Unit 5: Nanomaterials and Its Characterization techniques

Introduction of Nanomaterials, Synthesis of Nanomaterials (top

down and bottom up approach), Characterization of
Nanomaterials using X-Ray Diffraction spectroscopy (XRD),
Scanning Electron Microscopy (SEM), Transmission Electron
Microscopy (TEM), Atomic Force Microscopy (AFM), Carbon
Nanotubes, Graphene, Graphene Oxide, Applications of
Nanotechnology: Memoristic Device
Nanotechnology is the creation of functional materials, devices and systems,
through the understanding and control of matter at dimensions in the nanometer
scale length (1-100 nm), where new functionalities and properties of matter are
observed and harnessed for a broad range of applications.

Nanomaterials refers to materials that having nano scale in length and these
materials will dramatically change the chemical and physical properties of the
materials.
 What is nanometer?
A nanometer (nm) is one billionth of a
meter or 10-9 meter.
i.e. 10-9 meter = 1 nanometer

Nanoscale particles are so small that they

cannot be seen with the naked eye or even
under light microscope!

100 m = 1 meter: human being

10-3 m = 1 millimeter: mosquito

10-6 m = 1 micrometer: bacterium

10-9 m = 1 nanometer: DNA helix, virus,

wavelength of optical
spectrum
10-12 m = 1 picometer: wavelength of γ-rays
3
How small are nanostructures?

Single Hair

Width = 0.1 mm

= 100 micrometers
= 100,000 nanometers !

1 nanometer = one billionth (10-9) meter

 How small are nanostructures?
DNA
6,000 nanometers
Hair

.
Red blood cell

3 nanometers
Nano and Nature
 Example 1: Lotus Leaf

1. The lotus effect refers to self cleaning properties that are a result of ultra
hydrophobicity as exhibited by Lotus Flower.

2. Dirt particles are picked up by water droplets. Due to nanoscopic

architecture on the surface which minimizes the droplet adhesion to that
surface.

3. As a result of this effect there is difficulty to wet the leaves.

 Example 2: Shark Skin

The shark skin contains sleek scale. These are made up of tough material. The
various size, shape and texture of shark skin at the micro and nano levels
reduce drag and make shark very fast in Water.
 Example 3: Gecko Feet

1. There are several nanosized hairs on the toe of Gecko that help them for
adhesion.

2. The hairs help them to stick on smooth surfaces using Vander vaals forces
of attraction.
 Example 4: Butterfly Wings

1. The butterfly wings are made up of nano-thin layers that cause light to
reflect differently. As a result of this you will see different colors of butterfly
wing.

2. Taking this fact into consideration scientists and engineers are looking
forward to develop such intelligent Solar panel.
 Example 5: Peacock Feathers

1. The colors of peacock feathers are due to the nanosized holes present on it.

2. The nanoscale pattern is repeated on feathers. This nanoscale pattern

reflects light to create iridescent colours.
 Example 6: Toucan Beak

1. The exterior of beak is made up of overlapping nanosized tiles of keratin the

same protein makes up hair and fingernails.

2. The interior of the beak is a rigid foam made of a network of Nanosized bony
fibers connected by membranes.
 Classification of Nanomaterials
On the basis of number of dimensions of a material, which are outside the
nanoscale (< 100 nm) range, the nanomaterials are classified as.

1. Zero dimensional nanomaterials (0D): In these nanomaterials all the

dimensions are measured within the nanoscale (no dimensions are larger than
100 nm). E.g. Nanospheres, nanoparticles, fullerene.

(0D) Nanomaterials: e.g. nanospheres (All the dimensions are within the nanoscale)
2. One dimensional nanomaterials (1D): In these nanomaterials, one dimension
of the nanostructure is outside the nanoscale. E.g. Nanorods, nanotubes,
nanowires, CNTs.

(1D) Nanomaterials: e.g. nanorods (One dimension is outside the nanoscale)

3. Two dimensional nanomaterials (2D): In these nanomaterials, two dimensions
of the nanostructure is outside the nanoscale. E.g. Nanodiscs, nanoplates,
nanolayers, nanofilms, nanocoatings.

(2D) Nanomaterials: e.g. nanoplates (3D) Nanomaterials

(Two dimension is outside the nanoscale)

4. Three dimensional nanomaterials (3D): In these nanomaterials, all the

dimensions of the nanostructure are outside the nanoscale. E.g. Nanoflowers,
dispersion of nanoparticles, diamonds, graphite.
 Synthesis of nanomaterials
There are two general approaches for the synthesis of nanomaterials as,
1. Top-Down approach
2. Bottom-Up approach
1. Top-Down approach:
a. Top-Down approach involves the breaking down of the bulk material into
nanosized structures and particles.
b. In this approach, there is no control over the size and morphology of
particle.
c. In Top-Down approach there is certain amount of wasted material as some
parts are removed from the original structure.
d. It produces surface imperfections and crystallographic damage to the
processed pattern.
e. In Top-down techniques, the starting material is solid state.
f. Common methods of Top-Down approach are high-energy wet ball milling,
electron beam lithography, plasma arching, sputtering, gas-phase
condensation, aerosol spray, etc.
Advantages of Top-Down approach
1. Large scale production is possible
2. Deposition over large substrate is possible

Disadvantages of Top-Down approach

1. Broad size distribution (10-1000 nm)
2. Varied particle shapes and geometry
3. Control over deposition parameters is difficult to achieve
4. Impurities: stresses, defects and imperfections get introduced
5. Expensive
Ball milling method
1. Ball milling process is used in producing metallic and ceramic nano
materials.
2. These mills are equipped with grinding media composed of wolfram carbide
or steel.
3. Ball mills rotate around a horizontal axis, partially filled with the material to
be ground plus the grinding medium.
4. The balls rotate with high energy inside a drum and then fall on the solid
with gravity force and crush the solid into nano crystallite
6. The significant advantage of this method is that it can be readily
implemented commercially.
7. It is a preferred method for preparing metal oxide nano crystals like
Cerium(CeO2) and Zinc Oxide (ZnO).
8. Disadvantage: There is no control over size of nanoparticles. All particles
may not be of same size.

Thermal Evaporation method

2. Bottom-Up approach:
a. In bottom up approach, materials are built up atom by atom. The atoms and
molecules arrange themselves into definite pattern.
b. Bottom-up (“Molecular nanotechnology”) applies to building organic and
inorganic structures atom-by-atom and molecule-by-molecule.
c. All the Bottom-up techniques, the starting material is either gaseous state or
liquid state of matter.
d. Among the top-down and bottom-up approaches, the bottom-up approach is
more accepted in synthesis of nanoparticles due to many merits as fewer
defects, more homogenous chemical composition and better ordering.
e. Bottom-up approach products have a higher precision accuracy (more
control over the material dimensions) and therefore can manufacture
smaller structures compared to top-down approach.
f. Some of the methods used in bottom-up approach include plasma arcing,
chemical vapor deposition process, metal organic decomposition, colloidal
precipitation, laser pyrolysis, solgel method, wet synthesis, and self-
assembly processes.
Advantages of Bottom-Up approach
1. Ultrafine nanoparticles, nanoshells, nanotubes can be prepared
2. Deposition parameters can be controlled
3. Narrow size distribution is possible (1-20 nm)
4. Cheaper technique

Disadvantages of Bottom-Up approach

1. Large scale production is difficult
2. Chemical purification of nanoparticles is required
NADH NAD+ e_ H+ Ag+ e_ Ag
 Applications of nanomaterials

1. In Medicine
A) Nanomedicine is the medical use of molecular-sized particles to
deliver drugs, heat, light or other substances to specific cells in the
human body.

B) Nanoparticles can deliver drugs directly to diseased cells in your

body.
C) Cancer Therapy: Nano shells are injected into cancer area and they
recognize cancer cells. Then by applying near-infrared light, the heat
generated by the light-absorbing Nano shells successfully kill
tumor cells while leaving neighboring cells intact.
2. Sunscreens and cosmetics:
A) Nanosized titanium dioxide (TiO2) and zinc oxide (ZnO2) are
currently used in some sunscreens, as they absorb and reflect
ultraviolet (UV) rays.

B) Nanosized iron oxide (FeO2) is present in some lipsticks as a pigment.

3. Displays:
Nanocrystalline materials like tungstic oxide are used in
electrochromic displays. It displays information by changing colour
when voltage is applied. CNTs are being investigated for low voltage
field-emission displays; their strength, sharpness, conductivity and
inertness make them potentially very efficient and long-lasting
emitters.

4. Clothing:
Fabric coated with zinc oxide nanoparticles gives protection against
UV rays. Silver nanoparticles have antibacterial effect on clothes.
5. Self cleaning glass:
The glass coated with nanoparticles becomes photocatalytic and
hydrophilic. When UV rays are incident on glass, nanoparticles become
energized and begin to breakdown organic particles on the surface. Due to
hydrophilic nature, glass attracts water droplets and cleans it.

6. Catalysts:
Nanoparticles have a high surface area, and hence provide higher
catalytic activity for organic reactions.

7. Harder cutting tools:

Cutting tools made of nanocrystalline materials like tungsten carbide,
titanium carbide are harder, ware resistant and long lasting.

8. Ductile, machinable ceramics:

Nanocrystalline ceramics like silicon nitride are used in high strength
spring, ball bearing, valve lifter etc.
9. Molecular Electronics:
Nanomaterials are used in development of molecular electronics.
Molecular diodes and transistors lead to miniaturization of integrated circuits.
Nanodevices exhibit low power, high packaging density and high speed.

10. Computer memory:

Scientists have created an atomic scale memory using atoms of
silicon. Its storage capacity is million times greater than conventional CD-
ROM.

11. Military Battle Suits:

A) Nanomaterials are energy absorbing materials so the battle suit
prepared from such nanomaterials will withstand blast waves.

B) Nanopores that ‘close’ upon detection of a biological agent can be

used as sensors to detect or respond to chemical and biological
weapons.
12. Batteries:
A) Nanocrystalline materials are candidates for separator plates in
batteries because of their foam-like (aerogel) structure, which can
hold considerably more energy than conventional ones.

B) Nickel–metal hydride batteries made of nanocrystalline nickel and

metal hydrides are envisioned to require less frequent recharging and
to last longer because of their large grain boundary (surface) area.

13. Water Purification:

Nano-engineered membranes could potentially lead to more energy-
efficient water purification processes, notably in desalination process.
 Carbon nanotubes (CNTs)
1. Carbon nanotubes (CNTs) are cylindrical molecules that consist of rolled-up
sheets graphene with at least one end capped with a hemisphere of the
fullerene structure.
2. Graphene is one atom thick plane network of carbon atoms which are
interconnected into hexagonal rings. Each CNT is a single molecule
composed of millions of atoms.
3. The hexagonal structure gives them high tensile strength and elastic
properties.
4. The diameter of CNT is few nanometer and length varies from micrometer
to centimeter.

Graphine and CNT

5. Rolling of graphene sheets can takes place in different ways and there are
three types based on orientation of hexagons along the axis of nanotube as
shown in figure.
6. If hexagons are aligned parallel to the axis it is arm chair. If hexagons are
oriented in a circle around the axis of nanotube, it is zigzag and if there is
twist to the nanotube so that hexagons do not form any line are called
chiral.
Types of Carbon Nanotubes
There are two main types of nanotube
1. Single walled nanotubes (SWNT): SWNTs are composed of a single layer of
graphene which forms a cylindrical shape. SWNTs have a diameter of 1-2 nm and
a length that can be many thousands of times larger i.e. to the order of
centimeters.
2. Multiwalled nanotubes (MWNT): MWNTs made of multiple layers of graphene,
which formed in a concentric pattern around the smallest nanotube. MWNTs
generally have an inner diameter of 1–3 nm and an outer diameter of upto 25
nm. The distance between neighbouring tubes is 0.34 to 0.36 nm.

SWNT MWNT
Properties of Carbon Nanotubes
1) Mechanical properties:
CNT is nothing but single large molecule and hence it has very high tensile
strength. It can be bent like rubber.

2) Thermal properties:
Thermal conductivity of CNT is very high. CNTs conduct heat by vibrations of
covalent bonds between the carbon atoms. The vibrations get transmitted
quickly through the tube due to stiffness of the tube.

3) Electrical properties:
Electrical properties of CNTs depend on orientation. Armchair configuration is
good conductor of electricity. Its conductivity is even better than copper. CNTs
with zigzag and chiral configuration shows semiconducting behaviour. Electrical
resistance may change when other molecules are attached to carbon atoms.

4) Chemical properties:
A smaller nanotube diameter results in increased reactivity.
Applications of Carbon Nanotubes
1. Biotechnology - CNT is a building block in biomimetics.
2. Medical - SWCNTs are inserted around cancerous cells and excited with radio waves. It
heats up and kills the surrounding cells.
3. Electrical circuits - Armchair CNTs are used to make low resistance electrical wires used
in power and weight sensitive spacecraft, aeroplane. It is also used to connect devices in
integrated circuits. Semiconducting CNTs are used to build up smaller transistors that are
used in integrated circuits. Electric bulbs made from CNTs can be switched on instantly,
dim easily and do not contain toxic mercury vapours. The property to change the
resistance when other molecule is attached, is used to develop sensors that can detect
carbon monoxide or biological molecules.
4. Paper battery - Paper battery uses a paper thin sheet of cellulose infused with aligned
CNT. The CNT acts a electrode allowing the battery to conduct electricity.
5. Hydrogen storage - Due to capillary effect of CNT, it is possible to condense gas in high
density inside SWCNT. It is used for hydrogen storage.
6. Solar cell - CNTs are used in solar cells due to strong UV/Visible/IR absorption
characteristics
 Scanning Electron Microscopy
1. A scanning electron microscope (SEM) is an analytical testing method that
captures high-resolution images of objects as small as 15 nanometers by
scanning the surface of object with a focused beam of electrons.
2. The electrons interact with atoms in the sample, producing various signals
that contain information about the surface topography and composition of
the sample.
The major components of the Scanning Electron Microscope include,
1. Electron Source: This is where electrons are produced under thermal
heat at a voltage of 1-40kV. the electrons condense into a beam that is used
for the creation of an image and analysis. There are three types of electron
sources that can be used i. e Tungsten filament, Lanthanum hexaboride,
and Field emission gun.
2. Lenses: It has several condenser lenses that focus the beam of electrons
from the source through the column forming a narrow beam of electrons
that form a spot called a spot size.
3. Scanning Coil: They are used to deflect the beam over the specimen
surface.
4. Detector: It is made up of several detectors that are able to differentiate
the secondary electrons, backscattered electrons, and diffracted
backscattered electrons. The functioning of the detectors highly depends
on the voltage speed, the density of the specimen.
5. The display device (data output devices)
6. Power supply
7. Vacuum system
Scanning Electron Microscope
Working of SEM
1. The electrons are emitted after thermal energy is applied to the electron
source and allowed to move in a fast motion to the anode, which has a
positive charge. (Accelerate the electrons).
2. Condenser lens will form coherent beam of accelerated electrons.
3. Then scanning coil deflect electron beam in desired direction so that the
electron beam can strike at desired region of sample surface.
4. Once the electron beam is reflected. Them magnetic lens will focus electron
beam on desired spot on the sample surface.
5. Some electrons are scattered due to elastic scattering (the back scattered
electrons).
6. Some electrons are knocked off form the surface atoms (secondary
electrons).
7. Some electrons penetrate deep into the inner shells of the sample atoms to
knock off inner shells electrons. To fill these vacancy created at inner shells,
the outer shell electrons can jump to the inner shells due to which
characteristic X-rays are produced.
5. When the secondary electrons reach and enter the detector, they strike a
scintillator (a luminescence material that fluoresces when struck by a
charged particle or high-energy photon). This emits flashes of light which
get converted into an electric current by a photomultiplier, sending a signal
to the cathode ray tube. This produces an image that looks like a television
picture that can be viewed and photographed.
6. The quantity of secondary electrons that enter the detector is highly
defined by the nature of the specimen i.e. raised surfaces to receive high
quantities of electrons, entering the detector while depressed surfaces
have fewer electrons reaching the surface and hence fewer electrons enter
the detector.
7. Therefore raised surfaces will appear brighter on the screen while
depressed surfaces appear darker.
Applications of SEM
1. SEM Applications in Semiconductor Inspection: Semiconductor
technology forms the backbone of the global digital infrastructure, with
silicon wafers especially contributing enormously to consumer electronics,
telecommunications, photovoltaics, and so on. Inspecting silicon wafers for
morphological and topographical uniformity is one of the primary SEM
applications in modern engineering. Inspectors use what is known as defect
review SEM to magnify the surface of silicon wafers to detect and
characterize defects at specific localities and to subsequently determine
what causes the fault. This feeds back into a constant quality assurance loop
with SEM data providing rich insights for incoming materials screening,
process control, and more.
2. Applications in QA/QC: The SEM technique is used for micro- and
nanoscale screening of fibers, particles, and pigments in high-value
applications. Compositional analysis of paint, for instance, to determine the
presence of specific heavy metals, toxic elements, and desirable pigments
are one of a routine production-grade SEM application.
3. Microchip Assembly with SEM: Microchips remain a crucial part of
everyday life the world over, forming the basis of every electronic
subsystem at hand. The level of finite detail and electronic density that
manufacturers can achieve with new and emerging microelectronic systems
is incredible, with smaller, lower cost, and more efficient chipsets
spearheading the next generation of networked devices. This comes with its
own unique challenges. The extremely high resolution of SEM imaging
makes it uniquely suited as a supplementary technique for microchip
assembly, providing the three-dimensional magnifications necessary for
advanced SEM applications on the microelectronics production line.
4. SEM is used in the analysis of cosmetic components which are very tiny in
size.
5. SEM is used to study the filament structures of microorganisms.
6. Biological specimens like pollen grains can be studied.
7. Corroded layer on metal surface can be studied.
8. SEM is used to study the topography of elements used in industries.
 Transmission Electron Microscopy
1. A transmission electron microscope (TEM) provides, topographical,
morphological, compositional and crystalline information of biological or
non-biological material.
2. A high energy beam of electrons is shone through a very thin sample, and
the interactions between the electrons and the atoms can be used to obtain
valuable information on the inner structure of the sample, such as crystal
structure, morphology and stress state information.
The major components of the Transmission Electron Microscope include,
1. Electron Gun: The TEM consists of an electron emission source, which
may be a tungsten filament or a lanthanum hexaboride (LaB6) source,
known as electron gun. By connecting this gun to a high-voltage source of
about 100 – 300 kV, the gun begins to emit electrons by either thermionic
or field electron emission into the vacuum.
2. The condenser system: The intensity and angular aperture of the beam
are controlled by the condenser lens system between the gun and the
specimen.
3. The image producing system: It consists of objective lens, movable
specimen stage, objective, intermediate and projector lenses, which focus
the electrons passing through the specimen to form a real, highly
magnified image.
4. The image-recording system: It converts the electron image into some
form perceptible to the human eye. The image-recording system usually
consists of a fluorescent screen for viewing and focusing the image and a
digital CCD camera for permanent records.
Working of TEM
1. A heated tungsten filament in the electron gun produces electron beam.
2. The produced electron beam is accelerated towards the sample with the
help of anode which is kept at positive potential.
3. Then condenser lens of condenser system focuses the electron beam on to
the specimen. The intensity and angular aperture of the electron beam is
controlled by the condenser lens system.
4. On reaching the specimen, the specimen scatters the electrons focusing
them on the magnetic lenses forming a large clear image, and if it passes
through a fluorescent screen it forms a polychromatic image.
5. The objective lens and intermediate lens of the image producing system
focuses the electrons passing through the specimen to form real and
magnified image. The objective lens is of short focal length and produces
real intermediate image. The real image is further magnified by projector
lens.
6. Image recording system convert the electron image into the format that can
be seen by human eye. It consists of fluorescent screen for viewing and
Applications of TEM
1. To visualize and study cell structures of bacteria, viruses, and fungi.
2. To view bacteria flagella and plasmids.
3. To view the shapes and sizes of microbial cell organelles.
4. To study and differentiate between plant and animal cells.
5. It’s also used in nanotechnology to study nanoparticles such as ZnO
nanoparticles.
6. It is used to detect and identify fractures, damaged microparticles that
further enable repair mechanisms of the particles.
7. Cancer research: TEM is used in the studies of tumor cell ultrastructures.