UNIT –IV

NANOMATERIALS AND CHARACTERIZATION TECHNIQUES

Nanoscience:
1. Nanoscience can be defined as the study of phenomena and manipulation of materials at
atomic, molecular and macromolecular scales, where properties differ significantly from those at
a larger scale.
2. Nano means 10-9 m. One nanometer (nm) = 10-9 m (one billionth of a meter) = 10 Å.
Nanotechnology:
Nanotechnology can be defined as the design, characterization, production and application of
structures, devices and systems by controlling shape and size at the nanometer scale.
# Nanomaterials:
Nanomaterials can be defined as those materials which have structured components with size
less than 100 nm at least in one dimension.

# Classification of nanomaterials based on the dimension:

Based on the number of dimensions, nanomaterials are classified as
1. Zero dimensional

2. One dimensional

3. Two dimensional

4. Three dimensional

1. Zero dimensional: If all three dimensions of a material are in the nanometer scale, the
material falls into the 0-dimensional nanostructure category.
Examples: Quantum dots. Nanoparticles
2. One dimensional: If two dimensions of a material are in the nanometer scale, the material
falls into 1-dimensional nanostructure.
Examples: Nanorods, nanowires, etc.
3. Two dimensional: If one dimension of a material is in the nanometer scale, the material falls
into 2-dimensional nanostructure.
Examples: Nanolayers, Nanofilms, etc.
4. Three dimensional: 3D nanomaterials or bulk materials are nanomaterials that are not
confined to the nanoscale in any dimension or dimension range. All dimensions of a 3D material
are outside the nanometer range or greater than 100 nm, but the bulk material is made up of
individual blocks that are in the nanometer scale (1–100 nm).

# Basic principles of nanomaterials:

The general properties of nanomaterials different from the normal bulk materials for two
reasons:

(i) Increased relative surface area (ii) Quantum confinement effect.

(i) Increase in surface area to volume ratio:

1. Nano materials have a relatively larger surface area when compared to the same mass or
volume of material produced in a larger form.
2. As particle size decreases, a greater proportion of atoms are found at the surface compared to
those inside.
3. This can make materials more chemically reactive and affect their strength or electrical
properties.

(ii) Quantum confinement effect:

1. In nanomaterials, the electronic energy levels are not continuous as in the bulk but are
discrete (finite density of states), because of the confinement of the electronic wave
function to the physical dimension of the particles.
 2. Depending on the dimension of the confinement, three kinds of confined structures are
defined: quantum well (QW), quantum wire (QR) and quantum dot (QD).
3. Splitting of energy levels in quantum dots due to the quantum confinement effect,
semiconductor band gap increases with decrease in size of the nanocrystal, as shown in
below figure.

4. Quantum effects can begin to dominate the behavior of matter at the nanoscale affecting the
optical, electrical and magnetic behavior.

# Nanomaterials production techniques (Approaches):

There are two ways of approaching the nanoscale objects:

(i) Top –down approach.

(ii) Bottom –up approach.

(i) Top –down approach:

Top-down approach involves the breaking down of the bulk material into nanosized
structures or particles. Top-down synthesis techniques are extension of those that have
been used for producing micron sized particles.

Top-down approaches are inherently simpler and depend either on removal or division
of bulk material or on miniaturization of bulk fabrication processes to produce the
desired structure with appropriate properties.

The biggest problem with the top-down approach is the imperfection of surface structure.
This approach involves more wastage.

Ex: High-energy ball milling, gas-phase condensation, etc.

(ii) Bottom –up approach:

Bottom- up approach refers to the buildup of a material from the bottom i.e., atom by
atom & molecule by molecule or cluster by cluster. This approach involves less wastage.

Many of these techniques are still under development or are just beginning to be used for
commercial production of nanopowders.

Ex: Sol-gel synthesis, colloidal precipitation, hydrothermal synthesis, etc.

Fabrication of nanomaterials:

Characteristics of nanoparticles that should posses by any fabrication technique are

i) Identical size of particles

ii) Identical shape or morphology

Nanomaterials are produced by two methods. They are

1. Physical methods (Eg: Ball milling, Physical vapour deposition, Laser ablation,

Sputtering deposition, electric arc deposition, etc)

2. Chemical methods ( Eg: Sol-Gel, Combustion, Polyol, microemulsion, etc.)

A) Physical methods:

Ball Milling Method:

1. High energy ball milling is a top-down technique. Coarse grained materials are crushed
mechanically in rotating drums by hard steel and tungsten carbide balls.

3. A container is filled with stainless steel balls of a few millimeters in diameter as shown in
above fig. The material to be crushed is added in the form of a powder of about 50 diameter
grain size.
4. After filling the container with liquid nitrogen, a rotating shaft grinds the material. The
grinding periods are within the range of minutes to some 100 hours.
5. This process is simple. The main problem in this technique is the contamination due to milling
tools and atmosphere.
6. The use of tungsten carbide component and inert atmosphere and/or high vacuum can reduce
the impurity levels.
Advantages:
1. Main advantage is high production rates of nano
2. powders.
2. Magnetic and catalytic nanoparticles are usually produced by this method.

Disadvantages:
1. Low surface area, highly poly-disperse size distribution and partially amorphous state of the
powder.
2. We cannot be sure that all the particles are broken down to the required particle size.
3. Contamination by the milling tools and atmosphere.

B) Chemical methods:

Sol-Gel Method: (wet chemical synthesis of nanomaterials):

1. The Sol-Gel is a bottom-up technique.

2. Sol-gel processing refers to the hydrolysis and condensation of alkoxide-based precursors such
as Si(OEt) 4 (tetraethyl orthosilicate, or TEOS). The reactions involved in the sol-gel chemistry
based on the hydrolysis and condensation of metal alkoxides M(OR) can be described as follows
Hydrolysis: The chemical breakdown of a compound due to reaction with water.

Poly-condensation:

A chemical condensation leading to the formation of a polymer by the linking

together of molecules of a monomer and the releasing of water or a similar simple substance.

2. Sol: A colloid that is suspended in a liquid is called as sol.

The sol can be processed to obtain the substrate in a film, by either dip coating or spin coating.

3. Gel: The formation of a network in a continuous liquid phase (gel). Removal of the liquid
from the sol yields the gel.

4. The sol/gel transition controls the particle size and shape. Calcination of the gel produces the
oxide.

A schematic representation of sol-gel process of synthesis of nanomaterials is shown in fig.

The sol-gel process can be characterized by a series of distinct steps:

Step 1: Formation of different stable solutions of the alkoxide or solvated metal precursor (the
sol).

Step 2: Gel formation by a poly-condensation or poly-esterification reaction (increase in

viscosity of the solution).

Step 3: Aging of the gel (Gel transforms into a solid mass, accompanied by contraction of the
gel network and expulsion of solvent from gel pores).

Step 4: Drying of the gel. (Removal of water and other volatile liquids). If isolated by thermal
evaporation produce Xerogel. If the solvent (such as water) is extracted with drying, the product
is an Aerogel.

Step 5: Dehydration (surface-bound -OH groups are removed).

Step 6: Densification and decomposition of the gels at high temperatures (T > 8000C).

Advantages: 1.Main benefits of sol–gel processing are the high purity and uniform nanostructure
achievable at low temperatures. 2. Production of organic-inorganic hybrids
Disadvantages: High cost of the materials and long processing times

# Properties of nanomaterials:

A major fraction of atoms in a nanoparticle is located at the surface. Therefore, there is a change
in inter particle spacing and increase in surface to volume ratio, which had combined effect on
material properties.

Lattice parameters: The lattice parameters of nanomaterials decreases with decrease in size of
the particle, which is due to competition between the long-range electrostatic forces and short
range core-core repulsion.
Thermal properties
The melting point or phase transition temperature decreases with size and the rate of decrease
increases substantially at very small sizes. The following graph shows the decrease of melting
point with size of the particle.

Mechanical properties
In nanomaterials, the interface area within the material greatly increases, which enhances its
strength. For example, nanocrystalline nickel is as strong as hardened steel.

Magnetic properties
1. In nanoclusters, the magnetic moment of each atom interact with the moment of the other
atoms, as a result nonmagnetic atoms can have a net magnetic moment.
2. The magnetic moment increases as cluster size decreases. Nanoclusters are more magnetic
than that of bulk materials.
Electrical properties
1. Reduction in particle size has two different effects on electrical conductivity. Nanoparticle
product enhance the crystal perfection and reduce the defects. As a result electron scattering
reduces, which leads to reduction in resistivity.
2. In addition a reduction in particle size below a critical dimension, would result in a modified
electronic structure with wide and discrete band gap. The reduction of particle size into this
range would result in an increased electrical resistivity.
Optical properties
The energy levels separation in a nanocluster is different. Therefore, the clusters of different
sizes exhibit different colors due to different absorption spectra.

Chemical properties (Reactivity and catalytic properties):

1. The nanomaterials have high reactivity as compared to that of bulk, due to their high surface
to volume ratio.
2. The high surface area to volume ratio, and the variations in geometry and electronic structure
have a strong effect on catalytic properties. The hydrogen absorbing ability of a metal decreases
with size.

# Applications of nanomaterials in medical field:

Imaging (cell imaging, in vivo imaging, etc.)

Drug or gene delivery

Cancer treatment

Regenerative medicine
 Medical devices and sensors

1. Nanocrystalline zirconium oxide is used as a hard, wear resistant, bio- corrosion resistant
and bio-compatible material.
2. Nanocrystalline silicon carbide is used to make artificial heart valves.
3. Controlled drug delivery is possible using nanotechnology.
4. Nanostrucured ceramics are used as an implant material.
5. Further nanorobots inserted into our body can modify the neuron networks of brain to
enhance our intelligence.
# ELECTRON MICROSCOPY:
In electron microscopy, high resolution images are the result of using electrons as the
source of illumination. The resolution is about 0.01 nanometers (magnification up to 300,000X).
There are two main types of electron microscopes (EM), the scanning electron microscope
(SEM), and the transmission electron microscope (TEM).

# Scanning electron microscope (SEM)

Principle: Detection of back scattered electrons or secondary electrons after interaction with
sample.
SEM produces images of a sample by scanning the surface with a focused beam of electrons.
The electrons interact with atoms in the sample, producing various signals that contain
information about the surface topography and composition of the sample.
 Figure: Schematic diagram of a scanning electron microscopy (SEM).

It consists of an electron gun at the top and it generates an electron beam through
thermionic or field emission. The generated electron beam attracts towards the anode and
condensed by a condenser lens system. By using objective lens system, the condensed electron
beam is focused as a very fine point on the sample. The primary electrons of the electron beam
strike the sample surface and exhibit inelastic scattering by the atoms in the sample. The
scattered electrons are collected by secondary or backscatter detector and converted to a voltage,
and amplified. The amplified voltage is applied to the CRT grid and forms a clear image of the
sample. The interaction of electrons with the sample also produces X-rays and these X-rays are
detected by the SEM equipped with energy dispersive X-ray spectrometer (EDS) and wavelength
dispersive X-ray spectrometer (WDS), which can extend the possibility of elemental analysis.

Applications:

SEM is used in Materials science. SEMs are used in materials science for research, quality
control and failure analysis. Nanowires for gas sensing, Semiconductor inspection, Microchip
assembly, Forensic investigations, Biological sciences, Soil and rock sampling and Medical
science.
1. Used to topographical, morphological and compositional information

2. Can detect and analyze surface fractures

3. Provide information in microstructures, examine surface contaminations, reveal spatial

variations in chemical compositions, provide qualitative chemical analyses and identify
crystalline structures.

# Transmission electron microscope (TEM)

Principle: TEM operates on the same basic principle as the light microscope but uses electrons
instead of light. Because the wavelength of electrons is much smaller than that of light. Detection
of electrons transmitted through the sample.

Fig. Schematic diagram of a transmission electron microscopy (TEM).

The electron beam emitted from the electron gun travels through the column of the
microscope under high vacuum condition. Electromagnetic lenses are used to focus the electrons
into a very thin beam. This thin electron beam travels through the sample. Depending on the
density of the sample, some of the electrons get scattered and disappear from the beam. The
scattered electrons at the bottom of the microscope hit the fluorescent screen and give the image
of the sample. In the high resolution imaging mode, one can obtain the images for the crystal
lattice structure of a material as an interference pattern between transmitted and diffracted
beams, which allows to observe planar and line defects, grain boundaries, interfaces, etc., at the
atomic scale resolution.
Applications:
TEM is ideal for a number of different fields such as life sciences, nanotechnology, medical,
biological and material research, forensic analysis, gemology and metallurgy as well as industry
and education.
1. To provide high magnification images of the internal structure of a sample.
2. Can investigate the crystalline structure of an object, see the stress or internal fractures of a
sample, or even view contamination within a sample through the use of diffraction patterns.

# Atomic force microscope (AFM):

Atomic-force microscopy (AFM) provides 3D profile of the surface on a nanoscale, by
measuring forces between a sharp probe (< 10 nm) and a surface at a short distance (0.2 – 10 nm
probe-sample separation).

Principle: Interaction between cantilever tip and sample surface, and detection of cantilever
deflections to generate a map of the surface topography.
 An AFM uses a cantilever with a very sharp tip (probe) to scan over a sample surface.
Probes are typically made from Si3N4 or Si. Different cantilever lengths, materials and
shapes allow for varied spring constants and resonant frequencies.

As the tip approaches the surface, the close-range, attractive force between the surface
and the tip cause the cantilever to deflect towards the surface. The amount of force
between probe and sample is dependent on the spring constant of the cantilever and
distance between probe and sample surface.

A laser beam is used to detect cantilever deflections towards or away from the surface.

The position of the beam in the detector measures the deflection of the cantilever during
the tip is scanned over the surface. The measured cantilever deflections are used to
generate a map of the surface topography.

AFM can be operated in the following modes.

Contact mode: (< 0.5 nm probe-surface separation)
Measures repulsion between tip and sample. Force of tip against sample remains constant

Non-Contact mode: (0.1- 10 nm probe-surface separation)

Measures attractive forces between tip and sample. Tip doesn’t touch sample. Van der Waals
forces between tip and sample detected. Doesn’t degrade or interfere with sample- better for soft
samples

Tapping mode: (0.5- 2 nm probe-surface separation)

Tip vertically oscillates between contacting sample surface and lifting of at frequency of 50,000
to 500,000 cycles/sec.

Advantages: Easy sample preparation, Accurate height information, Works in vacuum, air &
liquids.
Disadvantages: Limited vertical range, Limited magnification range, Data not independent of
tip, Tip or sample can be damaged.
Applications:
Identifying atoms from samples
Evaluating force interactions between atoms
Studying the physical changing properties of atoms
Studying the structural and mechanical properties of protein complexes and assembly,
such as microtubules.
Used to differentiate cancer cells and normal cells.
Evaluating and differentiating neighbouring cells and their shape and cell wall rigidity.