NANOTECHNOLOGY

INTRODUCTION

 THE WORD NANO IS DERIVED FROM A GREEK WORD

MEANING EXTREMELY SMALL.
 1nm=10-19 m
 The term nanotechnology was first given by Norio
Taniguchi in 1974
WHY NANOTECHNOLOGY?
 With nanotechnology it is possible to control matter on every
important length scale. It enables design of materials. The
developments in nanotechnology can affect domains such as:
 (1) Materials: new materials which are harder, more durable and
resistant, lighter and less expensive can be produced.
 (ii) Electronics: electronic components will become smaller and
smaller, allowing the design of more powerful computers
 (iii) Energy: a vast increase in the potential of solar energy
generation.
 (iv) Health and biotechnology: great expectations are held in the
areas of prevention, diagnostics and treatment.
 QUANTUM CONFINEMENT
 A quantum confinement phenomenon occurs when electron
wave functions are constrained by the physical dimensions
of nanoparticles, leading to discrete energy levels.
 Quantum confinement comes when electrons and holes in a
material are confined to a potential well.
 (a) Quantum dot is a small sphere where all three
dimensions of nanoparticles confines exciton Bohr radius.
It is a zero-dimensional potential well.
 (b) Quantum wire is a structure where height and both
breadth are small and length is long. It is a one-
dimensional potential well.
 (c) Quantum well is a structure where height is about the
Bohr exciton and breadth and length are long. It is a two-
dimensional potential well.
SURFACE TO VOLUME RATIO
 Nanomaterials have a relatively larger surface
area when compared to the same mass of
material produced in a larger form.
 This can make nanomaterials more chemically
reactive and affect their strength or electrical
properties.
 In nanomaterials, many atoms, more than half,
will be near interfaces.
 Surface properties such as energy levels,
electronic structure, and reactivity can be quite
different from interior states, and give rise to
quite different material properties
SURFACE TO VOLUME RATIO

 As a particle decreases in size, a greater proportion of atoms are

found at the surface compared to those inside.
 For example, a particle of size 30 nm has 5% of its atoms on its
surface, at 10 nm 20% of its atoms, and at 3 nm 50% of its atoms.
 Thus, nanoparticles have a much greater surface area per unit mass
compared with larger particles.
 As growth and catalytic chemical reactions occur at surfaces, this
means that a given mass of material in nanoparticulate form will be
much more reactive than the same mass of material made up of
larger particles.
BOTTOM-UP METHOD

 Bottom-up method is a technique in which materials and devices are

built up atom by atom.
 Bottom-up manufacturing would provide components made of single
molecules which are held together by covalent forces.
 Furthermore, the amount of information that could be stored in
devices build from the bottom-up approach would be enormous.
SOL-GEL PROCESS
 This process is widely employed to prepare oxide materials. It can be understood a sSol-gel
= Sol (a colloidal solution made of solid particles few hundred nm in diameter, suspended in
a liquid phase) + Gel (a solid macromolecule immersed in a solvent)
 Step i - Preparation of stable solution: A stable solution of the alkoxide or solvated metal
precursor (raw material) is formed.
 Step ii - Formation of gel: An oxide (M-OH-M) or alcohol bridged (network) gel forms by a
polycondensation or polyesterification reaction that leads to increase in the viscosity of the
solution.
 Step iii - Aging of gel: The polycondensation reactions continue until the gel becomes a solid
mass along with contraction of the gel network and expulsion of solvent from gel pores.
 Step iv - Drying of the gel: Water and other volatile liquids are removed from the gel
network by drying. If the solvent such as water is extracted under super critical or near
super critical conditions, the product is an aerogel. If isolated by thermal evaporation the
resulting product is termed a xerogel.
 Step v - Dehydration: By drying, M-OH groups are removed and gel stabilizes. Heating the
xerogel at temperatures up to 800°C gel gets stabilized.
SOL-GEL PROCESS
SOL-GEL PROCESS
 (i) Disadvantages:
a) Controlling the growth of the particles is very difficult.
b) Stopping the newly formed particles from agglomeration is difficult.
 ii) Advantages: Sol-Gel synthesis is superior of all the available processes as it canproduce
(a) thin bond-coating to provide excellent adhesion between the metallic substrate and the top
coat.
(b) thick coating to provide corrosion protection.
(c) shape materials into complex geometries in a gel state.
(d) high purity products.(e) a simple, economic and effective method to produce high quality
coatings.
 (iii) Applications
(a) It can be used in ceramics manufacturing processes for producing very thin films of
metal oxides.
(b) Sol-Gel derived materials have diverse applications in optics, electronics, energy, space,
bio-sensors, medicine (e.g. controlled drug release) and separation technology (e.g.
chromatography).
(c) Used to carry out zeolite synthesis
PRECIPITATION SYNTHESIS METHOD
 The precipitation technique involves the precipitation of metal in the
form of hydroxide from a salt precursor with the help of a base in a
solvent.
 It is suitable for the synthesis of magnetic nanoparticles which have
many uses such as tumor and cancer diagnosis, magnetic resonance
imaging for diagnosis and treatment and magnetic drug target (the
specific delivery of cancer drugs to their desired targets).
 Principle: Two or more chemicals are mixed to react each other. The
product will settle down as precipitate.
PRECIPITATION SYNTHESIS METHOD
 Experimental method: An example of copper oxide
nanoparticles synthesis is used to explain a general
concept of precipitation. This method involves the
precipitation of nano particles within continuous fluid
solvent.
 (a) 55g of copper sulphate pentahydrate (CuSO,5H,O) is
mixed with 25g of hydroxyl ammonium chloride (NH,OH
HCI) in 125 ml of distilled water.
 (b) The mixture is cooled in a cold-water bath with
constant swirling.
 (c) A solution containing 40g of sodium hydroxide in 750
ml of distilled water is added to the mixture.
 (d) The precipitate is settled down and the supernatant
liquid poured off.2CuSO, + 2NH,OH HCI + 6NaOH → CO, +
N2 + 2NaSO, + 7H,0 + 2NaCI(by-products)
 (e) The precipitate is washed several times with distilled
water until it is chloride free.
 (f) The precipitate is dried at 200°C - 250°C.(g) When the
precipitate is heated to 300°C in open air, CuO nano-
particles are formed.Сио -→ CuO
PRECIPITATION SYNTHESIS METHOD

 Advantages: The advantages are

 (a) It is a simple, low cost and rapid method for preparation of
nanoparticles.
 (b) In precipitation method reaction temperature is low.
 (c) This method gives fine and uniform size particles
COMBUSTION METHOD
 Combustion is a chemical process in which a substance reacts rapidly
with oxygen and gives off heat. The original substance is called the fuel,
and the source of oxygen is called the oxidizer. The combustion synthesis
method is useful for the synthesis of a variety of nanoscale materials,
such as oxides, metals, alloys, and sulfides. Combustion method is a low
temperature (approximately 500°C, generally metal oxides in traditional
method needs a temperature of above 2000°C), time saving (it
completes in less than 10 minutes), energy efficient method.
COMBUSTION METHOD
 Procedure: It has following steps.
(a) The uniformly mixed solution of all the reactants is kept in a furnace maintained
at 500 degrees
(b) The solution undergoes evaporation and concentrated, uniformly mixed viscous-
gel typesubstance is obtained.
(c) After some time, the viscous-gel catches fire and propagates spontaneously in
the redox mixture in the form of either a flame type or smoldering type.
(d) This combustion lasts for about 1 to 2 minutes.
(e) During the propagation a large quantity of gases and high temperature are
produced, and it results in the formation of nano metal oxide.
 Advantages:
(a) time and energy efficiency.
(b) the equipment is simple, and the raw materials are usually less expensive.
(c) a molecular level mixing for the raw materials.
(d) the composition of products can be tuned.
COMBUSTION METHOD

 Applications:
(a) SCS is used to fabricate various materials for many applications of
catalysis, luminescent materials, fuel cells, energy conversion, and
energy storage.
(b) Complicated garnets (a brittle and more or less transparent usually
red silicate mineral)are also widely synthesized by SCS.
(c) It is also applied to synthesize thin films of metal oxides.
 TOP DOWN FABRICATION- BALL MILLING
 Top-down fabrication involves removing existing material
from larger entities to fabricate devices. In top-down
manufacturing, parts are constructed by cutting,
carving, and molding.

 High energy ball milling is a top-down approach

technique. Coarse grained materials are crushed
mechanically in rotating drums by hard steel and
tungsten carbide balls. Powder samples are reduced to
nanometer range by mechanical deformation produced
by ball milling process.

 Disadvantages: (a) Though the process is simple, but all

the particles are not broken down to the required
particle size.
(b) During mechanical attrition, contamination by the
milling tools (Fe) and atmosphere (trace elements of
Oxygen, Nitrogen in rare gases) can be a problem.
 Advantages:(a) The main advantage of this top-down
approach is high production rates of nano-powders.
PHYSICAL VAPOUR DEPOSITION
(PVD)
 Physical vapour deposition is a vaporization
coating technique where the raw materials
(precursors) are in solid form.
 (i) Steps: It has following steps
(a) Evaporation: Material to be deposited as
coating is taken in the form of target and is
bombarded by a high energy source (such as a
beam of electrons or ions or heating by a
filament) in a vacuum chamber. The source
material gets heated and starts to boil
and then evaporate.
(b) Transport: In transportation vaporized atoms
from the target material move to the substrate
to be coated.
(c) Reaction: The transported atoms react with
appropriate gas in transportation stage.
(d) Deposition: Here coating builds up on the
substrate surface.
PHYSICAL VAPOUR DEPOSITION
(PVD)
 Advantages:
(a) Almost any type of inorganic and organic material can be used
(b) The Process is more environmental friendly than processes such as
electroplating

 Disadvantages:
a) Extremely difficult to coat undercuts and similar surface features.
b) High capital cost is required.
c) Operates at high vacuums and temperatures.
d) PVD requires skilled operators.
e) The rate of coating deposition is usually quite slow.
CHEMICAL VAPOUR DEPOSITION (CVD)

 Chemical Vapor Deposition is a well known process in which a solid is

deposited on a heated surface by a chemical reaction from a vapour or
gas phase. CVD is mostly useful in micro-fabrication processes such as
monocrystalline, polycrystalline, amorphous and epitaxial. These
materials include silicon, fibre,carbon nanofibres, carbon nanotubes, SiO2
and synthetic diamonds.
CHARACTERIZATION TECHNIQUES

 The structure, morphology and properties of nanoparticles are

characterized by Transmission Electron Microscope (TEM), Scanning
Electron Microscope (SEM) and X Ray Diffraction (XRD).
TRANSMISSION ELECTRON
MICROSCOPE (TEM)
 The transmission electron microscope is an extremely useful tool for material
character-ization. The resolution of TEM is about 0.2 nm, which is about 1000x
better than ordinary light microscope. The first TEM was developed in 1933 by Max
Knoll and Ernst Rukasa and the first commercial TEM in 1939. In 1986, Ruska was
awarded the Nobel Prize in Physics for the development of transmission electron
microscopy. TEM can be used to study the growth of layers and to analyze the
quality, shape, size and density of quantum wells, wires and dots. The TEM operates
on the same basic principles as the light microscope but uses electrons instead of
light. Because the wavelength of electrons is much smaller than that of light, the
resolution much better than that from a light microscope.
 (i) Principle: A beam of high velocity electrons accelerated under vacuum, focused
by condenser lens (electromagnetic bending of electron beam) onto specimen and
emergent electron beam is focused by objective lens. Final image forms on a
fluorescent screen or camera for the image viewing.
 ii) Components: The major components are vacuum system, specimen stage,
electron gun, electron lens and computer. The acceleration voltages, 120 to 200 kV
determines the velocity, wavelength and hence the resolution of the microscope.
TRANSMISSION ELECTRON
MICROSCOPE (TEM)
 (i) TEM Applications:
(a) Transmission Electron Microscope is ideal for
life sciences, nanotechnology, medical,
biological and material research, forensic
analysis, gemology and metallurgy, industry
and education.
(b) TEMs provide topographical (accurate
representation of the physical features of an
area, morphological (structure of things),
compositional and crystalline information.
(c) The images allow researchers to view
samples on a molecular level, making it
possible to analyze structure and texture.
(d) Useful in the study of crystals and metals,
but also has industrial applications.
(e) TEMs can be used in semiconductor analysis
and production and the manufacturing of
computer and silicon chips.
SCANNING ELECTRON MICROSCOPE
(SEM)
 In scanning electron microscope (SEM) electrons are used to form an
image for a resolution better than 1 nanometer. SEM is useful because of
its higher magnification, larger depth of field, greater resolution and
compositional and crystallographic information it gives.
 (i) Principle: In a scanning electron microscope, the specimen is exposed
to a narrow electron beam from an electron gun, which rapidly moves
over or scans the surface of the specimen. This causes the release of a
shower of secondary electrons and other types (backscattered electrons,
diffracted backscattered electrons, photons) of radiations from the
specimen surface. Due to the very narrow electron beam, SEM
micrographs have a large depth of field giving structure of a sample.
 (ii) Components: Electron Source, Electron Lenses, Sample Stage,
Detectors for all signals of interest, Display / Data output devices.
SCANNING ELECTRON MICROSCOPE
(SEM)
 (iii) Scanning process: The electron beam,
which typically has an energy ranging from
0.2 keV to 40 keV, is focused by one or two
condenser lenses to a spot about 0.4 nm to
5 nm in diameter. The beam passes through
pairs of deflector so that it scans in a
rectangular pattern of image of the sample
surface. When the primary electron beam
interacts with the sample, the energy
exchange happens between the electron
beam and the sample. This results in the
reflection of high-energy electrons,
secondary electrons and EM radiation.
Images may be captured a high-resolution
cathode ray tube, but in modern machines
they are digitized and saved.
ANALYSIS OF NANO MATERIALS BY X-
RAY DIFFRACTION
 X-ray diffraction (XRD) is a powerful method for the study of nanomaterials. The wavelength of
X-rays is on the atomic scale, so X-ray diffraction (XRD) is a primary tool for probing structure
of nano-materials. The intensities measured with XRD can provide quantitative, accurate
information on the atomic arrangements at interfaces. X-ray diffractograms of nanomaterials
provide a wealth of information from phase composition to crystallite size, from lattice strain to
crystallographic orientation.
 (i) Experimental Arrangements: In powder or polycrystalline diffraction it is important to have a
sample with a smooth plane surface. A typical powder XRD instrumentation consist of four main
components such as X-ray source, specimen stage, receiving optics and X-ray detector.
 (ii) Analysis: XRD analysis is based on Bragg's law and Bragg's angle. When a beam of X-rays is
incident on the sample, X-rays are scattered by each atom in the sample. If the scattered
beams are in phase, they interfere constructively and give maximum intensity.
 Applications: The most traditional use of XRD is: (a) Identification: Phase identification,
investigation of high/low temperature phases, solid solutions and determinations of unit cell
parameters of new materials.(c) Texture analysis: The determination of the preferred
orientation of the crystallites in polycrystalline aggregates is referred to as texture analysis.
(d) Advantages: It is a powerful and rapid technique for identification of an unknown material.
In most cases, it provides an unambiguous phase determination. It requires minimal sample
preparation. XRD units are widely available. The Data interpretation is relatively
straight forward.