering time, one or more

layers of these atoms can be created, enabling the
production of precise layered thin-film structures.

• Electrons released during Argon ionization are

accelerated to the anode substrate, subsequently
colliding with additional Argon atoms, creating
more ions and free electrons in the process,
continuing the cycle.
Synthesis of nanomaterials (Chemical Methods)
Chemical Vapor Deposition (CVD)
• Chemical Vapor Deposition (CVD) is a thin film deposition technique that uses
chemical reactions to deposit high quality layers of a designated material.

• In this technique, the predefined mix of reactive gases are introduced at the
specified flow rate into the reaction chamber at ambient temperature.
Synthesis of nanomaterials (Chemical Methods)
Chemical Vapor Deposition (CVD)
• This gas moves towards the heated substrate and the reacting gas adsorbed on
the surface of the substrate and undergo chemical reactions there.

• As a result of this chemical reaction, a thin film is formed on the surface of the
substrate.
Synthesis of nanomaterials (Chemical Methods)
Chemical Vapor Deposition (CVD)
• During this chemical reaction, some byproducts are going to form which will
desorbed and evacuated from the reaction chamber by means of carrier gas
flow.

• To avoid undesired chemical reactions, the substrate surface temperature,

deposition time, pressure and type of surface is carefully selected.
Synthesis of nanomaterials (Chemical Methods)
Chemical Vapor Deposition (CVD)
Synthesis of nanomaterials (Chemical Methods)
Advantages of Chemical Vapor Deposition (CVD)
• Uniform thickness of the film

• Flexibility of using wide range of chemical precursors

• Require Low deposition temperature

• Ability to control crystal structure

• Deposition rate can easily be adjusted

• It can be adapted to many process variations

Synthesis of nanomaterials (Chemical Methods)
Disadvantages of Chemical Vapor Deposition (CVD)
• Safety and health hazards as precursor gases are toxic, corrosive, flammable.

• Require numerous test runs to determine and reach suitable growth

parameters
Synthesis of nanomaterials (Chemical Methods)
Types of CVD processes
• APCVD-Atmospheric Pressure CVD

• MOCVD-Metal Organic CVD

• PECVD-Plasma Enhanced CVD

• LPCVD-Low pressure CVD

• PCVD-Photochemical Vapour Deposition

• CVI-Chemical Vapour Infiltration

• CBE-Chemical Beam Epitaxy

Synthesis of nanomaterials (Chemical Methods)
Sol-Gel method
• Sol-Gel method is an example of wet chemical
synthesis of nanomaterials. It is based on
inorganic polymerization reaction.

• It is generally carried out at room temperature

and includes four steps: Hydrolysis,
polycondensation, drying and thermal
decomposition.

• This method is widely used to synthesize oxide

particles and as the name suggests Sol-Gel
involves two types of materials or components
namely, ‘Sol’ and ‘Gel’.
Synthesis of nanomaterials (Chemical Methods)
Sol-Gel method
• Sol is a liquid solution with solid particles
suspended in it. Gel is nothing but a continuous
network of a solid particles with pores filled with
liquid.

• The reactions and steps involved in the sol-gel

process can be described as follows:
Synthesis of nanomaterials (Chemical Methods)
Sol-Gel method
• A stable solution of the alkoxide or solvated metal
precursor (the sol) is formed.

• An oxide- or alcohol- bridged network (the gel)

forms by a polycondensation reaction.

• The polycondensation reactions continue until the

gel transforms into a solid mass.

• Drying of the gel by thermal evaporation or

supercritical condition resulting into the product
xerogel/aerogel.
Synthesis of nanomaterials (Chemical Methods)
Advantages of Sol-Gel method
• It is used to synthesize nano materials of very high purity.

• It is economically cheap.

• Moderate temperatures are sufficient for drying or calcination of the sample.

• It is suitable to produce extremely homogeneous nano composites.

• One material can be coated on other during the sol-gel process.

Disadvantages of Sol-Gel method

• It is qualitative approach ; therefore, the output of the product is very less.
 Characterization of Nanomaterials
Scanning Electron Microscope (SEM)
• Scanning Electron Microscope (SEM) is used to
study the surface topography of material.

• An electron gun made up of Tungsten Filament or

Lanthanum Hexaboride crystal is used as a source
of electron.

• This emitted electrons are accelerated to an

energy between 1-30 keV by means of anode and
directed towards magnetic lens (condenser lens).

• The electron beam then passes through the

magnetic lens and get focus into a small region of
size 40-50 Angstrom.
 Characterization of Nanomaterials
Scanning Electron Microscope (SEM)
• Scanning Coil provides movement to the electron
beam in both the x and y directions over the
material. This type of scanning is known as Raster
Scanning.

• The electron beam then passes through an

objective lens and is focused onto the surface of
the material, resulting in the generation of
Backscattered electrons, Secondary electrons and
X-rays.

• They then analyzed and an enlarged version is

displayed on the monitor.
 Characterization of Nanomaterials
Scanning Electron Microscope (SEM)
 Characterization of Nanomaterials
Transmission Electron Microscope (SEM)
Principle:

• Electrons of very high energy typically >50 keV are

made to pass through the specimen and the
image is formed on the fluorescent screen, either
by using the transmitted beam or by using the
diffracted beam.

Construction:
• It consists of an electron gun to produce
electrons.

• Magnetic condensing lens is used to condense the

electrons and to adjust the size of the electron.
 Characterization of Nanomaterials
Transmission Electron Microscope (SEM)
• The specimen is placed in between the
condensing lens and the objective lens as shown.

• The magnetic objective lens is used to block the

high angle diffracted beam and the aperture is
used to eliminate the diffracted beam (if any) and
in turn increases the contrast of the image.

• The magnetic projector lens is placed above the

fluorescent screen in order to achieve higher
magnification.

• The image can be recorded by using a fluorescent

(Phosphor) screen.
 Characterization of Nanomaterials
Transmission Electron Microscope (TEM)
Working:

• Stream of electrons are produced by the electron

gun and is made to fall over the specimen using
the magnetic condensing lens.

• Based on the angle of incidence the beam is

partially transmitted and partially diffracted. Both
these beams are recombined at the E-wald sphere
to form the image.

• The combined image is called the phase contrast

image.
Characterization of Nanomaterials
 Characterization of Nanomaterials
X-ray Diffraction (XRD) and Bragg’s Law
 Characterization of Nanomaterials
Single Crystal Method for XRD
• In this method, monochromatic X-rays are
incident on a crystal rotating about an axis.

• A single crystal of about 1 mm in size is placed on

a rotating shaft.

• When the crystal is rotated, angle 𝝷 for different

plane changes continuously.

• Whenever a set of 𝝺, 𝝷 and d satisfy Bragg’s

condition Bragg peak (spot) appears.

• A cylindrical photographic film is used to record

the diffracted beams.
 Characterization of Nanomaterials
Single Crystal Method for XRD
• This process can be performed in 2-ways.

Method of Complete Rotation:

• In this method, the crystal is uniformly rotated

through 360 0 . In a complete rotation, some of
the planes are repeated and thus overlapping of
spots occurs.

Oscillating Crystal Method:

• To reduce the overlapping of spots, the crystal is

oscillated through some angle. Spot pattern is not
symmetric.
 Characterization of Nanomaterials
Powder Method for XRD
• In this method, instead of a single crystal the
specimen is used in the form of powders of
different particle size.

• The powder is filled in a narrow, needle shaped

glass tube and a monochromatic beam of X-ray is
going to incident on the powder specimen.

• The specimen is not rotated as different

microcrystals have already different oriented
planes in them.

• A strip shaped photographic film encircles the

powder specimen inside of the cylindrical drum.
 Characterization of Nanomaterials
Powder Method for XRD
• When a monochromatic beam of X-ray is allowed
to fall on the powder sample, Bragg’s condition is
satisfied by many planes in differently oriented
microcrystals and a diffracted beams of conical
shape emerging out.

• This diffracted beams are going to record by a

photographic film and produce a pattern as
shown in figure.

• This method is used to determine lattice

constants. Since lattice constants are unique for a
material, this method is used for the identification
of materials.
 Nanostructures
As discussed in the beginning of the session, nanostructures are those materials
which are having their dimensions in the nanometer scale.

Following are the well-known nanostructure

Graphene: It is a single atom thick layer of carbon

atom where in the carbon atoms are tightly packed
in a hexagonal lattice.

Carbon nanotubes: is a cylindrical rolled up sheet of

graphene.

Fullerenes: It is the form of carbon having a large

spheroidal molecule consisting of a hollow cage of
sixty atoms.
 Carbon Nanotubes
• In 1991, Sumio Ijima discovered Carbon Nano Tubes (CNT). They are
allotropes of carbon atoms with a cylindrical nanostructure.

• CNTs are large molecules of pure carbon that are long and thin shape like
tubes having diameter of 1-3 nm.
 Carbon Nanotubes
SINGLE WALLED CNT: A single graphene tube (Graphite layer) having diameter
of 2 nm and length of 100 μm is called single walled CNT (SWCNT).

MULTI WALLED CNT: Two or more than two graphene tubes (Graphite layers)
having diameter in few nanometers is called multi walled CNT. (MWCNT)
 Carbon Nanotubes
CHIRAL VECTOR (CH): The structure of nanotube can be specified by a vector
Ch, which is given by Ch = na1+ma2 in an infinite graphene sheet. where n & m
are the unit vector of graphite in real space.

Translational Vector (T): The angle which is normal to

chiral vector, is known as translational vector.

Chiral Tube: A tube obtained by folding the sheet

along chiral angle is called chiral tube.

Chiral Angle (ϴ): The angle (ϴ) between X axis and

chiral vector (Ch) is known as chiral angle. It is also
used to denote the folding types. The angle
between 0° < ϴ < 30° are sufficient to uniquely
define different types of nanotubes.
 Carbon Nanotubes
Sr. Various
Armchair Zigzag Chiral / Helical
No. Parameters
1. Definition CNTs having value of CNTs having value of CNTs having valueof
chiral angle equalto 30° chiral angle equalto 0° chiral angle in between
and T is parallel to C-C and T isn’t parallel to C-C 0° – 30° and T isn’t
bondof carbon hexagons bondof carbon hexagons parallelto C-C bond of
are known as armchair are known as zigzagCNTs. carbon hexagons are
CNTs. known as
Helical CNTs.
2. Chiral Vector (Ch) Ch = (n, m) Ch = (n, 0) Ch = (n, m) where,
where n=m where, m=0 n, m≠0, n≠m.

3. Chiral Angle (ϴ) 30° 0° 0° < ϴ < 30°

4. Chirality Achiral Achiral Chiral

Metallic or
Semiconducting
5. Types Metallic Semiconducting
depending upon
chirality
 Carbon Nanotubes
Characteristics of Carbon Nanotubes (CNTs):

• CNTs have high electrical and thermal conductivity.

• CNTs are very elastic.

• CNTs have high tensile strength.

• CNTs are highly flexible.

• CNTs have low thermal expansion.

• CNTs are good electron field emitter.

Thank you
For
Your Time