Unit-VIII

Nanomaterials

Introduction

Nanoscience is a phenomenon of manipulation of materials at the atomic, molecular and

macromolecular scales, where properties differ significantly from those at larger scales.
Nanotechnology is the design, characterisation, production and application of structures, devices
and systems by controlling shape and size at the nanometre scale.
Nanomaterials are defined as particles in the form of crystals, rods, or spheres having size between
1 nm and 100 nm at least in one dimension.
A nanometre is one billionth of a meter, or 10-9 m. Materials in this range of size exhibit some
remarkable specific properties. For example crystals in the nanometre scale have a low melting
point and reduced lattice constants.
Nanosystems display electronic, photochemical, electrochemical, optical, magnetic, mechanical
or catalytic properties that differ significantly not only from those of molecular units, but also
from those of macroscopic systems.

Physical properties that make nanomaterials different from bulk (macroscale) materials

1. Due to smallness of nanomaterials, their mass is extremely small and gravitational forces
become negligible, instead electromagnetic forces are dominant in determining the behaviour of
atoms and molecules.

2. For objects of very small mass, such as electrons, (wave – particle duality of matter) wave like
nature has more pronounced effect. The position of electrons are represented by wave function.
Quantum mechanics is used to describe motion and energy instead of classical mechanics.

3. The consequence of this is the tunnelling. It is the penetration of an electron into an energy
region that is classically forbidden. For a particle having less energy than the energy required to
overcome a potential barrier, there is no probability of finding the particle on the other side of
the barrier according to classical theory. But quantum mechanically, there is a finite probability
of the particle tunnelling through the barrier. The condition for this to happen is that the thickness
(energy potential) of the barrier must be comparable to the wavelength of the particle. This is
observed at nanometre scale.

4. Quantum confinement – In a nanomaterial, such as a metal, electrons are confined in space

rather than free to move in the bulk of the material.

5. Quantisation of energy – Electrons in a nanomaterial can exist at discrete energy levels.

6. At nanoscale, the random motions are of same scale as the size of the material. This has an
influence on how particle behave.
7. Increased surface to volume ratio – One of the distinguishing properties of nanomaterials is
that they have increased surface area. This leads to unique properties of materials at nanoscale.
Synthesis of nanomaterials

There are two general approaches to the synthesis of nanomaterials

and the fabrication of nanostructures. They are
(1) top-down method of miniaturizing materials,

(2) bottom-up method of building molecular structures atom by

atom or molecule by molecule.
The top-down approach has been advanced by Richard Feynman
in 1959 lecture stating that “there is plenty of room at the bottom”
and it is ideal for obtaining structures with long-range order and for
making connections with macroscopic world.
The bottom-up approach was pioneered by Jean-Marie Lehn
(revealing that “there is plenty of room at the top”) and it is best
suited for assembly and establishing short-range order at the
nanoscale.

Top-down approach

This approach use larger (macroscopic) initial structures, which can be externally controlled in
the processing of nanostructures.
Typical examples are photolithography, etching through the mask, ball milling and application
of severe plastic deformation.
1. Top-Down: lithography - The most used top-down approach is photolithography. It has
been used to manufacture computer chips and produce structures smaller than 100 nm.
Typically, an oxidized silicon (Si) wafer is coated with a 1μm thick photoresist layer.
After exposure to ultraviolet (UV) light, the photoresist undergoes a photochemical
reaction, which breaks down the polymer by rupturing the polymer chains. Subsequently,
when the wafer is rinsed in a developing solution, the exposed areas are removed leading
to nanosize material. The other methods are electron-beam lithography and X – ray
lithography.
In a ball milling process a powder mixture placed in the ball mill (a cylinder with steel balls
which are rotating at high speeds) is subjected to high-energy collision from the balls. At the
initial stage of ball milling, the powder particles are flattened by the compressive forces due to
the collision of the balls. Micro-forging leads to changes in the shapes of individual particles, or
cluster of particles being impacted repeatedly by the milling balls with high kinetic energy.At
the intermediate stage of the mechanical alloying process, the intimate mixture of the powder
constituents decreases the diffusion distance to the micrometre range. Fracturing and cold
welding are the dominant milling processes at this stage. At the final stage of the mechanical
alloying process, considerable refinement and reduction in particle size is achieved.
Bottom-up approach

This approaches include the miniaturization of materials components (up to atomic level) with
further self assembly process leading to the formation of nanostructures. During self-assembly
the physical forces operating at nanoscale are used to combine basic units into larger stable
structures. Examples- 1. sol-gel processing, 2. chemical vapour deposition (CVD), 3. plasma or
flame spraying synthesis, 4. laser pyrolysis, 5. atomic or molecular condensation – Inert gas
condensation.
1. The sol-gel technique for synthesis of nanomaterials is a wet- chemical technique. Such
techniques are used for the fabrication of materials starting from a chemical solution (sol,
short for solution) which acts as the precursor for an integrated network (or gel) of either
discrete particles or network polymers. Precursors in the form of acetates or carbonates or
nitrates are taken and then dissolved in deionized water. This starting material is used to
produce a colloidal suspension known as gel. After that a gelling agent for example,
polyvinyl alcohol is added and this will produce a gel. A thin film coating is made on a
substrate for example, Ni or Ti sheets and glass. At last the film is annealed at suitable
temperature and then characterized.
2. In a chemical vapour deposition process, vapour is formed in a reaction chamber by
pyrolysis reduction, oxidation or nitridation, and then deposited on the surface. Areas of
growth are controlled by patterning processes like photolithography or photomasking
(deposition patterns are etched on to the surface layers of the wafers).
3. The inert gas condensation (IGC) process is one of the most known and simplest
technique for production of nanoparticles (in particular, Me nanopowders). An inorganic
material is vaporized inside a vacuum chamber into which an inert gas (typically argon
or helium) is periodically admitted. Once the atoms boil off, they quickly lose their energy
by colliding with the inert gas. The vapour cools rapidly and supersaturates to form
nanoparticles with sizes in the range 2–100 nm that collect on a finger cooled by liquid
nitrogen.
4. The production route for 1-D rod-like nanomaterials by liquid phase methods is similar
to that for the production of nanoparticles. CVD methods have been adapted to make 1-
D nanotubes and nanowires. Catalyst nanoparticles are used to promote nucleation.
Nanowires of other materials such as silicon (Si) or germanium (Ge) are grown by
vapour- liquid-solid (VLS) methods.

Classification of nanomaterials
Classification is based on the number of dimensions, which are not confined to the nanoscale range
(<100 nm).
(1) zero-dimensional (0-D),

(2) one-dimensional (1-D),

(3) two-dimensional (2-D), and

(4) three-dimensional (3-D).

 _

Zero dimensional nanomaterials

Materials wherein all the dimensions are measured within the nanoscale (no dimensions, or 0-D,
are larger than 100 nm). The most common representation of zero-dimensional nanomaterials are
nanoparticles and quantum dots or nano-clusters - self-assembled nanoislands and chemically
synthesized nanoparticles

Nanoparticles can be amorphous or crystalline, be single crystalline or polycrystalline, be

composed of single or multi-chemical elements, exhibit various shapes and forms, exist
individually or incorporated in a matrix, be metallic, ceramic, or polymeric.

One-dimensional nanomaterials

One dimension is outside the nanoscale. This leads to needle like-shaped nanomaterials. 1-D
materials include nanotubes, nanorods, and nanowires.
1-D nanomaterials can be amorphous or crystalline, single crystalline or polycrystalline,
chemically pure or impure, standalone materials or embedded in within another medium, be
metallic, ceramic, or polymeric. Typical example— carbon nanotube and silicon nanowires

Two-dimensional nanomaterials

Two of the dimensions are not confined to the nanoscale. 2-D nanomaterials exhibit plate-like
shapes. They include nanofilms, nanolayers, and nanocoatings.
2-D nanomaterials can be amorphous or crystalline, made up of various chemical compositions,
used as a single layer or as multilayer structures, deposited on a substrate, integrated in a
surrounding matrix material, be metallic, ceramic, or polymeric. Typical example—
semiconductor quantum wells.

Three-dimensional nanomaterials

Bulk nanomaterials are materials that are not confined to the nanoscale in any dimension. These
materials are thus characterized by having three arbitrarily dimensions above 100 nm. Materials
possess a nanocrystalline structure or involve the presence of features at the nanoscale. In terms
of nanocrystalline structure, bulk nanomaterials can be composed of a multiple arrangement of
nanosize crystals, most typically in different orientations.
With respect to the presence of features at the nanoscale, 3-D nanomaterials can contain
dispersions of nanoparticles, bundles of nanowires, and nanotubes as well as multinanolayers.

Fullerenes

Fullerene is any molecule in the form of a hollow sphere, ellipsoid or

tubular structure composed entirely of carbon. They are commonly referred to
as “Buckyballs” – named after Buckminster Fuller who designed geodesic
physical structures and buildings based on this geometry. Discovered in 1985
by Smalley, Curl and Kroto., it is the roundest and most symmetrical large
molecule known to man.
Using a laser to vapourise graphite rods in an atmosphere of helium gas, these chemists obtained
cage like molecules composed of 60 carbon atoms joined together by single and double bonds
to form a hollow sphere with 12 pentagonal and 20 hexagonal faces.
The C60 molecule undergoes a wide range of novel chemical reactions. It readily accepts and
donates electrons, a behaviour that suggests applications in batteries and advanced electronic
devices.

Graphene

It is one-atom-thick planar sheet of sp2 -bonded carbon atoms that are densely packed in a
honeycomb (hexagonal) crystal lattice. It can be viewed as an atomic-scale chicken wire made of
carbon atoms and their bonds. The carbon-carbon bond length in graphene is about 0.142 nm.
Graphene is the basic structural element of some carbon allotropes including graphite, carbon
nanotubes and fullerenes. It has the ability to conduct electrons and is transparent. Those qualities
make graphene a tantalizing alternative for use as a transparent conductor, the sort now found in
everything from computer displays and flat panel TVs to ATM touch screens and solar cells.

Carbon nanotubes (CNT) - Graphene is the basic structural

building block of carbon nanotubes. Carbon nanotubes (CNT)
also known as ‘buckytubes’ have a cylindrical
nanostructure in the form of a tube and an engineered CNT typically has a nanoscale thick wall,
geometrically shaped similar to a Buckyball, with a nanoscale diameter, and a length that may
exceed 100 nm. Carbon nanotubes are manufactured as single wall carbon nanotubes (SWCNT)
or multiwall carbon nanotubes (MWCNT). They are synthesized in a variety of ways, including
arc discharge, laser ablation and chemical vapor deposition. With respect to tensile strength,
carbon nanotubes are the strongest and stiffest materials yet discovered, more than 5 times
stronger than Kevlar. Since CNTs have a very low density, their specific strength is 300 times
greater than stainless steel, though under compression CNTs appear to be a lot weaker.
Nanotubes properties

1. Molecular perfection: essentially nearly free of defects

2. Electrical conductivity: probably the best conductor of electricity on a nanoscale level that
can ever be possible
3. Thermal conductivity: comparable to diamond along the tube axis

4. Mechanical: probably the stiffest, strongest, and toughest fiber that can ever exist

5. Chemistry of carbon: can be reacted and manipulated with the richness and flexibility of
other carbon molecules.
6. Self-assembly: strong van der Waals attraction leads to spontaneous roping of many nanotubes.

Quantum dots

Quantum dots, also known as nanocrystals, are another form of nanomaterial and are a specific
type of semiconductor. They are 2-10 nanometers (10-50 atoms) in diameter, and because of their
electrical characteristics, they are [electrically] tunable. The electrical conductivity of
semiconductors can change due to external stimulus such as voltage or exposure to light, etc. As
quantum dots have such a small size they show different properties to bulk material. Hence the
‘tunability’, for example, sensitivity to different wavelengths of light, can be adjusted by the
number of atoms or size of the quantum dot. Quantum dots are typically made from CdSe, ZnS
or CdTe compounds,
Quantum dots (QD) are semiconductor nanostructures that act as artificial atoms by confining
electrons and holes in 3-dimensions. Quantum dots absorb light, then quickly re-emit the light
but in a different colour. They have extremely sharp (delta-function-like) density of the available
energy states and the strong confinement of electron and hole wave functions inside the dots. As
a result, electrons are confined to specific – discrete – energy levels, similar to conditions that
resemble those in an individual atom.
The confinement can be due to electrostatic potentials, (generated by external electrodes, doping,
strain, impurities), the presence of an interface between different semiconductor materials (e.g.
in core-shell nanocrystal systems), the presence of the semiconductor surface (e.g. semiconductor
nanocrystal), or a combination of these.

In fluorescent dye applications, emission frequencies increase as the size of the quantum dot
decreases, resulting in a colour shift from red to blue in the light emitted. Excitation and emission
of the quantum dot are therefore highly tunable. Because the size of the crystals can be controlled
during synthesis, the conductive properties can be carefully controlled.

Main applications: optical and optoelectronic devices, quantum computing, and information
storage. Semiconductors with QDs as Material for Cascade Lasers. Semiconductors with QDs as
Material for IR Photodetectors and Injection Lasers with QDs

Nanoparticles

Nanoparticles (NP) are synthesized or machined. They range in size from 2 nm to 100 nm.
Nanoparticle materials vary depending on their application. Because Nanoparticles are invisible
to the naked eye, they are usually supplied suspended in a liquid. The color is due to the refraction
of light the surface area of the particular nanoparticle reflects. Different sized nanoparticles
exhibit different colours based on its surface area.

Nanofibers and Nanowires

Nanofibers are slightly larger in diameter than the typical nanomaterial definition, though still
invisible to the naked-eye. Their size ranges between 50 nm - 300 nm in diameter and are generally
produced by electro spinning in the case of inorganic nanofibers or catalytic synthesis for carbon
nanotubes. Nanofibers can be electrostatically aligned and biochemically aligned. Similar to
nanofibers are nanowires, though nanowires are considerably smaller in diameter, of the order of 4
nm and conduct electricity.

Electron confinement or Quantum effects

The phenomenon of altering of a material’s electronic properties as it decreases in size is referred

to as the quantum size effect. The overall behavior of bulk crystalline materials changes when
the dimensions are reduced to the nanoscale.
For 0-D nanomaterials, where all the dimensions are at the nanoscale, an electron is confined in
3- D space. No electron delocalization (freedom to move) occurs.
For 1-D nanomaterials, electron confinement occurs in 2-D, whereas delocalization takes place
along the long axis of the nanowire/rod/tube.
In the case of 2-D nanomaterials, the conduction electrons will be confined across the thickness
but delocalized in the plane of the sheet.
The effect of confinement on the resulting
energy states can be calculated by quantum
mechanics, as the “particle in the box”
problem. An electron is considered to exist
inside of an infinitely deep potential well
(region of negative energies), from which it
cannot escape and is confined by the
dimensions of the nanostructure.
The above expressions give the energies in different dimensional nanoparticles. In the expression
h is Planck’s constant, m is the mass of the electron, L is the width (confinement) of the infinitely
deep potential well, and nx, ny and nz are the principal quantum numbers in the three dimensions
x, y, and z. The smaller the dimensions of the nanostructure (smaller L), the wider is the separation
between the energy levels, leading to a spectrum of discreet energies.

Density of states – Energy levels

The density of states is the number of quantum states per unit energy. In other words, the density of
states, denoted by g(E) , indicates how densely packed quantum states in a particular system.
Consider the expression g(E)dE . Integrating the density of the quantum states over a range of energy
will produce
E
a number of states. N (E) g(E)dE . Thus g(E)dE represents the number of states
E
between
E and dE . (In the diagram D(E) dE = g(E)dE) The above diagrams show that as we move to 3D from
0D the energy levels become discrete. The number of quantum states become important in the
determination of optical properties of a material such as a semiconductor (i.e. carbon nanotubes or
quantum dots).
Properties of nanomaterials

1. Surface properties :

When a bulk material is subdivided into materials on the nano scale, the total volume remains
the same but the collective surface area is increased. This results in increase of surface to volume
ratio at nanoscale as compared to bulk materials. The ratio of surface area to volume of a
material is

given by 𝑎𝑟𝑒𝑎 = 4𝜋𝑟2 = 3 . Thus as the radius of a given material is decreased, its surface

to

𝑣𝑜𝑙𝑢𝑚𝑒 4 𝜋𝑟3 𝑟

3
volume ratio increases. This results in more number of atoms or molecules on the surface as
compared to its number inside the volume in a nanomaterial.
The molecules or atoms at the surface of a nanomaterial possess high surface energy and have
high reactivity and have greater tendency to agglomerate. Thus, as the nanomaterials have s
significant proportion of atoms existing at the surface, this has profound effect on reactions that
occur at the surface such as catalysis reactions and detection reactions.
The melting point of nanomaterials are reduced as compared to bulk counterpart due to larger
surface atoms present.

2. Electrical properties :

In bulk metals, the valence and conduction bands overlap, while in metal nanoparticles there is
a gap between these bands. The gap observed in metal nanoparticles can be similar in size to that
seen in semiconductors (< 2 eV) or even insulators (> 2 eV). This results in a metal becoming a
semiconductor. For example, carbon nanotubes can be either conductors or semiconductors
depending on their nano structure. Another example is super capacitors which has effectively no
resistance which disobey ohm’s law.

3. Optical properties :

Nanomaterials, in general have peculiar optical properties as a result of the way light interacts
with their nano structure. In nanosized semiconductors there exists discrete energy states. Thus
bands split and become discrete. Light of only certain wavelengths of certain dimensions are
absorbed. This leads to emission of certain monochromatic wavelengths. Due to quantum
confinement, energy gap increases. Thus more energy is required for absorption. Higher energy
means shorter wavelength of light is emitted resulting in blue Shift. Tuning the nanosize of a
semiconductor means tuning of bandgap leading to light of certain wavelength being emitted.
Thus the same material emits different colours depending on its size.
Scattering of light depends on the size of a particle. By using nanomaterials in sunscreens, the
wavelength of scattered light shifts towards shorter wavelengths and appear transparent instead
of white. Metallic Nanoparticles show changes in colour (gold or silver nano particles) in spectra
due to Surface Plasmons (a group of surface conduction that travel parallel to metal interface).
Due to localization of these electrons, they oscillate leading to resonance when light of suitable
frequency is absorbed them.

4. Magnetic properties
The magnetic properties of a magnet are described by its magnetisation curve (called hysteresis
curve which is the variation of intensity of magnetisation with applied magnetic field). These
curves show the property like whether a magnet can be used as permanent magnet or a
electromagnet etc…. The size of the material can change the property of a magnet by changing
the
magnetisation curves. Thus nanostructuring of bulk magnetic materials leads to changes in the
curves which can produce soft or hard magnets with improved properties.

5. Mechanical properties

Mechanical properties of nanomaterials may reach the theoretical strength, which are one or two
orders of magnitude higher than that of single crystals in the bulk form. The enhancement in
mechanical strength is simply due to the reduced probability of defects. Carbon nanotubes are 100
times stronger than steel but six times lighter.

Applications of nanotechnology in various fields:

Nanotechnology offers an extremely wide range of potential applications from electronics,

optical communications and biological systems to new materials.

Nanomaterials having wide range of applications in the field of electronics, fuel cells, batteries,
agriculture, food industry, and medicines, etc... It is evident that nanomaterials split their
conventional counterparts because of their superior chemical, physical, and mechanical
properties and of their exceptional formability.

1. Fuel cells

A fuel cell is an electrochemical energy conversion device that converts the chemical energy from
fuel (on the anode side) and oxidant (on the cathode side) directly into electricity. The heart of
fuel cell is the electrodes.
Microbial fuel cell is a device in which bacteria consume water-soluble waste such as sugar,
starch and alcohols and produces electricity plus clean water. This technology will make it
possible to generate electricity while treating domestic or industrial wastewater. Microbial fuel
cell can turn different carbohydrates and complex substrates present in wastewaters into a source
of electricity. The efficient electron transfer between the microorganism and the anode of the
microbial fuel cell plays a major role in the performance of the fuel cell. The organic molecules
present in the wastewater possess a certain amount of chemical energy, which is released when
converting them to simpler introduction to Nanomaterials molecules like CO 2 The microbial
fuel cell is thus a device that converts the chemical energy present in water-soluble waste into
electrical energy by the catalytic reaction of microorganisms.
Carbon nanotubes (CNTs) have chemical stability, good mechanical properties and high surface
area, making them ideal for the design of sensors and provide very high surface area due to its
structural network. Since carbon nanotubes are also suitable supports for cell growth, electrodes
of microbial fuel cells can be built using of CNT. Due to three-dimensional architectures and
enlarged electrode surface area for the entry of growth medium, bacteria can grow and proliferate
and get immobilized. Multi walled CNT scaffolds could offer self-supported structure with large
surface area through which hydrogen producing bacteria can eventually grow and proliferate.
2. Catalysis

Higher surface are available with the nanomaterial counterparts, nano-catalysts tend to have
exceptional surface activity. For example, reaction rate at nano-aluminum can go so high, that it
is utilized as a solid-fuel in rocket propulsion, whereas the bulk aluminum is widely used in
utensils. Nano-aluminum becomes highly reactive and supplies the required thrust to send off
pay loads in space. Similarly, catalysts assisting or retarding the reaction rates are dependent on
the surface activity, and can very well be utilized in manipulating the rate-controlling step.

3. Phosphors for High-Definition TV

The resolution of a television, or a monitor, depends greatly on the size of the pixel. These pixels
are essentially made of materials called "phosphors," which glow when struck by a stream of
electrons inside the cathode ray tube (CRT). The resolution improves with a reduction in the size
of the pixel, or the phosphors. Nanocrystalline zinc selenide, zinc sulfide, cadmium sulfide, and
lead telluride synthesized by the sol-gel techniques are candidates for improving the resolution
of monitors.

4. Next-Generation Computer Chips

The microelectronics industry has been emphasizing miniaturization, whereby the circuits, such
as transistors, resistors, and capacitors, are reduced in size. By achieving a significant reduction
in their size, the microprocessors, which contain these components, can run much faster, thereby
enabling computations at far greater speeds.

5. Nanowires for junctionless transistors

Transistors are made so tiny to reduce the size of sub assemblies of electronic systems and make
smaller and smaller devices, but it is difficult to create high-quality junctions. In particular, it is
very difficult to change the doping concentration of a material over distances shorter than about 10
nm. Researchers have succeeded in making the junctionless transistor having nearly ideal electrical
properties. It could potentially operate faster and use less power than any conventional transistor
on the market today.
The device consists of a silicon nanowire in which current flow is perfectly controlled by a silicon
gate that is separated from the nanowire by a thin insulating layer. The entire silicon nanowire is
heavily n-doped, making it an excellent conductor. However, the gate is p-doped and its presence
has the effect of depleting the number of electrons in the region of the nanowire under the gate.
The device also has near-ideal electrical properties and behaves like the most perfect of transistors
without suffering from current leakage like conventional devices and operates faster and using
less energy.

6. Elimination of Pollutants
Nanomaterials possess extremely large grain boundaries relative to their grain size. Hence, they
are very active in terms of their chemical, physical, and mechanical properties. Due to their
enhanced chemical activity, nanomaterials can be used as catalysts to react with such noxious
and toxic gases as carbon monoxide and nitrogen oxide in automobile catalytic converters and
power generation equipment to prevent environmental pollution arising from burning gasoline
and coal.

7. Sun-screen lotion

Prolonged UV exposure causes skin-burns and cancer. Sun-screen lotions containing nano-TiO2
provide enhanced sun protection factor (SPF) while eliminating stickiness. The added advantage
of nano skin blocks (ZnO and TiO2) arises as they protect the skin by sitting onto it rather than
penetrating into the skin. Thus they block UV radiation effectively for prolonged duration.
Additionally, they are transparent, thus retain natural skin colour while working better than
conventional skin-lotions.

8. Sensors

Sensors rely on the highly active surface to initiate a response with minute change in the
concentration of the species to be detected. Engineered monolayers (few Angstroms thick) on the
sensor surface are exposed to the environment and the peculiar functionality (such as change in
potential as the CO/anthrax level is detected) is utilized in sensing.