NANO TECHNOLOGY

UNIT 2
CARBON NANOTUBES
Carbon nanotubes (CNTs) are allotropes of carbon.

These cylindrical carbon molecules have interesting properties that make them potentially
useful in many applications in nanotechnology, electronics, optics and other fields of
materials science, as well as potential uses in architectural fields. They exhibit extraordinary
strength and unique electrical properties, and are efficient conductors of heat. Their final
usage, however, may be limited by their potential toxicity.

There are two distinct families of carbon nanotubes, MWCNTs and SWCNTs.

SWCNT is a single, seamless, wrapped graphene sheet which has the form of hexagonal
aromatic ring patterns. It can be rolled up in many different ways.

The structure of SWCNT can be classified into three basic types:

(a) armchair (b) zigzag (c) chiral (d) MWCNTs consist of coaxial SWCNT

FABRICATION:

 Arc Discharge
 Laser Ablation
 Chemical Vapor Deposition (CVD)
 Ball Milling

ARC DISCHARGE

A potential (~18V) is applied across two electrodes, which are usually carbon rods of few
millimeters in diameter, separated by a certain distance (~1mm) in helium.

A high current discharge (~100A) passes through the opposing carbon anode and cathode,
where plasma is generated, and carbon atoms are evaporated onto the electrodes.

Without catalysts, CNTs are formed as MWCNTs.

To produce SWCNTs, a small amount of transition metal (usually iron, cobalt or nickel) is
incorporated as a catalyst in the central region of the anode.

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Advantage:

 Simple procedure
 High quality product
 Inexpensive
Disadvantage:
 Requires further purification
 Tubes tend to be short with random sizes

LASER ABLIATION (FIG.2)

A quartz tube containing inert gas and a graphite target with the catalyst is plased in a furnace
and maintained at 12000C.

A water cooled copper collector is partially contained in the tube.

An intense pulsed laser beam is incident on the target, evaporating carbon from the graphite.

The inert gas, such as argon, then sweeps the carbon atoms from the high-temperature zone
onto the colder copper collector where they condense into nanotubes.

MWCNTs with 5-20nm in diameter and tens to hundreds of micrometers in length haven
made by this method.

Advantage:
 Good diameter control
 Few defects
 Pure product

Disadvantage:
 Expensive because of lasers and high powered equipment

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CHEMICAL VAPOUR DECOMPOSITION

Catalytic chemical vapor deposition (CCVD) processes are simple and low cost.
For this method, substrates with catalysts are placed in the tube furnace and heated up to 500
to 1000ºC.
At this temperature, a continuous flow of hydrocarbon gas (mainly CH4, C2H2, C2H4 or
C6H6, usually as a mixture with either H2 or an inert gas such as Ar and N2) is then
introduced over a period of time.
The catalyst decomposes the hydrocarbon, releasing hydrogen and carbon, which is free to
form nanotubes.

Advantage:
 Easy to increase scale to industrial production
 Large length
 Simple to perform
 Pure product

Disadvantage:
 Defects are common

PROPERTIES:
Electrical properties:If the nanotube structure is armchair then the electrical properties are
metallic.If the nanotube structure is chiral then the electrical properties can be either
semiconducting with a very small band gap, otherwise the nanotube is a moderate
semiconductorIn theory, metallic nanotubes can carry an electrical current density of 4×109
A/cm2 which is more than 1,000 times greater than metals such as copper
Thermal properties: All nanotubes are expected to be very good thermal conductors along
the tube, but good insulators laterally to the tube axis. It is predicted that carbon nanotubes
will be able to transmit up to 6000 watts per meter per Kelvin at room temperature; compare
this to copper, a metal well-known for its good thermal conductivity, which transmits 385
watts per meter per K. The temperature stability of carbon nanotubes is estimated to be up to
2800oC in vacuum and about 750oC in air.
Strength properties:Carbon nanotubes have the strongest tensile strength of any material
known.It also has the highest modulus of elasticity.young’s modulus is the measure of how
stiff or flexible a material is.Tensile strength is a measure of the amount of stress needed to
pull amaterial part.The tensile strength of the CNT is about 45billion pascals.CNT are about
20 times stronger than steel. Young modulus of CNT ranges from 1.28 to 1.8 TPa, 10 times
greater than steel.

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METAL NANOCLUSTERS
Metal Nano clusters have physical properties differing significantly from their bulk counterparts.
Metallic properties such as delocalization of electrons in bulk metals which imbue them with high
electrical and thermal conductivity, light reflectivity and mechanical ductility may be wholly or
partially absent in metal Nano clusters, while new properties develop.
Physical properties of material can be characterized by some critical length, a thermal
diffusion length, or a scattering length. Perhaps a working definition of a an aggregate of
atoms between 1 and 100 nm viewed as a subdivision of a bulk material, and of dimension
less than the characteristic length of some phenomena.
Cluster formation: A device is used to form cluster of metal atoms.
A high- intensity laser beam is incident on a metal rod, causing evaporation of atoms from
the surface of the metal.
The atoms are then swept away by a burst of helium and passed through an orifice into a
vacuum where the expansion of the gas causes cooling and formation of clusters of the metal
atoms. These clusters are then ionized by UV radiation and passed into a mass spectrometer
that measures theirmass : charge ratio.

Fig. shows the mass spectrum data of lead clusters formed (fig.2)
The data show that clusters of 7 and 10 atoms are more likely than other clusters, which
means that these clusters are more stable than clusters of other sizes.
(fig. 3) This is a plot of the ionization potential of atoms number Z, which is the number of
electrons in the atom. The ionization potential is the energy necessary to remove the outer
electron from the atom. The maximum ionization potentials occur for the rare-gas atoms 2He,
Ne,and 18 Ar because their outermost s and p orbitals are filled. More energy is required to
remove electrons from filled orbitals than from unfilled orbitals.
Below fig. shows the ionisation potential of sodium clusters as a function of the number of
atoms in a cluster.Peaks are observed at clusters having two and eight atoms. These numbers
are referred to as electronic magic numbers. Their existence suggests that clusters can be
viewed as superatoms, and this result motivated the development of the jellium model of
clusters.

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RARE GAS AND MOLECULER CLUSTER

Nanoparticles assembled from rare gases such as krypton and xenon, and molecules such as
water are called rare gas cluster.
Xenon clusters are formed by adiabatic expansion of a supersonic jet of the gas through a
small capillary into a vacuum. The gas is then collected by a mass spectrometer, where it is
ionized by an electron beam, and its mass : charge ratio measured.
The forces that bond inert gas atoms into clusters are weak and thus they possess
instantaneous electric dipole movement P1 because of the movement of electrons about the
atoms.
An electric dipole moment occurs when a positive charge and a negative charge are separated
by some distance. This dipole produces an electric field 2𝑃1/𝑅 3 at another atom a distance R
away. This, in turn, induces a dipole moment, P2, on the second atom, 2𝛼𝑃1/𝑅 3 , where α. is
called the
electronic polarizability. Thus two inert-gas atoms will have an attractive potential

This is known as the Van der Waals potential and it is effective at relatively large
separations of the atoms. As the two atoms get much closer together, there will be repulsion
between the electronic cores of each atom. Thus the overall potential between two inert two
inert gas atoms has the form

This is known as Lennard-Jones potential, and it is used to calculate the structure of

inert gas clusters.

Molecular cluster:
Individual molecules can form clusters. One of the most common examples of this is the
water molecule. The H atom of one molecule forms a bond with the oxygen atom of another.
At ambient conditions 80% of water molecules are bonded into clusters and as the
temperature is raised, the clusters dissociate into isolated H2O molecules. There are other
examples of molecular clusters such as (NH3)" +, (CO2)44 and (C4H8)30.

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METHODS OF SYNTHESIS
Challenges for nanomaterial synthesis
 Overcome the huge surface energy, a result of enormous surface area or large surface
to volume ratio.
 Ensure all nanomaterials with desired size, uniform size distribution, morphology,
crystallinity, chemical composition, and microstructure, that altogether result in
desired physical properties.
 Prevent nanomaterials and nanostructures from coarsening through either Ostwald
ripening or agglomeration as time evolutes.

Synthesis methods:

Top Down Approach

Top down method for manufacturing involves the construction of parts through methods such
as cutting, carving and molding.
Using these methods, we have been able to fabricate a remarkable variety of machinery and
electronics devices.
However, the sizes at which we can make these devices are severely limited by our ability to
cut, carve and mold.
Milling, Nano-lithography, hydrothermal technique (for some materials), laser ablation,
physical vapor deposition, electrochemical method (electroplating) uses top down approach
for nano-scale material manufacturing.

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Advantages:
• Mechanical force is used in making nanosized particles
• This method is used to produce nano-sized particles on large scale
Disadvantages:
• Polydispersity, formation of variable nano-sized particles
• Surface dislocations occur during attrition/silicing/ball milling
• During synthesis, crystallographic damage occurs to the processed patterns.
Sometimes, aggregates or cluster formed
• Morphology control of NPs is difficult
Bottom Up Approach
Bottom up approach refers to the buildup of a material from the bottom: atom by atom,
molecule by molecule or cluster by cluster. Though the bottom up approach often referred in
nanotechnology, it is not a newer concept. All the living beings in nature observe growth by
this approach only and also it has been in industrial use for over a century.
Advantages:
• Bottom up approach produces nano structures with less defects, more homogeneous
chemical composition.
• Size and shape of NPs can be controlled
• Good quality NPs can be prepared for applications in functional devices

RF PLASMA METHOD
RF Plasma is a method of nanoparticle synthesis that utilizes a plasma generated by RF
heating coils. The starting metal is contained in a pestle in an evacuated chamber. The metal
is heated· above its evaporation point using high voltage RF coils wrapped around the
evacuated system in the vicinity of the pestle. Helium gas is then, allowed to enter the
system, forming a high temperature plasma in the region of the coils. The metal vapor
nucleates on the He gas atoms. and diffuses up to a colder collector rod where nanoparticles
are formed. The particles are generally passivated by the introduction of some gas such as
oxygen. In the case of aluminum nanoparticles the oxygen forms a layer of aluminum oxide
about the particle.

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THERMOLYSIS

Nanoparticles can be made by decomposing solids at high temperature having metal cations,
and molecular anions or metal organic compounds. The process is called thermolysis. For
example, small lithium particles can be made by decomposing lithium azide, LiN3. The
material is placed in an evacuated quartz tube and heated to 400°C in the apparatus shown in
Fig. At about 370°C the LiN3 decomposes, releasing N2 gas, which is observed by an
increase in the pressure on the vacuum gauge. In a few minutes the pressure drops back to its
original low value, indicating that all the N2 has been removed. The remaining lithium atoms
coalesce to form small colloidal metal particles. Particles less than 5 nm can be made by this
method.Passivation can be achieved by introducing an appropriate gas.
The presence of these nanoparticles can be detected by electron paramagnetic resonance
(EPR) of the conduction electrons of the metal particles. Electron paramagnetic resonance,
measures
the energy absorbed when electromagnetic radiation such as microwaves induces. A
transition between the spin states ms split by a DC magnetic field. Generally the experiment
measures the derivative of the absorption as a function of an increasing DC magnetic field.
Normally because of the low· penetration depth of the microwaves into a metal, it is not
possible to observe the EPR of the conduction electron.

PULSED LASER METHOD

Pulsed lasers have been used in the synthesis of nanoparticles of silver. Silver nitrate solution
and a reducing agent are flowed through a blender like device. In the blender there is a solid
disk, which rotates in the solution. The solid disk is subjected to pulses from a laser beam
creating hot spots on the surface of the disk. The apparatus is illustrated in Fig.. Silver nitrate
and the reducing agent reacts at these spots, resulting in the formation of small silver
particles, which can be separated from the solution using a centrifuge. The size of the
particles is controlled by the energy of the laser and the rotation speed of the disk. This
method is capable of a high rate of production of 2-3 g/min.

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CHEMICAL METHOD
Probably the most useful methods of synthesis in terms of their potential are to be scaled up
are chemical methods. There are a number of different chemical methods that can be used to
make nanoparticles of metals. Several types of reducing agents can be used to produce
nanoparticles such as LiBEt3H, and NaBl4 where Et denotes the ethyl (·C2H5) radical.
For example nanoparticles of molybdenum (Mo) can be reduced in toluene solution with
NaBEt3H at room temperature, providing a high yield of Mo nanoparticles .dimensions of 1-
5 nm. The equation for the reaction is

Nanoparticles of aluminumbave been made by decomposing Me2EtNAlH3 in toluene and

heating the solution to 105°C for 2 h (Me is methyl, ·CH3). Titanium isoproxide is added to
the solution. The titanium acts as a catalyst for the reaction .The choice of catalyst determines
the size of the particles produced. For instance 80 nm particles have been made using
titanium. A surfactant such as oleic acid can be added to the solution to coat the particles and
prevent aggregation.

Advantages:
 The primary advantage of chemical processing is its versatility in designing and
synthesizing new materials that can be refined into the final end products.
 The secondary most advantage that the chemical processes offer over physical
methods is good chemical homogeneity, as a chemical method offers mixing at the
molecular level.
Disadvantage:
 Chemical methods frequently involve toxic reagents and solvents for the synthesis of
nanostructured materials.
 Chemical methods is the unavoidable introduction of byproducts, which require
subsequent purification steps after the synthesis in other words, this process is time
consuming.

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SOL GEL METHOD

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

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

Step 2: Gelation resulting from the formation of an oxide- or alcohol- bridged network (the
gel) by a polycondensation or polyesterification reaction that results in a dramatic increase in
the viscocity of the solution.

Step 3: Aging of the gel (Syneresis), during which the polycondensation reactions continue
until the gel transforms into a solid mass, accompanied by contraction of the gel network and
expulsion of solvent from gel pores. Ostwald ripening (also referred to as coarsening, is the
phenomenon by which smaller particles are consumed by larger particles during the growth
process) and phase transformations may occur concurrently with syneresis. The aging process
of gels can exceed 7 days and is critical to the prevention of cracks in gels that have been
cast.

Step 4: Drying of the gel, when water and other volatile liquids are removed from the gel
network. This process is complicated due to fundamental changes in the structure of the gel.
The drying process has itself been broken into four distinct steps: (i) the constant rate period,
(ii) the critical point, (iii) the falling rate period, (iv)the second falling rate period.

If isolated by thermal evaporation, the resulting monolith is termed a xerogel. If the solvent
(such as water) is extracted under supercritical or near super critical conditions, the product is
an aerogel.

Step 5: Dehydration, during which surface- bound M-OH groups are removed, there by
stabilizing the gel against rehydration. This is normally achieved by calcining the monolith at
temperatures up to 8000C.

Step 6: Densification and decomposition of the gels at high temperatures (T>8000C). The
pores of the gel network are collapsed, and remaining organic

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CARBON MOLECULE

Carbon is not really a ceramic, but one of its allotropic form, diamond may be considered as a
ceramic.

Diamond has very interesting and even unusual properties such as:
 -possesses diamond-cubic structure (like Si, Ge)
 -consists covalent C-C bonds
 -having highest hardness of any material known
 -very high thermal conductivity (unlike ceramics)
 -transparent in the visible and infrared, with high index of refraction
 -semiconductor (can be doped to make electronic devices)
 -meta-stable (transforms to carbon when heated)

Synthetic diamonds are made by application of high temperatures and pressures or by

chemical vapor deposition. Future applications of this latter, cheaper production method
include hard coatings for metal tools, ultra-low friction coatings for space applications, and
microelectronics.

Graphite, another allotropic form of carbon, has a layered structure with very strong
hexagonal bonding within the planar layers (using 3 of the 3 bonding electrons) and weak,
van der Waals bonding between layers using the fourth electron. This leads to easy inter-
planar cleavage and applications as a lubricant and for writing (pencils). Graphite is a good
electrical conductor and chemically stableeven at high temperatures. Applications include
furnaces, rocket nozzles, electrodes in batteries, etc.

Recently (1985) discovered allotropic form of carbon is the C60 molecule, also known as
fullereneor bucky-ball(after the architect Buckminster Fuller who designed the geodesic
structure that C60 resembles.). Structure of this form resembles a hallow spherical cluster of
60 atoms, and is found to consist of 20 hexagons and 12 pentagons where no two pentagons
share a common edge. Fullerenes and related structures like nanotubes are exceptionally stiff,
strong, and ductile. Future applications of fullerenes are as a structural material and possibly
in microelectronics, due to the unusual properties that result when fullerenes are doped with
other atoms.

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CARBON CLUSTER (C60)

C60 is the third major form of pure carbon; graphite and diamond are the other two.
Buckyballs were discovered in 1985 - the product of an experiment on carbon molecules in
space. In C60, hexagons and pentagons of carbon link together in a coordinated fashion to
form a hollow, geodesic dome with bonding strains equdistributed among 60 carbon atoms.

Buckminsterfullerene or "buckyballs"--named for the American architect R. Buckminster

Fuller, whose geodesic domes had a similar structure--is the roundest, most symmetrical large
molecule known. It is exceedingly rugged and very stable, capable of surviving the
temperature extremes of outer space.

Evidence experiment for a C60 molecule:

In this experiment a graphite disk is heated by a high-intensity laser beam that produces a hot
vapor of carbon. A burst of helium gas then sweeps the vapour out through an opening where
the beam expands. The expansion cools the atoms and they condense into clusters. This
cooled cluster beam is then narrowed by a skimmer and fed into a mass spectrometer, which'
is a device designed to measure the mass of molecules in the clusters. When 'the experiment
was done using a- graphite disk, the mass spectrometer, yielded an unexpected result. A mass
number of 720 that would consist of 60 carbon atoms, each of mass 12, was observed.
Evidence for ' a C60 molecule had been found!
Structure:

1t has 12 pentagonal (5 sided)and 20 hexagonal (6 sided) faces symmetrically arrayed to form

a molecular ball. In fact a soccer ball has the same geometric configuration as fullerene.
These ball-like molecules bind with each other in the solid state to form a crystal lattice
having a face centered cubic structure .In the lattice each C60 molecule is separated from its
nearest neighbor by 1 nm (the distance between their Centers is 1 nm), and they are held
together by weak forces called van der Waals forces.

Because C60 is soluble in benzene, single crystals of it can be grown by evaporation from
benzene solutions.

Alkali-Doped

In the face-centered cubic fullerene, structure, 26% of the volume of the unit cell is empty, so
alkali atoms can fit into the empty spaces between the molecular balls of the material. When
C60 crystals and potassium metal are placed in evacuated, tubes and heated to 400°C,
potassium vapor diffuses, into the empty spaces to form the compound K3C60. When C60 is
doped with potassium to form K3C6Q, the potassium atoms become ionized to form K+ and
their electrons become associated with the C60, which becomes a C603- triply negative ion.
Thus each C60 has three extra electrons that are loosely bonded to the C60 and can move
through the lattice making C60 electrically conducting. In this case the C60 is said to be
electron-doped.

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SOLID DISORDERS NANOSTRUCTURES

Bulk nanostructured materials are solids having a nanosized microstructure.
The nanoparticles can be disordered with respect to each other, where their symmetry axes
are randomly oriented and their spatial positions display no symmetry.
The particles can also be ordered in lattice arrays displaying symmetry.
Example

Solid Disordered Nanostructured

Methods of Synthesis:

(compaction and consolidation)

Nanostructured Cu-Fe alloy

 Mixtures of iron and copper powders having the composition Fe85Cu15 are ball
milled for 15 h at room temperature.
 The material is then compacted using a tungsten-carbide die at a pressure of 1 GPa for
24 h.
 This compact is then subjected to hot compaction for 30 min at temperatures in the
vicinity of 400°C and pressure upto 870 Mpa.
 The final density of the compact is 99.2% of the maximum possible density.

Stress- Strain Curve

 The deviation from linearity in the stress-strain curve shows there is a ductile region
before fracture where the material displays elongation.
 The data show that fracture occurs at 2.8 GPa which is about 5 times the fracture
stress of iron having larger grain sizes, ranging from 50 to 150 µm.
 Significant modifications of the mechanical properties of disordered bulkmaterials
having nanosized grains is one of the most important properties of such materials.
 Making materials with nanosized grains has the potential to provide significant
increases in yield stress and has many useful applications such as stronger materials for
automobile bodies.

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Rapid solidification:(chill block melt spinning)

RF (radiofrequency) heating coils are used to melt a metal, which is then forced through a
nozzle to form a liquid stream. This stream is continuously sprayed over the surface of a
rotating metal drum under an inert-gas atmosphere.

The process produces strip or ribbons ranging in thickness from 10 to l00µm.

The parameters that control the nanostructure of the material are nozzle size, nozzle-to-drum
distance, melt ejection pressure, and speed of rotation of the metal drum. The need for light
weight, high strength materials has led to the development of 85-94% aluminum alloys with
other metals such as Y, Ni, and Fe made by this method. A melt spun alloy of AI-Y -Ni-Fe
consisting of 10-30-nm AI particles embedded in an amorphous matrix can have a tensile
strength in excess of 1.2 Gpa.

The high value is attributed to the presence of defect free aluminum nanoparticles.

Gas Atomization

A high-velocity inert-gas beam impacts a molten metal.

A fine dispersion of metal droplets is formed when the metal is impacted by the gas, which
transfers kinetic energy to the molten metal. This method can be used to produce large
quantities nanostructured, which are then subjected to hot consolidation to form bulk
samples.

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INTRODUCTION

What is nanotechnology?

It is a manipulation of matter on atomic, molecular and supramoleculer scale.

It has become one of the most important and exciting forefront fields in physics, chemistry,
engineering and biology.

Importance: advances in wide range of applications.

Why?

Nanotechnology is based on the recognition that particles less than the size of 100
nanometers (a nanometer is the billionth of a meter) impart to nanostructures built from them
new properties and behavior. This happens because particles which are smaller than the
characteristic lengths associated with particular phenomena often display new chemistry and
physics, leading to new behavior which depends on size.

So, for example, the electronic structure, conductivity, reactivity, melting temperature, and
mechanical properties have all been observed to change when particles become smaller than a
critical size.

“One nanometer is a magical point on the dimensional scale”. Why?

One nanometer is a magical point on the dimensional scale. Because there is a sudden
shift of all properties of material when they just enters into the nanoscale.

As material size reduces from centimeter (bulk) to nanometer scale, properties mostly
decreases as much as six orders of magnitude to that at macro level. The reason for this
change is due to the nature of interactions among the atoms that are averaged out of existence
in the bulk material. The same can be explained in another way i.e., surface energy increases
with the overall surface area which in turn strongly dependent on the dimension of material.
As nanostructures are having reduced dimensions, it leads to increase in surface energy via
increase in surface area.

The change in properties from macro scale to nano scale can be observed by taking a
simple example as given below.

Let us take an imaginary cube of gold 3 feet on each side. It is sliced in half along its
length, width and height to produce eight little cubes, each 18 inches on a side. If we continue

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cutting the gold in this way from inches to centimeters, from centimeters to millimeters, and
from millimeters to microns; we still notice no change in properties of gold between each
stage except cash value and weight. All gold cubes are soft, shiny yellow and having same
melting point.

But when these µm size gold particles are further sliced into nano size particles, every
thing will be changed including gold’s color, melting point and chemical properties.

Melting point of nano gold is less than that of bulk gold melting point. Similarly
instead of yellow color, nano gold particles appear in different color. This color depends on
the size of the particle.

Not only for gold, all the materials will show the peculiar behavior and change in their
properties when they enter into the nano scale. That is why one nanometer is called as a
magical point on the dimensional scale.

Potential:

Examples of products that are produced currently using nanotechnologies include:

Sunscreens and cosmetics;

Longer-lasting tennis balls and light-weight, stronger tennis racquets;

Stain-free clothing and mattresses;

Polymer films used in displays for laptops, cell phones, digital cameras;

Coatings for easier cleaning glass;

Bumpers and catalytic converters on cars; and

Protective and glare-reducing coatings for eyeglasses and cars.

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Applications:

History:
It is not clear when human first began to take advantage of nanosized materials.

In fourth century A.D. Roman glassmakers were fabricating glasses containing nanosized
metals.

Evidence: A cup called Lycurgus, resides in the British Museum in London. The cup, is made
from soda lime glass containing silver and gold nanoparticles. The color of cup changes from
green to a deep red when a light source is placed inside it.

In 1857 Michael Faraday published a paper in the Philosophical Transactions of the Royal
Society ,which attempted to explain how metal particles affect the color of church windows.

In 1908,Gustav Mie published a paper and he was the first to provide an explanation of the
dependence of the color of the glasses on metal size and kind.

In 1965, Richard Feyman was awarded by the Nobel prize in physics for his contributions to
quantum electrodynamics, a subject far removed from nanotechnology.

The American physicist Richard Feynman lectured, "There's Plenty of Room at the Bottom"
at an American Physical Society meeting at Caltech on December 29, 1959, which is often
held to have provided inspiration for the field of nanotechnology.

He envisioned etching lines a few atoms wide with beam of electrons, effectively predicting
the existence of electron beam lithography, which is used today to make silicon chips.

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He proposed manipulating individual atoms to make new small structures having very
different properties. Indeed, this has now been accomplished using a scanning tunneling
microscope.

He envisioned building circuits on the scale of nanometers that can be used as elements in
more powerful computers.

He recognized the existence of nanostructured in biological systems also and most of his
predictions have become reality.

In 1974, The Japanese scientist called Norio Taniguchi of the Tokyo University of Science
was the first to use the term "nano-technology. He describe semiconductor processes such as
thin film deposition and ion beam milling exhibiting characteristic control on the order of a
nanometer. His definition was, "'Nano-technology' mainly consists of the processing of,
separation, consolidation, and deformation of materials by one atom or one molecule."
However, the term was not used again until 1981 when Eric Drexler, who was unaware of
Taniguchi's prior use of the term, published his first paper on nanotechnology in 1981.

In the 1980s the idea of nanotechnology as a deterministic, rather than stochastic, handling of
individual atoms and molecules was conceptually explored in depth by K. Eric Drexler, who
promoted the technological significance of nano-scale phenomena and devices through
speeches and two influential books.

His 1991 Ph.D. work at the MIT Media Lab was the first doctoral degree on the topic of
molecular nanotechnology and (after some editing) his thesis, "Molecular Machinery and
Manufacturing with Applications to Computation, "was published as Nanosystems:
Molecular Machinery, Manufacturing, and Computation, which received the Association of
American Publishers award for Best Computer Science Book of 1992. Drexler founded the
Foresight Institute in 1986 with the mission of "Preparing for nanotechnology.” Drexler is no
longer a member of the Foresight Institute.

Moore’s Laws:

Gordon Moore, one of the founders of the Intel corporation, came up with two empirical laws
to describe the amazing advances in integrated circuit electronics.

Moore’s first law (usually referred to simply Moore’s law) says that the amount of
space required to install a transistor on a chip shrinks by roughly half every 18 months. This
means that the spot that could hold one transistor 15 years ago can hold 1000 transistors
today. Moore’s first law is good news.

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The bad news is Moore’s second law. It is really a corollary to the first, which gloomily
predicts that the cost of building a chip manufacturing plant (also called a fabrication line or
just fab) doubles with every other chip generation, or roughly every 36 months. The
following figure shows Moore’s laws in a graphical way.

NANOSTRUCTURES

Atoms self-organize in crystals, most of the time. The crystalline lattice is a periodic array of
the atoms. When the solid is not crystalline, it is called amorphous. Examples of crystalline
solids are metals, diamond and other precious stones, ice, graphite. Examples of amorphous
solids are glass, amorphous carbon (a-C), amorphous Si, most plastics

To discuss crystalline structures it is useful to consider atoms as being hard spheres, with
well-defined radii. In this scheme, the shortest distance between two like atoms is one
diameter.

Most nanostructures are crystalline, meaning that their thousands of atoms have a regular
arrangement in space on what is called a crystal lattice.

Unit Cell:The crystal structure of a material (the arrangement of atoms within a given type of
crystal) can be described in terms of its unit cell. The unit cell is a small box containing one
or more atoms arranged in 3-dimensions. The unit cells stacked in three-dimensional space
describe the bulk arrangement of atoms of the crystal. The unit cell is represented in terms of
its lattice parameters, which are the lengths of the cell edges (a, b and c) and the angles
between them (alpha, beta and gamma), while the positions of the atoms inside the unit cell
are described by the set of atomic positions (xi , yi , zi) measured from a lattice point.
Commonly, atomic positions are represented in terms of fractional coordinates, relative to the
unit cell lengths.The most common types of unit cells are the faced-centered cubic (FCC),
the body-centered cubic (FCC) and the hexagonal close-packed (HCP). Other types exist,

particularly among minerals .

ENERGY BANDS
When two valence electron atomic orbitals in a simple molecule such as hydrogen combine to
form a chemical bond, two possible molecular orbitals result. One molecular orbital is

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lowered in energy relative to the sum of the energies of the individual electron orbitals, and is
referred to as the 'bonding' orbital. The other molecular orbital is raised in energy relative to
the sum of the energies of the individual electron orbitals and is termed the 'anti-bonding'
orbital.

In a solid, the same principles apply. If N valence electron atomic orbitals, all of the same
energy, are taken and combined to form bonds, N possible energy levels will result. Of these,
N/2 will be lowered in energy and N/2 will be raised in energy with respect to the sum of the
energies of the N valence electron atomic orbitals.

However, instead of forming N/2 bonding levels all of the exact same energy, the allowed
energy levels will be smeared out into energy bands. Within these energy bands local
differences between energy levels are extremely small. The energy differences between the
levels within the bands are much smaller than the difference between the energy of the
highest bonding level and the energy of the lowest anti-bonding level. Like molecular
orbitals, and also atomic orbitals, each energy level can contain at most two electrons of
opposite spin.

The allowed energy levels are so close together that they are sometimes considered as being
continuous. It is very important to bear in mind that, while this is a useful and reasonable
approximation in some calculations, the bands are actually composed of a finite number of
very closely spaced electron energy levels.

If there is one electron from each atom associated with each of the N orbitals that are
combined to form the bands, then because each resulting energy level can be doubly
occupied, the 'bonding' band, or valence band will be completely filled and the 'anti-bonding'
band, or conduction band will be empty. This is depicted schematically in the picture above
by the grey shading of the valence band.

Electrons cannot have any values of energy that lie outside these bands. An electron can only
move ('be promoted') from the valence band to the conduction band if it is given an energy at
least as great as the band gap energy. This can happen if, for example, the electron were to
absorb a photon of sufficiently high energy.

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If, as in the above one-dimensional schematic, a band is completely filled with electrons, and
the band immediately above it is empty, the material has an energy band gap. This band gap
is the energy difference between the highest occupied state in the valence band and the lowest
unoccupied state in the conduction band. The material is either a semiconductor if the band
gap is relatively small, or an insulator if the band gap is relatively large.

The distinction between an insulator and a semiconductor is less precise. In general, a

material with a band gap of less than about 3 eV is regarded as a semiconductor. A material
with a band gap of greater than 3 eV will commonly be regarded as an insulator. A number of
ceramics such as silicon carbide (SiC), titanium dioxide (TiO2), barium titanate (BaTiO3)
and zinc oxide (ZnO) have band gaps around 3 eV and are regarded by ceramicists as
semiconductors. Such ceramics are often referred to as wide-band-gap semicondutors.

The distinction between semiconductors and insulators arises because in small band gap
materials at room temperature a small, but appreciable, number of electrons can be excited
from the filled valence bands into the unfilled conduction bands simply by thermal vibration.
This leads to semiconducting materials having electrical conductivities between those of
metals and those of insulators.

Localized Particles
When a type V atom such as ~ As, or Sb; which has five electrons in its outer or valence
elctron shell, is a substitutional impurity in Si it uses four of these electrons to satisfy the
valence requirements of the four nearest-neighbor silicons, and the one remaining electron
remains weaklyl bound. The atom easily donates or passes on this electron to the conduction·
band. so it is called doner, and the electron is called a donor electron. This occurs because
the donor energy levels lie in the forbidden region close to the conduction band edge by the
amount ∆ED relative to the thermal energy value kBT, as indicated in Fig.

A type III atom such as Al or Ga, called an acceptor atom, which has three electrons in its
valence shell, can serve as a substitutional defect in Si, and in this role it requires four

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valence electrons to bond with the tetrahedron of nearest neighbor Si atoms. To accomplish
this, it draws or accepts an electron from the valence band, leaving behind a hole at the top
of this band. This occurs easily because the energy levels of the acceptor atoms are· in the
forbidden gap slightly above the valence band edge by the amount ∆EA relative to kB T, as
indicated in above Fig. In other words, the excitation energies needed to ionize the donors
and to add electrons to the acceptors are much less than the thermal energy at room
temperature = 300K.,that is, , ∆ED, ∆EA « kBT, so virtually all donors are positively ionized
and virtually all acceptors are negatively ionized at room temperature

Methods of Measuring Properties:

Atomic Size:

Most nanostructures are crystalline, meaning that their thousands of atoms have a regular
arrangement in space on what is called a crystal lattice. This lattice can be described by
assigning the positions of the atoms in a unit cell, so the overall lattice arises from the
continual replication of .this unit cell throughout space.

There are 17 possible types of crystal structures called space groups; meaning 17 possible
arrangement of atoms in unit cells in two dimensions, and these are divided between the four
crystal systems inthe manner indicated in column 4 of the table.

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X-Ray Diffraction (Crystallography)

The discovery of X-rays in 1895 enabled scientists to probe crystalline structure at the atomic
level. X-ray diffraction has been in use in two main areas, for the fingerprint characterization
of crystalline materials and the determination of their structure. Each crystalline solid has its
unique characteristic X-ray powder pattern which may be used as a "fingerprint" for its
identification. Once the material has been identified, X-ray crystallography may be used to
determine its structure, i.e. how the atoms pack together in the crystalline state and what the
interatomic distance and angle are etc. X-ray diffraction is one of the most important
characterization tools used in solid state chemistry and materials science. We can determine
the size and the shape of the unit cell for any compound most easily using X-ray diffraction.

Diffraction is a phenomena that occurs when light encounters an obstacle. The waves of light
can either bend around the obstacle, or in the case of a slit, can travel through the slits. The
resulting diffraction pattern will show areas of constructive interference, where two waves
interact in phase, and destructive interference, where two waves interact out of
phase. Calculation of the phase difference can be explained by examining figure 1 below.

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In the figure below, two parallel waves, BD and AH are striking a gradient at an angle
θo. The incident wave BD travels farther than AH by a distance of CD before reaching the
gradient. The scattered wave (depicted below the gradient) HF, travels father than the
scattered wave DE by a distance of HG. So the total path difference between path AHGF and
BCDE is CD - HG. To observe a wave of high intensity (one created through constructive
interference), the difference CD - HG must equal to an integer number of wavelengths to be
observed at the angle psi, CD−HG=nλ, where λ is the wavelength of the light. Applying some
basic trigonometric properties, the following two equations can be shown about the lines:

CD=xcos(θo) and HG=xcos(θ)

where x is the distance between the points where the diffraction repeats. Combining the two
equations,

x(cosθo−cosθ)=nλ

Bragg's Law

Diffraction of an x-ray beam, occurs when the light interacts with the electron cloud
surrounding the atoms of the crystalline solid. Due to the periodic crystalline structure of a
solid, it is possible to describe it as a series of planes with an equal interplaner distance. As an
x-ray's beam hits the surface of the crystal at an angle ?, some of the light will be diffracted at
that same angle away from the solid (see figure 2 below). The remainder of the light will
travel into the crystal and some of that light will interact with the second plane of atoms.
Some of the light will be diffracted at an angle theta, and the remainder will travel deeper
into the solid. This process will repeat for the many planes in the crystal. The x-ray beams
travel different path lengths before hitting the various planes of the crystal, so after
diffraction, the beams will interact constructively only if the path length difference is equal to
an integer number of wavelengths (just like in the normal diffraction case above). In the

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figure below, the difference in path lengths of the beam striking the first plane and the beam
striking the second plane is equal to BG + GF. So, the two diffracted beams will
constructively interfere (be in phase) only if BG+GF=nλ. Basic trigonometry will tell us that
the two segments are equal to one another with the interplaner distance times the sine of the
angle θ. So we get:

BG=BC=dsinθ (1)
2dsinθ=nλ (2)

This equation is known as Bragg's Law, named after W. H. Bragg and his son, W. L. Bragg;
who discovered this geometric relationship in 1912. {C}{C}Bragg's Law relates the distance
between two planes in a crystal and the angle of reflection to the x-ray wavelength. The x-
rays that are diffracted off the crystal have to be in-phase in order to signal. Only certain
angles that satisfy the following condition will register:

sinθ=nλ2d (3)

For historical reasons, the resulting diffraction spectrum is represented as intensity vs. 2θ.

Microscopy
Microscopy is the technical field of using microscope to view objects and areas of objects
that cannot be seen with the naked eye (objects that are not within the resolution range of
the normal eye).

There are three well-known branches of microscopy:

 Transmission Electron Microscopy

 Field Ion Microscopy
 Scanning Microscopy

TRANSMISSION ELECTRON MICROSCOPY

TEM consists of a cylindrical tube. The tube contains a vacuum, that is - there is no air or
other gas inside the part of the tube where the specimen is located. This is because molecules
of gases, such as those in air, absorb electrons.

The "electron gun" upper part of the TEM works by emitting electrons from a cathode, then
accelerating them through an anode, after which the electrons pass through an aperture into
the vacuum tube.

As it passes down through the tube the electron beam is controlled by electromagnetic lenses
formed by coils around the tube (whose effect is moderated by adjusting the electricity
flowing through the coils). These electromagnetic lenses direct the electron beam through the
centre of the tube to a very thin specimen located part-way down the tube.

Formation of an image of the specimen is possible because the electrons in the beam are
affected by different regions of the specimen in different ways:

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1. Some parts of the specimen might allow electrons to pass through unaffected.
2. Other regions within the specimen absorb some or all of the electrons that reach them
- so that fewer, if any, electrons continue from that part of the specimen further down
the tube to the image-formation plane, and those that do continue may do so with less
energy because some of their energy has been absorbed by, or "passed to", the part of
the specimen that the electron(s) passed through.
3. Some tiny regions of the specimen may deviate the path of the electrons forming the
beam so that the electrons "bounce" off those precise positions or areas within the
specimen in a range of directions. That is, instead of either continuing down the tube
as in 1., or stopping (or at least slowing-down) by being absorbed as in 2., some parts
of the specimen may cause the electrons to "bounce off in different directions" - that
is, to scatter the electrons.

Depending on if and how they have been affected by the specimen, electrons continue down
the tube (through further electromagnetic lenses) with a range of energies. They eventually
form an image when they reach an image plane where they are detected by a suitable
sensitive material such as a fluorescent film.

The image produced is a greyscale (not colour) image.

The darker areas represent regions of greater absorption of electrons by the specimen while
lighter areas correspond to parts of the specimen that absorbed fewer, if any, electrons. A
very simple way to think of this is that denser regions contain more matter so are able to
absorb more energy from the electron beam whereas less dense regions such as gaps between
the material forming the sample cannot absorb as much, if any, energy from the beam - hence
the resulting micrograph may be thought of as a representation of which parts of the
specimen absorbed relatively more or less energy from the original electron beam.

The advantages of a TEM over a light microscope

Resolution: Electron microscopes can resolve very much greater detail than light
microscopes because the electron beam has a much shorter wavelength than the (comparably
longer) wavelength of visible light that forms the image in a light microscope.
Magnification: Electron microscopes can form much higher magnification images due to the
high magnification 'power' of the electromagnetic lenses, especially the magnetic objective.
The high magnification power is possible due to high voltage applied to the electromagnetic
objective

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Field ion microscopy (FIM) is an analytical technique used in materials science. The field ion
microscope is a type of microscope that can be used to image the arrangement of atoms at the
surface of a sharp metal tip.

In a field ion microscope a wire with a fine tip located in a high-vaccum chamber is given a
positive charge.' The electric field and electric field gradient in the neighborhood of the tip
are both quite high and residual gas molecules that comes close to the tip become ionized by
them, transferring electrons to the tip, thereby acquiring a positive charge, These gaseous
cations are repelled by the tip and move directly outward toward a photographic plate where,
on impact, they create spots. Each spot on the plate close to an atom on the tip, so the
distribution of atoms on the' photographic plate represents a highly enlarged image of the
distribution of atoms on the tip.

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Scanning Microscopy

A scanning electron microscope (SEM) is a type of electron microscope that produces

images of a sample by scanning it with a focused beam of electrons. The electrons interact
with atoms in the sample, producing various signals that can be detected and that contain
information about the sample's surface topography and composition. The electron beam is
generally scanned in a raster scan pattern, and the beam's position is combined with the
detected signal to produce an image. SEM can achieve resolution better than 1 nanometer.
Specimens can be observed in high vacuum, in low vacuum, in wet conditions (in
environmental SEM), and at a wide range of cryogenic or elevated temperatures.

• The types of signals produced by a SEM include secondary electrons (SE), back-
scattered electrons (BSE), characteristic X-rays.

The most common SEM mode is detection of secondary electrons emitted by atoms excited
by the electron beam. The number of secondary electrons depends on the angle at which
beam meets surface of specimen i.e. on specimen topography. By scanning the sample and
collecting the secondary electrons with a special detector, an image displaying the
topography of the surface is created.

Back-scattered electrons (BSE) are beam electrons that are reflected from the sample by
elastic scattering. BSE are often used in analytical SEM along with the spectra made from the
characteristic X-rays, because the intensity of the BSE signal is strongly related to the atomic
number (Z) of the specimen. BSE images can provide information about the distribution of
different elements in the sample.

Characteristic X-rays are emitted when the electron beam removes an inner shell electron
from the sample, causing a higher-energy electron to fill the shell and release energy. These
characteristic X-rays are used to identify the composition and measure the abundance of
elements in the sample.

Sample Preparation:

• All samples must be of an appropriate size to fit in the specimen chamber.

• Proper cleaning and mounting of specimen on stub.

• Specimens must be electrically conductive at least at the surface, and electrically

grounded.

• Nonconductive specimens are usually coated with an ultrathin coating of electrically

conducting material, deposited on the sample by high-vacuum evaporation.

• specimen coating include gold, gold/palladium alloy, platinum, osmium, iridium,

tungsten, chromium, and graphite.

• Additionally, coating with heavy metals may increase signal/noise ratio for samples of
low atomic number (Z)

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Biological sample

• For SEM, a specimen is normally required to be completely dry, since the specimen
chamber is at high vacuum.

• Hard, dry materials such as wood, bone, feathers, dried insects, or shells can be
examined with little further treatment, but living cells and tissues and whole, soft-
bodied organisms usually require chemical fixation to preserve and stabilize their
structure.

• Fixation is usually performed by incubation in a solution of a buffered chemical

fixative, such as glutaraldehyde, sometimes in combination with formaldehyde and
other fixatives.

Scanning process and image formation

In a typical SEM, an electron beam is thermionically emitted from an electron gun fitted with
a tungsten filament cathode. Tungsten is normally used in thermionic electron guns because it
has the highest melting point and lowest vapour pressure of all metals, thereby allowing it to
be heated for electron emission, and because of its low cost.

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 scanning coils or pairs of deflector plates in the electron column, typically in
the final lens, which deflect the beam in the x and y axes so that it scans in a raster fashion
over a rectangular area of the sample surface.

When the primary electron beam interacts with the sample, the electrons lose energy by
repeated random scattering and absorption within a teardrop-shaped volume of the specimen
known as the interaction volume, which extends from less than 100 nm to approximately
5 µm into the surface. The size of the interaction volume depends on the electron's landing
energy, the atomic number of the specimen and the specimen's density. The energy exchange
between the electron beam and the sample results in the reflection of high-energy electrons
by elastic scattering, emission of secondary electrons by inelastic scattering and the emission
of electromagnetic radiation, each of which can be detected by specialized detectors. The
beam current absorbed by the specimen can also be detected and used to create images of the
distribution of specimen current. Electronic amplifiers of various types are used to amplify
the signals, which are displayed as variations in brightness on a computer monitor (or, for
vintage models, on a cathode ray tube). Each pixel of computer videomemory is
synchronized with the position of the beam on the specimen in the microscope, and the
resulting image is therefore a distribution map of the intensity of the signal being emitted
from the scanned area of the specimen. In older microscopes image may be captured by
photography from a high-resolution cathode ray tube, but in modern machines image is saved
to a computer data storage.

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Scanning Tunneling Microscopy

A scanning tunneling microscope utilizes a wire with a very fine point. This fine point is
positively charged and acts as a probe. Probe is lowered to a distance of about 1 nanometer
above the surface under study. Electrons at individual surface atoms are attracted to the
positive charge of the probe wire and jump (tunnel) up to it, thereby generating a weak
electric current. The probe wire is scanned back and forth across the surface in a raster
pattern.

Constant Height Mode: In the constant-probe-height mode the tip is constantly changing its
distance from the surface. This is reflected in variations of the recorded tunneling current as
the probe scans. The feedback loop establishes the initial probe height and is then turned off
during the scan. The scanning probe provides a mapping of the distribution of the atoms on
the surface

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Constant Current Mode: In the constant current mode a feedback loop maintains . a
constant probe height above the sample surface profile and the up/down probe variations are
recorded.The SEM often employs a piezoelectric tripod scanner.A piezoelectric is a material
in which an applied voltage elicits a mechanical response, and the reverse.Applied voltages
induce piezo transducers to move the scanning probe (or the sample) in nanometer
increments along the x, y or z directions .The initial setting is accomplished with the aid of a
stepper motor and micrometer screws. The tunneling current, which varies expo-nentially
with the probe-surface atom separation, depends on the nature of the probe tip and the
composition of the sample surface.

Atomic Force Microscopy

General Application

Materials Investigated: Thin and thick film coatings, ceramics, composites, glasses, synthetic
and biological membranes, metals, polymers, and semiconductors.

Used to study phenomena of: Abrasion, adhesion, cleaning, corrosion, etching, friction,
lubricating, plating, and polishing.

AFM can image surface of material in atomic resolution and also measure force at the nano-
Newton scale.

Parts of AFM

1. Laser – deflected off cantilever

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2. Mirror –reflects laser beam to photodetector

3. Photodetector –dual element photodiode that measures differences in light intensity and
converts to voltage

4. Amplifier

5. Register

6. Sample

7. Probe –tip that scans sample made of Si

8. Cantilever –moves as scanned over sample and deflects laser beam

An atomic force microscope includes a tip mounted on a micromachined cantilever. As the

tip scans a surface to be investigated, interatomic forces between the tip and the sample
surface induce displacement of the tip and corresponding bending of the cantilever.

A laser beam is transmitted to and reflected from the cantilever for measuring the cantilever
orientation. The reflected laser beam is detected with a position-sensitive detector, preferably
a bicell. The output of the bicell is provided to a computer for processing of the data for
providing a topographical image of the surface with atomic resolution.

Cantilever can be bended not only by the direct contact forces under the tip-sample surface
interaction, but also by far-ranging forces: van der Waals, magnetic, electric etc. Vibrating
can proceed in direct contact of the tip with the sample surface, without touching the surface
under vibration and with Intermittent-contact ( Semicontact) under vibration. Scanning can be
many-passing, each next pass can give additional information concerning sample under
investigation.

Advantages

Easy sample preparation

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Accurate height information

Works in vacuum, air, and liquids
Living systems can be studied

Disadantages

Limited vertical range

Limited magnification range
Data not independent of tip
Tip or sample can be damaged

SPECTROSCOPY
Infrared spectroscopy is certainly one of the most important analytical tech-niques available
to today’s scientists. One of the great advantages of infraredspectroscopy is that virtually any
sample in virtually any state may be studied.Liquids, solutions, pastes, powders, films, fibres,
gases and surfaces can all be examined with a judicious choice of sampling technique.

Infrared spectroscopy is a technique based on the vibrations of the atoms of a molecule. An

infrared spectrum is commonly obtained by passing infrared radiation through a sample and
determining what fraction of the incident radiation is absorbed at a particular energy. The
energy at which any peak in an absorption spectrum appears corresponds to the frequency of
a vibration of a part of a sample molecule.

Commercial Infrared instruments fall into three categories: Grating Dispersive, Filter
dispersive and Fourier Transform Infrared Spectroscopy

The original infrared instruments were of the dispersive type. These instruments separated
theindividual frequencies of energy emitted from the infrared source. This was accomplished
by the use of a prism or grating. An infrared prism works exactly the same as a visible prism
which separates visible light into its colors (frequencies). A grating is a more modern
dispersive element which better separates the frequencies of infrared energy. The detector
measures the amount of energy at each frequency which has passed through the sample. This
results in aspectrum which is a plot of intensity vs. frequency.

Fourier transform infrared spectroscopy is preferred over dispersive or filter methods of

infrared
spectral analysis for several reasons:
•It is a non-destructive technique
•It provides a precise measurement method which requires no external calibration
•It can increase speed, collecting a scan every second
•It can increase sensitivity – one second scans can be co-added together to ratio out random
noise

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•It has greater optical throughput

•It is mechanically simple with only one moving part

Fourier Transform Infrared (FT-IR) spectrometry

Fourier Transform Infrared (FT-IR) spectrometry was developed in order to overcome the
limitations encountered with dispersive instruments. The main difficulty was the slow
scanning process. A method for measuring all of the infrared frequencies simultaneously,
rather than individually, was needed. A solution was developed which employed a very
simple optical device called an interferometer. The interferometer produces a unique type of
signal which has all of the infrared frequencies “encoded” into it. The signal can be measured
very quickly, usually on the order of one second or so. Thus, the time element per sample is
reduced to a matter of a few seconds rather than several minutes.

Most interferometers employ a beam splitter which takes the incoming infrared beam and
divides it into two optical beams. One beam reflects off of a flat mirror which is fixed in
place. The other beam reflects off of a flat mirror which is on a mechanism which allows this
mirror to move a very short distance (typically a few millimeters) away from the beam
splitter. The two beams reflect off of their respective mirrors and are recombined when they
meet back at the beam splitter. Because the path that one beam travels is a fixed length and
the other is constantly changing as its mirror moves, the signal which exits the interferometer
is the result of these two beams “interfering” with each other. The resulting signal is called an
interferogram which has the unique property that every data point (a function of the moving
mirror position) which makes up the signal has information about every infrared frequency
which comes from the source.

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This means that as the interferogram is measured; all frequencies are being measured
Simultaneously. Thus, the use of the interferometer results in extremely fast measurements.
Because the analyst requires a frequency spectrum (a plot of the intensity at each individual
frequency) in order to make identification, the measured interferogram signal cannot be
interpreted directly. A means of “decoding” the individual frequencies is required. This can
be accomplished via a well-known mathematical technique called the Fourier transformation.
This transformation is performed by the computer which then presents the user with the
desired spectral information for analysis.

Advantages:
 Speed: Because all of the frequencies are measured simultaneously, most
measurements by FT-I R are made in a matter of seconds rather than several minutes.
This is sometimes referred to as theFelgett Advantage
 Sensitivity: Sensitivity is dramatically improved with FT-IR for many reasons. The
detectors employed are much more sensitive, the optical throughput is much higher
(referred to as the Jacquinot Advantage)
 Mechanical Simplicity: The moving mirror in the interferometer is the only
continuously moving part in the instrument. Thus, there is very little possibility of
mechanical breakdown.
 Internally Calibrated: These instruments employ a HeNe laser as an internal
wavelength calibration standard (referred to as the Connes Advantage).
IR Analysis:
IR spectroscopy is a great method for identification of compounds, especially for
identification of functional groups. Therefore, we can use group frequencies for structural
analysis. Group frequencies are vibrations that are associated with certain functional groups.
It is possible to identify a functional group of a molecule by comparing its vibrational
frequency on an IR spectrum to an IR stored data bank.

Here, we take the IR spectrum of Formaldehyde for an example. Formaldehyde has a C=O
functional group and C-H bond. The value obtained from the following graph can be
compared to those in reference data banks stored for Formaldehyde. A molecule with a C=O
stretch has an IR band which is usually found near 1700 cm-1 and around 1400 cm-1 for CH2
bend. It's important to note that this value is dependent on other functional groups present on
the molecule. The higher 1700 cm-1 indicates a large dipole moment change. It is easier to
bend a molecule than stretch it, hence stretching vibrations have higher frequencies and
require higher energies than bending modes. The finger print region is a region from 1400-
650 cm-1. Each molecule has it's own characteristic print and is often cumbersome to attach
any values to this region.

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Raman Spectroscopy
Raman spectroscopy is a spectroscopic technique based on inelastic scattering of
monochromatic light, usually from a laser source.Inelastic scattering means that the
frequency of photons in monochromatic light changes upon interaction with a sample.
Photons of the laser light are absorbed by the sample and then reemitted. Frequency of the
reemitted photons is shifted up or down in comparison with original monochromatic
frequency, which is called the Raman effect.This shift provides information about vibrational,
rotational and other low frequency transitions in molecules. Raman spectroscopy can be used
to study solid, liquid and gaseous samples.

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When light interacts with matter, the photons which make up the light may be absorbed or
scattered, or may not interact with the material and may pass straight through it. If the energy
of an incident photon corresponds to the energy gap between the ground state of a molecule
and an excited state, the photon may be absorbed and the molecule promoted to the higher
energy excited state. It is this change which is measured in absorption spectroscopy by the
detection of the loss of that energy of radiation from the light. However, it is also possible for
the photon to interact with the molecule and scatter from it. In this case there is no need for
the photon to have an energy which matches the difference between two energy levels of the
molecule. The scattered photons can be observed by collecting light at an angle to the
incident light beam, and provided there is no absorption from any electronic transitions which
have similar energies to that of the incident light, the efficiency increases as the fourth power
of the frequency of the incident light.

When the x-rays hit a sample, the oscillating electric field of the electrom a gnetic radiation
interacts with the electrons bound in an atom. Either the radiation will be scattered by these
electrons, or absorbed and excite the electrons.

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