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Carbon Nanotubes

Carbon, a group IV element, has two crystalline forms: diamond


and graphite. Carbon nanotubes (CNTs) are allotropes of carbon.
These cylindrical carbon molecules have novel 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. CNTs are members of the fullerene structural
family, which also includes the spherical buckyballs 1. The ends of a
CNT might be capped with a hemisphere of the buckyball structure.
Carbon nanotubes are one of the most commonly mentioned
building blocks of nanotechnology. With one hundred times the
tensile strength of steel, thermal conductivity better than all but the
purest diamond, and electrical conductivity similar to copper, but
with the ability to carry much higher currents, they seem to be a
wonder material. However, when we hear of some companies
planning to produce hundreds of tons per year, while others seem to
have extreme difficulty in producing grams, there is clearly more to
this material than meets the eye.
Carbon nanotubes, long thin cylinders of carbon, were
discovered in 1991 by Iijimas. Carbon nanotubes (CNTs) are
allotropes of carbon which are members of the fullerene structural
family, which also includes the spherical buckyballs. These are large
macromolecules which are unique for there size, shape and
remarkable physical properties.
The nature of the bonding of a nanotube is described by applied
quantum chemistry, specifically, orbital hybridization. The chemical
bonding of nanotubes is composed entirely of sp2 bonds, similar to
those of graphite. This bonding structure, which is stronger than the
sp3 bonds found in diamond, provides the molecules with their
unique strength. Nanotubes naturally align themselves into ropes
held together by Van der Waals forces. Under high pressure,
nanotubes can merge together, trading some sp bonds for sp
bonds, giving the possibility of producing strong, unlimited-length
wires through high-pressure nanotube linking.
CNTs are named on the basis of derived from their size, since
the diameter of a nanotube is on the order of a few nanometers,
while they can be up to several millimeters in length CNTs are
categorized as single-walled nanotubes (SWNTs) and multi-walled
nanotubes (MWNTs) depending upon the number of walls. CNTs may

consist of one up to tens and hundreds of concentric shells of


carbons with adjacent shells separation of 0.34 nm i.e. (002). The
carbon network of the shells is closely related to the honeycomb
arrangement of the carbon atoms in the graphite sheets. The
amazing mechanical and electronic properties of the nanotubes
stem in their quasi-one dimensional (1D) structure and the graphitelike arrangement of the carbon atoms in the shells. Thus, the
nanotubes have high Youngs modulus and tensile strength, which
makes them suitable for composite materials with improved
mechanical properties. The nanotubes can be metallic or semi
conducting depending on their structural parameters.
The term nanotube is normally used to refer to the carbon
nanotube, which has received enormous attention from researchers
over the last few years and promises, along with close relatives
such as the nanohorn, a host of interesting applications. There are
many other types of nanotube, from various inorganic kinds, such
as those made from boron nitride, to organic ones, such as those
made from self assembling cyclic peptides (protein components) or
from naturally-occurring heat shock proteins (extracted from
bacteria that thrive in extreme environments). However, carbon
nanotubes excite the most interest, promise the greatest variety of
applications, and currently appear to have by far the highest
commercial potential. Only carbon nanotubes will be covered in this
white paper.

NANOTUBES are the most successful materials that are now


attracting a broad range of scientists and industries due to their

fascinating physical and chemical properties. In this review, we


enlighten you about this material. We are introducing here, the
structure, synthesis and the most important applications of carbon
nanotubes in different fields. The session will feature technology
that exploits novel electronic, electro-mechanical, transistors, and
electrical circuits, optical and structural properties of a carbon
nanotube for the solution of engineering problems.
Nanotubes are members of the fullerene structural family,
which also includes the spherical buckyballs, and the ends of a
nanotube may be capped with a hemisphere of the buckyball
structure. Their name is derived from their long, hollow structure
with the walls formed by one-atom-thick sheets of carbon, called
graphene.

Graphene:Graphene is an allotrope of carbon, whose structure is one-atomthick planar sheets of sp2-bonded carbon atoms that are densely
packed in a honeycomb crystal lattice, the term graphene was
coined as a combination of graphite and the suffix -ene by HannsPeter Boehm who described single-layer carbon foils in 1962.
Graphene is most easily visualized as an atomic-scale chicken
wire made of carbon atoms and their bonds. The crystalline or
"flake" form of graphite consists of many graphene sheets stacked
together.
The carbon-carbon bond length in graphene is about
0.142 nanometres. Graphene sheets stack to form graphite with an
interplanar spacing of 0.335 nm, which means that a stack of
three million sheets would be only one millimetre thick. Graphene is
the basic structural element of some carbon allotropes including
graphite, charcoal, carbon and fullerenes. It can also be considered
as an indefinitely large aromatic molecule, the limiting case of the
family of flat polycyclic aromatic hydrocarbons.
Graphene is a flat monolayer of carbon atoms tightly packed into a
two-dimensional (2D) honeycomb lattice, and is a basic building
block for graphitic materials of all other dimensionalities. It can be
wrapped up into 0D fullerenes, rolled into 1D nanotube or stacked
into 3D graphite.
Graphene is an isolated atomic plane of graphite. From this
perspective, graphene has been known since the invention of X-ray
crystallography. Graphene planes become even well separated in
intercalated graphite compounds. In 2004 physicists at
the University of Manchester and the Institute for Microelectronics

Technology, Chernogolovka, Russia, first isolated individual


graphene planes by using adhesive tape. They also measured
electronic properties of the obtained flakes and showed their unique
properties.
The Nobel Prize in Physics for 2010 was awarded to Andre
Geim and Konstantin Novoselovfor groundbreaking experiments
regarding the two-dimensional material graphene".

The Royal Swedish Academy of Sciences has awarded


the Nobel Prize in Physics for 2010 to Andre Geim and
Konstantin Novoselov, both of the University of Manchester,
"for groundbreaking experiments regarding the twodimensional material graphene."

A thin flake of ordinary carbon, just one atom thick, lies behind
this year's Nobel Prize in Physics. Geim and Novoselov have shown

that carbon in such a flat form has exceptional properties that


originate from the remarkable world of quantum physics.
Geim and Novoselov extracted the graphene from a piece of
graphite such as is found in ordinary pencils. Using regular adhesive
tape they managed to obtain a flake of carbon with a thickness of
just one atom. This at a time when many believed it was impossible
for such thin crystalline materials to be stable.
However, with graphene, physicists can now study a new class of
two-dimensional materials with unique properties. Graphene makes
experiments possible that give new twists to the phenomena in
quantum physics. Also a vast variety of practical applications now
appear possible including the creation of new materials and the
manufacture of innovative electronics. Graphene transistors are
predicted to be substantially faster than today's silicon transistors
and result in more efficient computers.
Since it is practically transparent and a good conductor,
graphene is suitable for producing transparent touch screens, light
panels, and maybe even solar cells.
When mixed into plastics, graphene can turn them into conductors
of electricity while making them more heat resistant and
mechanically robust. This resilience can be utilized in new super
strong materials, which are also thin, elastic and lightweight. In the
future, satellites, airplanes, and cars could be manufactured out of
the new composite materials.

Graphene formation:The Manchester group obtained graphene by


mechanical exfoliation of graphite. They used cohesive tape to
repeatedly split graphite crystals into increasingly thinner pieces.
The tape with attached optically transparent flakes was dissolved in
acetone, and, after a few further steps, the flakes including
monolayers were sedimented on a silicon wafer. Individual atomic
planes were then hunted in an optical microscope. A year later, the
researchers simplified the technique and started using dry
deposition, avoiding the stage when graphene floated in a liquid.
Relatively large crystallites (first, only a few micrometers in size but,
eventually, larger than 1 mm and visible by a naked eye) were
obtained by the technique. It is often referred to as a scotch tape or
drawing method. The latter name appeared because the dry
deposition resembles drawing with a piece of graphite. The key for
the success probably was the use of high-throughput visual
recognition of graphene on a properly chosen substrate, which
provides a small but noticeable optical contrast. The Optical
properties section below has a photograph of what graphene looks
like.

There were a number of previous attempts to make atomically thin


graphitic films by using exfoliation techniques similar to the drawing
method. Multilayer samples down to 10 nm in thickness were
obtained. These efforts were reviewed in 2007. Furthermore, a
couple of very old papers were recently unearthed in which
researchers tried to isolate graphene starting with intercalated
compounds. These papers reported the observation of very thin
graphitic fragments (possibly minelayers) by transmission electron
microscopy. Neither of the earlier observations was sufficient to
"spark the graphene gold rush", until the Science paper did so by
reporting not only macroscopic samples of extracted atomic planes
but, importantly, their unusual properties such as the bipolar
transistor effect, ballistic transport of charges, large quantum
oscillations, etc. The discovery of such interesting qualities intrinsic
to graphene gave an immediate boost to further research and
several groups quickly repeated the initial result and moved further.
These breakthroughs also helped to attract attention to other
production techniques, such as epitaxial growth of ultra-thin
graphitic films. In particular, it has later been found that graphene
monolayers grown on SiC and Ir are weakly coupled to these
substrates and the graphene-substrate interaction can be
passivated further.
The weak van der Waals force that provides the cohesion of
multilayer graphene stacks does not always affect the electronic
properties of the individual graphene layers in the stack. That is,
while the electronic properties of certain multilayered epitaxial
graphenes are identical to that of a single graphene layer, in other
cases the properties are affected as they are for graphene layers in
bulk graphite. This effect is theoretically well understood and is
related to the symmetry of the interlayer interactions.
Experimental methods for the production of graphene ribbons
are reported consisting of cutting open nanotubes. In one such
method multi walled carbon nanotubes are cut open in solution by
action of potassium permanganate and sulfuric acid. In another
method graphene nanoribbons are produced by plasma etching of
nanotubes partly embedded in a polymer film.

Properties of graphene:Atomic structure:The atomic structure of isolated, single-layer graphene was


studied by transmission electron microscopy (TEM) on sheets of
graphene suspended between bars of a metallic grid. Electron
diffraction patterns showed the expected hexagonal lattice of
graphene. Suspended graphene also showed "rippling" of the flat
sheet, with amplitude of about one nanometer. These ripples may
be intrinsic to graphene as a result of the instability of twodimensional crystals or may be extrinsic, originating from the
ubiquitous dirt seen in all TEM images of graphene. Atomic
resolution real-space images of isolated, single-layer graphene on
SiO2 substrates were obtained by scanning tunneling microscopy.
Graphene processed using lithographic techniques is covered
by photoresist residue, which must be cleaned to obtain atomicresolution images.
Graphene sheets in solid form (density > 1 g/cm3) usually
show evidence in diffraction for graphite's 0.34 nm (002) layering.
This is true even of some single-walled carbon nanostructures.
Transmission electron microscope studies show faceting at defects
in flat graphene sheets.

Electronic property:Graphene differs from most conventional three-dimensional


materials. Intrinsic graphene is a semi-metal or zerogap semiconductor. Understanding the electronic structure of
graphene is the starting point for finding the band structure of
graphite. It was realized as early as 1947 by P. R. Wallace that the Ek relation is linear for low energies near the six corners of the twodimensional hexagonal Brillouin zone, leading to zero effective for
electrons and holes. Due to this linear (or conical") dispersion
relation at low energies, electrons and holes near these six points,
two of which are inequivalent, behave like relativistic particles
described by the Dirac equation for spin 1/2 particles. Hence, the
electrons and holes are called Dirac fermions, and the six corners of
the Brillouin zone are called the Dirac points.
The equation describing the E-k relation is

The Fermi velocity vF ~ 106m/s

Thermal properties:The near-room temperature thermal conductivity of


graphene was recently measured to be between
(4.840.44) 103 to (5.300.48) 103Wm1K1. These
measurements, made by a non-contact optical
technique, are in excess of those measured for carbon
nanotubes or diamond. It can be shown by using
the Wiedemann-Franz law, that the thermal conduction
is phonon-dominated. However, for a gated graphene
strip, an applied gate bias causing a Fermi energy shift
much larger than kBT can cause the electronic
contribution to increase and dominate over
the phonon contribution at low temperatures.

Mechanical properties:Graphene appears to be one of the strongest materials


ever tested. Measurements have shown that graphene
has a breaking strength 200 times greater than steel,
with a tensile strength of 130GPa (19,000,000 psi).
Using an atomic force microscope (AFM), the spring
constant of suspended graphene sheets has been
measured. Graphene sheets, held together by van der
Waals forces, were suspended over SiO2 cavities where
an AFM tip was probed to test its mechanical
properties. Its spring constant was in the range 15
N/m and the Young's modulus was 0.5 TPa, which
differs from that of the bulk graphite. These high
values make graphene very strong and rigid. These
intrinsic properties could lead to using graphene

for NEMS applications such as pressure sensors and


resonators.

HISTORY:
The history of carbon nanotubes is not entirely clear even for those
in the science therefore giving proper credit to the person that
invented the carbon nanotube has been the subject of several high
tech debates among the scientific communities.
The initial history of nanotubes started in the 1970s. A preparation
of the planned carbon filaments was completed by Morinobu
Endo who was earning his Ph.D. at the University of Orleans, France.
This was still a highly important development in the history of
carbon nanotubes, but it just wasnt the right time to be considered
the first recognized invention.
Giving the proper credit to who invented carbon nanotubes would
not come along for another 20 years. In 1991 the true first invention
of nanotube was finally made. It seems as though there was a race
between Russian nanotechnologists and Sumio Iijima of IBM.
The first observation of the multiwalled carbon nanotubes was
credited to Iijima.

There are some that hold the belief that in the 1950s there was an
initial discovery of what could have possibly been seen as the first
carbon nanotubes had Roger Bacon had the high powered electron
microscope that would have been necessary.

He was credited with the first visual impression of the tubes of


atoms that roll up and are capped with fullerene molecules by many
scientists in the field. Some state that his discovery just wasnt
taken very seriously at the time because science did not know how
this discovery could impact scientific research.

It would be in 1993 that Iijima and Donald Bethune found single


walled nanotubes known as buckytubes. This helped the scientific
community make more sense out of not only the potential for
nanotube research, but the use and existence of fullerenes.
With this information, the complete discovery of carbon nanotubes
was realized and Iijima and Bethune were ultimately credited with
their discovery in their entirety. Russian nanotechnologists were
independently discovering the same visual affirmation. They were
just a little bit later in their announcement and the potential affect
of this discovery.
The continuation of research revealed a great deal about nanotubes
and their place in scientific discovery. The research has indicated
that there are three basic types of nanotubes (zigzag, armchair, and
chiral) as well as single walled and multiwalled nanotubes.
There are buckytubes, which are completely hollow molecules that
are crafted from pure carbon and are bonded together in a pattern
of specific hexagon patterns. The multiwalled nanotubes are likely to
suffer from defects. These defects happen in more than half of all
multiwalled nanotubes.
The multiwalled nanotubes have already made appearances in
practical applications like creating tennis rackets that are stronger
than steel but are ultra light in weight. These nanotubes are also
responsible for creating sunscreen and other skin care products that

are clear or able to be blended into the skin without leaving behind
residue as well as the creation of UV protective clothing.
As nanotechnologists continue to research nanotubes, there is still a
race to discover something new within the science. Scientists are
researching the potential for life saving techniques as well as the
potential to create nanotubes that can be tailored toward specific
designated jobs.
With the creation of specified nanotubes, the potential for their use
will become unlimited and there will be a nanotechnology world
hard at work crafting all kinds of products from the convenient to
the life saving.

TYPES OF CARBON NANOTUBES:a) SINGLE-WALLED CNTs


These are the stars of the nanotube world, and somewhat reclusive
ones at that, being much harder to make than the multi-walled
variety. The oft-quoted amazing properties generally refer to SWNTs.
As previously described, they are basically tubes of graphite and are
normally capped at the ends although the caps can be removed.
The caps are made by mixing in some pentagons with the hexagons
and are the reason that nanotubes are considered close cousins of
buckminsterfullerene a roughly spherical molecule made of sixty
carbon atoms, that looks like a soccer ball

and is named after the architect Buckminster Fuller (the word


fullerene is used to refer to the variety of such molecular cages,
some with more carbon atoms than buckminsterfullerene, and some
with fewer).

The theoretical minimum diameter of a carbon nanotube is around


0.4 nanometers, which is about as long as two silicon atoms side by
side, and nanotubes this size have been made. Average diameters
tend to be around the 1.2 nanometer mark, depending on the
process used to create them.
SWNTs are more pliable than their multi-walled counterparts and can
be twisted, flattened and bent into small circles or around sharp
bends without breaking.
Most single-walled nanotubes (SWNT) have a diameter close to 1nm,
with a tube length that can be many thousands of times longer.
SWNTs are very important carbon nanotube because they exhibit
important electric properties that are not shared by the multi-walled
carbon nanotubes (MWNT) variants.
SWNTs can be excellent conductors and the most building block
of SWNT system is the electric wires. One useful application of
SWNTs is in the development of the first intramolecular field effect
transistors (FETs).

STRUCTURE:
The bonding in carbon nanotubes is sp, with each atom joined
to three neighbours, as in graphite. The tubes can therefore be
considered as rolled-up graphene sheets (graphene is an individual
graphite layer). There are three distinct ways in which a graphene
sheet can be rolled into a tube, as shown below.
The terms armchair and zig-zag refer to the arrangement of
hexagons around the circumference. The third class of tube, which
in practice is the most common, is known as chiral, meaning that it
can exist in two mirror-related forms. An example of a chiral
nanotube is as shown in fig. below.

In the ideal case, a carbon nanotube consists of either one


cylindrical graphene sheet (single-wall nanotube, SWNT) or of
several nested cylinders with an interlayer spacing of
0.34 0.36 nm that is close to the typical spacing of turbostratic
graphite (multiwalled nanotube, MWNT).

There are many possibilities to form a cylinder with a graphene


sheet: the simplest way of visualizing this is to use a "de Heer
abacus":

A de Heer abacus: to realize a (n,m) tube, move n times a1


and m times a2 from the origin to get to point (n,m) and roll-up the
sheet so that the two points coincide...
Basically, one can roll up the sheet along one of the symmetry axis:
this gives either a zig-zag tube or an armchair tube. It is also
possible to roll up the sheet in a direction that differs from a
symmetry axis: one obtains a chiral nanotube, in which the
equivalent atoms of each unit cell are aligned on a spiral. Besides
the chiral angle, the circumference of the cylinder can also be
varied. In general, the whole family of nanotubes is classified as
zigzag, armchair, and chiral tubes of different diameters:

Models of different single wall nanotubes (generated with


Mathematica on the left, and taken from Saito et al., APL 60, 2204
(1992) on the above).
This diversity of possible configurations is indeed found in practice,
and no particular type is preferentially formed. The lengths of SWNTs
and MWNTs are usually well over 1 m and diameters range from
~1 nm (for SWNTs) to ~50 nm (for MWNTs). Pristine SWNTs are
usually closed at both ends by fullerene-like half spheres that
contain both pentagons and hexagons. As shown in the electron
microscopy images below, a SWNT has a well-defined spherical tip,
whereas the shape of a MWNT cap is more polyhedral than
spherical. An open MWNT, as the name implies, doesn't have a cap
and the ends of the graphene layers and the internal cavity of the
tube are exposed.

Transmission electron microscopy (TEM) pictures of the ends of


different nanotubes. Each black line corresponds to one graphene
sheet viewed edge-on.

Defects in the hexagonal lattice are usually present in the form of


pentagons and heptagons. Pentagons produce a positive curvature
of the graphene layer and are mostly found at the cap. Heptagons
give raise to a negative curvature of the tube wall. Defects
consisting of several pentagons and/or heptagons have also been
observed.

A simple model indicates that the diameter and/or chirality of the tube are changed
from one side of the defect to the other. Such an arrangement forms therefore a link
between two different tubes and is accordingly called a junction.

b) MULTI-WALLED CNTs:
Multi-walled nanotubes (MWNT) consist of multiple rolled in on
themselves to form a tube shape. There are two models which can
be used to describe the structures of multi-walled nanotubes. In the
Russian Doll model, sheets of graphite are arranged in concentric
cylinders. In the Parchment model, a single sheet of graphite is
rolled in around itself, resembling a scroll of parchment or a rolled
up newspaper. The interlayer distance in multi-walled nanotubes is
close to the distance between graphene layers in graphite,
approximately 0.33 nm.

Although it is easier to produce significant quantities of MWNTs than


SWNTs, their structures are less well understood than single-wall
nanotubes because of their greater complexity and variety.
Multitudes of exotic shapes and arrangements, often with
imaginative names such as bamboo-trunks, sea urchins, necklaces
or coils, have also been observed under different processing
conditions. The variety of forms may be interesting but also has a
negative sideMWNTs always (so far) have more defects than
SWNTs and these diminish their desirable properties.
Many of the nanotube applications now being considered or put into
practice involve multi-walled nanotubes, because they are easier to
produce in large quantities at a reasonable price and have been
available in decent amounts for much longer than SWNTs. In fact
one of the major manufacturers of MWNTs at the moment, Hyperion
Catalysis, does not even sell the nanotubes directly but only premixed with polymers for composites applications. The tubes
involved typically have 8 to 15 walls and are around 10 nanometres
wide and 10 micrometers long.
Companies are moving into this space, notably formidable players
like Mitsui, with plans to produce similar types of MWNT in hundreds
of tons a year, a quantity that is greater, but not hugely so, than the
current production of Hyperion Catalysis. This is an indication that
even these less impressive and exotic nanotubes hold promise of
representing a sizable market in the near future.

SYNTHESIS:There are a number of methods of making CNTs and fullerenes.


Fullerenes were first observed after vaporizing graphite with a shortpulse, high-power laser, however this was not a practical method for
making large quantities.
CNTs have probably been around for a lot longer than was first
realized, and may have been made during various carbon
combustion and vapor deposition processes, but electron
microscopy at that time was not advanced enough to distinguish
them from other types of tubes. The first method for producing CNTs
and fullerenes in reasonable quantities was by applying an electric
current across two carbonaceous electrodes in an inert gas
atmosphere. This method is called plasma arcing. It involves the
evaporation of one electrode as cations followed by deposition at
the other electrode. This plasma-based process is analogous to the
more familiar electroplating process in a liquid medium. Fullerenes
and CNTs are formed by plasma arcing of carbonaceous materials,
particularly graphite. The fullerenes appear in the soot that is
formed, while the CNTs are deposited on the opposing electrode.
Another method of nanotube synthesis involves plasma arcing
in the presence of cobalt with a 3% or greater concentration. As
noted above, the nanotube product is a compact cathode deposit of
rod like morphology. However when cobalt is added as a catalyst,
the nature of the product changes to a web, with strands of 1mm or
so thickness that stretch from the cathode to the walls of the
reaction vessel. The mechanism by which cobalt changes this
process is unclear, however one possibility is that such metals affect
the local electric fields and hence the formation of the fivemembered rings.
Synthesis of carbon nanotubes can be done by different
methods:-

1) Arc discharge method


2) Laser ablation method
3) Chemical vapour deposition method
a) plasma enhanced chemical vapour deposition
b) Thermal chemical vapour deposition
c) Vapour phase growth

a) ARC DISCHARGE METHOD


Nanotubes were observed in 1991 in the carbon soot of graphite
electrodes during an arc discharge, by using a current of 100
amperes that was intended to produce fullerenes.

The carbon arc discharge method, initially used for producing C60
fullerenes, is the most common and perhaps easiest way to produce
CNTs, as it is rather simple. However, it is a technique that produces
a complex mixture of components, and requires further purification to separate the CNTs from the soot and the residual catalytic metals
present in the crude product. This method creates CNTs through arcvaporization of two carbon rods placed end to end, separated by
approximately 1mm, in an enclosure that is usually filled with inert
gas at low pressure. Recent investigations have shown that it is also
possible to create CNTs with the arc method in liquid nitrogen. A
direct current of 50 to 100 A, driven by a potential difference of
approximately 20 V, creates a high temperature discharge between
the two electrodes.

The discharge vaporizes the surface of one of the carbon


electrodes, and forms a small rod-shaped deposit on the other
electrode. Producing CNTs in high yield depends on the uniformity of
the plasma arc, and the temperature of the deposit forming on the
carbon electrode. The carbon contained in the negative electrode
sublimates because of the high temperatures caused by the
discharge. Because nanotubes were initially discovered using this
technique, it has been the most widely used method of nanotube
synthesis.

The yield for this method is up to 30 percent by weight and it


produces both single- and multi-walled nanotubes with lengths of up
to 50 micrometers.

b) LASER ABLATION PROCESS


In the laser ablation process, a pulsed laser vaporizes a graphite
target in a high temperature reactor while an inert gas is bled into
the chamber. The nanotubes develop on the cooler surfaces of the
reactor, as the vaporized carbon condenses. A water-cooled surface
may be included in the system to collect the nanotubes.
In 1996 CNTs were first synthesized using a dual-pulsed laser and
achieved yields of >70wt% purity. Samples were prepared by laser
vaporization of graphite rods with a 50:50 catalyst mixture of Cobalt
and Nickel at 1200C in flowing argon, followed by heat treatment in
a vacuum at 1000C to remove the C60 and other fullerenes. The
initial laser vaporization pulse was followed by a second pulse, to
vaporize the target more uniformly. The use of two successive laser
pulses minimizes the amount of carbon deposited as soot. The
second laser pulse breaks up the larger particles ablated by the first
one, and feeds them into the growing nanotube structure.

The material produced by this method appears as a mat of ropes,


10-20nm in diameter and up to 100m or more in length. Each rope
is found to consist primarily of a bundle of single walled nanotubes,
aligned along a common axis. By varying the growth temperature,

the catalyst composition, and other process parameters, the


average nanotube diameter and size distribution can be varied. Arcdischarge and laser vaporization are currently the principal methods
for obtaining small quantities of high quality CNTs. However, both
methods suffer from drawbacks. The first is that both methods
involve evaporating the carbon source, so it has been unclear how
to scale up production to the industrial level using these
approaches. The second issue relates to the fact that vaporization
methods grow CNTs in highly tangled forms, mixed with unwanted
forms of carbon and/or metal species. The CNTs thus produced are
difficult to purify, manipulate, and assemble for building nanotubedevice architectures for practical applications

This method has a yield of around 70% and produces primarily


single-walled carbon nanotubes with a controllable diameter
determined by the reaction temperature.

c) CHEMICAL VAPOUR DEPOSITION


Chemical vapor deposition of hydrocarbons over a metal catalyst is
a classical method that has been used to produce various carbon
materials such as carbon fibers and filaments. For over twenty
years. Large amounts of CNTs can be formed by catalytic CVD of
acetylene over Cobalt and iron catalysts supported on silica or
zeolite. The carbon deposition activity seems to relate to the cobalt
content of the catalyst, whereas the CNTs selectivity seems to be a
function of the pH in catalyst preparation.
Fullerenes and bundles of single walled nanotubes were also found
among the multi walled nanotubes produced on the carbon/zeolite
catalyst. Some researchers are experimenting with the formation of
CNTs from ethylene. Supported catalysts such as iron, cobalt, and
nickel, containing either a single metal or a mixture of metals, seem
to induce the growth of isolated single walled nanotubes or single
walled nanotubes bundles in the ethylene atmosphere. The
production of single walled nanotubes, as well as double-walled
CNTs, on molybdenum and molybdenum-iron alloy catalysts has also
been demonstrated. CVD of carbon within the pores of a thin
alumina template with or without a Nickel catalyst has been
achieved. Ethylene was used with reaction temperatures of 545C
for Nickel-catalyzed CVD, and 900C for an uncatalyzed process. The
resultant carbon nanostructures have open ends, with no caps.
Methane has also been used as a carbon source. In particular it has
been used to obtain nanotube chips containing isolated single
walled nanotubes at controlled locations. High yields of single walled
nanotubes have been obtained by catalytic decomposition of an
H2/CH4 mixture over well-dispersed metal particles such as Cobalt,
Nickel, and Iron on magnesium oxide at 1000C. It has been
reported that the synthesis of composite powders containing welldispersed CNTs can be achieved by selective reduction in an H2/CH4
atmosphere of oxide solid solutions between a non-reducible oxide

such as Al2O3 or MgAl2O4 and one or more transition metal oxides.


The reduction produces very small transition metal particles at a
temperature of usually >800C. The decomposition of CH4 over the
freshly formed nanoparticles prevents their further growth, and thus
results in a very high proportion of single walled nanotubes and
fewer multi walled nanotubes.
These are the basic principles of the CVD process. In the last
decennia, different techniques for the carbon nanotubes synthesis
with CVD have been developed, such as plasma enhanced CVD,
thermal chemical CVD, alcohol catalytic CVD, vapour phase growth,
aero gel-supported CVD and laser-assisted CVD. These different
techniques will be explained more detailed in this chapter.

Using CVD, a substrate is prepared with a layer of metal catalyst


particles, most commonly nickel, cobalt, iron, or a combination. The
diameters of the nanotubes that are to be grown are related to the
size of the metal particles. This can be controlled by
patterned deposition of the metal, annealing, or by plasma etching
of a metal layer. The substrate is heated to approximately 700C. To
initiate the growth of nanotubes, two gases are bled into the
reactor: a process gas (such as ammonia, nitrogen, hydrogen, etc.)
and a carbon-containing gas (such as acetylene, ethylene, ethanol,
methane, etc.). Nanotubes grow at the sites of the metal catalyst;
the carbon-containing gas is broken apart at the surface of the
catalyst particle, and the carbon is transported to the edges of the
particle.
CVD is a common method for the commercial production of carbon
nanotubes.. For this purpose, the metal nanoparticles will be
carefully mixed with a catalyst support (e.g., MgO, Al2O3, etc) to
increase the specific surface area for higher yield of the catalytic

reaction of the carbon feedstock with the metal particles. One issue
in this synthesis route is the removal of the catalyst support via an
acid treatment, which sometimes could destroy the original
structure of the carbon nanotubes. However, alternative catalyst
supports that are soluble in water have been shown to be effective
for nanotube growth. If plasma is generated by the application of a
strong electric field during the growth process (plasma enhanced
chemical vapor deposition), then the nanotube growth will follow the
direction of the electric field. By properly adjusting the geometry of
the reactor it is possible to synthesize vertically aligned carbon
nanotubes.

1) Plasma enhanced chemical vapour deposition


The plasma enhanced CVD method generates a glow discharge in a
chamber or a reaction furnace by a high frequency voltage applied
to both electrodes.
Figure shows a schematic diagram of a typical plasma CVD
apparatus with a parallel plate electrode structure.

Figure: Schematic diagram of plasma CVD


apparatus.
A substrate is placed on the grounded electrode. In order to form a
uniform film, the reaction gas is supplied from the opposite plate.
Catalytic metal, such as Fe, Ni and Co are used on for example a Si,
SiO2, or glass substrate using thermal CVD or sputtering. After
nanoscopic fine metal particles are formed, carbon nanotubes will
be grown on the metal particles on the substrate by glow discharge
generated from high frequency power. A carbon containing reaction
gas, such as C2H2, CH4, C2H4, C2H6, CO is supplied to the chamber
during the discharge.

The catalyst has a strong effect on the nanotube diameter, growth


rate, wall thickness, morphology and microstructure. Ni seems to be
the most suitable pure-metal catalyst for the growth of aligned
multi-walled carbon nanotubes (MWNTs)36. The diameter of the
MWNTs is approximately 15 nm. The highest yield of carbon
nanotubes achieved was about 50% and was obtained at relatively
low temperatures (below 330o C).

2) Thermal chemical vapour deposition


In this method Fe, Ni, Co or an alloy of the three catalytic metals is
initially deposited on a substrate. After the substrate is etched in a
diluted HF solution with distilled water, the specimen is placed in a
quartz boat. The boat is positioned in a CVD reaction furnace, and
nanometer-sized catalytic metal particles are formed after an
additional etching of the catalytic metal film using NH 3 gas at a
temperature of 750 to 1050 o C. As carbon nanotubes are grown on
these fine catalytic metal particles in CVD synthesis, forming these
fine catalytic metal particles is the most important process.
Figure shows a schematic diagram of thermal CVD apparatus in the
synthesis of carbon nanotubes.

Figure: Schematic diagram of thermal CVD


apparatus.
When growing carbon nanotubes on a Fe catalytic film by thermal
CVD, the diameter range of the carbon nanotubes depends on the
thickness of the catalytic film. By using a thickness of 13 nm, the
diameter distribution lies between 30 and 40 nm. When a thickness
of 27 nm is used, the diameter range is between 100 and 200 nm.
The carbon nanotubes formed are multiwalled.

3) Vapour phase growth


Vapour phase growth is a synthesis method of carbon nanotubes,
directly supplying reaction gas and catalytic metal in the chamber
without a substrate 39.
Figure shows a schematic diagram of a vapour phase growth
apparatus. Two furnaces are placed in the reaction chamber.
Ferrocene is used as catalyst. In the first furnace, vaporization of
catalytic carbon is maintained at a relatively low temperature. Fine
catalytic particles are formed and when they reach the second
furnace, decomposed carbons are absorbed and diffused to the
catalytic metal particles. Here, they are synthesized as carbon
nanotubes. The diameter of the carbon nanotubes by using vapour
phase growth are in the range of 2 - 4 nm for SWNTs 40 and between
70 and 100 nm for MWNTs.

Chemical
Method

Arc
discharge
vapour
method
deposition

Who

Ebbesen
Ajayan,
Japan 1992

How

Connect
twoPlace substrate inBlast graphite with
graphite rods to aoven,
heat
tointense laser pulses;
o
power
supply,600 C,
anduse the laser pulses
place them a fewslowly
add
arather
than
millimeters apart,carbon-bearing
electricity
to
and
throw
thegas
such
asgenerate carbon gas
switch.
At
100methane. As gasfrom which the NTs
amps,
carbondecomposes
itform;
try
various
vaporizes
andfrees up carbonconditions until hit
forms hot plasma. atoms,
whichon one that produces
recombine in theprodigious amounts
form of NTs
of SWNTs

15

Laser
ablation
(vaporization)

andEndo,
ShinshuSmalley, Rice, 199514
NEC,University,
Nagano, Japan 53

Chemical
Method
Typical
yield

Arc
discharge
vapour
method
deposition

Laser
ablation
(vaporization)

30 to 90%

Up to 70%

20 to 100 %

SWNT

Short tubes withLong tubes withLong


bundles
of
diameters of 0.6 -diameters
tubes (5-20 microns),
1.4 nm
ranging from 0.6-with
individual
4 nm
diameter from 1-2
nm.

M-WNT

Short tubes withLong tubes withNot


very
much
inner diameter ofdiameter ranginginterest
in
this
1-3 nm and outerfrom 10-240 nm technique, as it is too
diameter
of
expensive,
but
approximately 10
MWNT synthesis is
nm
possible.

Pro

Can
easilyEasiest to scalePrimarily SWNTs, with
produce
SWNT,up to industrialgood
diameter
MWNTs.
SWNTsproduction; longcontrol
and
few
have
fewlength,
simpledefects. The reaction
structural defects;process,
SWNTproduct is quite pure.
MWNTs
withoutdiameter
catalyst, not toocontrollable, quite
expensive,
openpure
air
synthesis
possible

Con

Tubes tend to beNTs are usuallyCostly


technique,
short with randomMWNTs and oftenbecause it requires
sizes
andriddled
withexpensive lasers and
directions;
oftendefects
high
power
needs a lot of
requirement, but is
purification
improving
Table 2-2: A summary of the major production methods
and their efficiency

Characterization
nanotubes:-

of

carbon

The experimental techniques used for growth and characterization


of carbon nanotubes are discussed. Plasma enhanced chemical
vapor deposition (PECVD) method was used for the deposition of
these films. Scanning electron microscopy (SEM), Transmission
electron microscopy (TEM), Energy dispersive X-ray spectroscopy
(EDS), Raman spectroscopy and X-ray diffraction were used for the
characterization of carbon nanostructures and catalyst
nanoparticles.

SEM:A scanning electron microscope (SEM) is a type of


electron microscope that images a sample by scanning it with a
high-energy beam of electrons in a raster scan pattern. The
electrons interact with the atoms that make up the sample
producing signals that contain information about the sample's
surface topography, composition, and other properties such as
electrical conductivity.
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. Other types of electron emitters include lanthanum
hexaboride (LaB6) cathodes, which can be used in a standard
tungsten filament SEM if the vacuum system is upgraded and field
emission guns (FEG), which may be of the cold-cathode type using
tungsten single crystal emitters or the thermally-assisted Schottky
type, using emitters of zirconium oxide.

The electron beam, which typically has an energy ranging from 0.5
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 around
5 m 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 cathode ray tube. The raster scanning of the CRT display is
synchronized with that 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. The image may be captured by photography from a
high resolution cathode ray tube, but in modern machines is
digitally captured and displayed on a computer monitor and saved
to a computer's hard disk.

TEM:Transmission electron microscopy (TEM) is a microscopy


technique whereby a beam of electrons is transmitted through an
ultra thin specimen, interacting with the specimen as it passes
through. An image is formed from the interaction of the electrons
transmitted through the specimen; the image is magnified and
focused onto an imaging device, such as a fluorescent screen, on a
layer of photographic film, or to be detected by a sensor such as a
CCD camera.

TEMs are capable of imaging at a significantly higher resolution than


light microscopes, owing to the small de Broglie wavelength of
electrons. This enables the instrument's user to examine fine detail
even as small as a single column of atoms, which is tens of
thousands times smaller than the smallest resolvable object in a
light microscope. TEM forms a major analysis method in a range of
scientific fields, in both physical and biological sciences. TEMs find
application in cancer research, virology, materials science as well as
pollution, nanotechnology, and semiconductor research.

XRD:X-ray scattering techniques are a family of non-destructive


analytical techniques which reveal information about the
crystallographic structure, chemical composition, and physical
properties of materials and thin films. These techniques are based
on observing the scattered intensity of an X-ray beam hitting a
sample as a function of incident and scattered angle, polarization,
and wavelength or energy.
In an X-ray diffraction measurement, a crystal is mounted on a
goniometer and gradually rotated while being bombarded with Xrays, producing a diffraction pattern of regularly spaced spots
known as reflections. The two-dimensional images taken at different
rotations are converted into a three-dimensional model of the
density of electrons within the crystal using the mathematical
method of Fourier transforms, combined with chemical data known
for the sample. Poor resolution (fuzziness) or even errors may result
if the crystals are too small, or not uniform enough in their internal
makeup.
X-ray crystallography is related to several other methods for
determining atomic structures. Similar diffraction patterns can be
produced by scattering electrons or neutrons, which are likewise
interpreted as a Fourier transform. If single crystals of sufficient size
cannot be obtained, various other X-ray methods can be applied to
obtain less detailed information; such methods include fiber
diffraction, powder diffraction and small-angle X-ray scattering
(SAXS). If the material under investigation is only available in the
form of nano-crystalline powders or suffers from poor crystallinity,
the methods of electron crystallography can be applied for
determining the atomic structure.

RAMAN SPECTROSCOPY:Raman spectroscopy (named after C. V. Raman) is


spectroscopic technique used to study vibrational, rotational, and
other low-frequency modes in a system. It relies on inelastic
scattering, or Raman scattering, of monochromatic light, usually
from a laser in the visible, near infrared, or near ultraviolet range.
The laser light interacts with molecular vibrations, phonons or other
excitations in the system, resulting in the energy of the laser
photons being shifted up or down. The shift in energy gives
information about the vibrational modes in the system. Infrared
spectroscopy yields similar, but complementary, information.
Typically, a sample is illuminated with a laser beam. Light from the
illuminated spot is collected with a lens and sent through
a monochromatic. Wavelengths close to the laser line, due to
elastic Rayleigh scattering, are filtered out while the rest of the
collected light is dispersed onto a detector.
Spontaneous Raman scattering is typically very weak, and as a
result the main difficulty of Raman spectroscopy is separating the
weak inelastically scattered light from the intense Rayleigh
scattered laser light.

Raman spectra are typically expressed in wave numbers, which


have units of inverse length. In order to convert between spectral
wavelength and wave numbers of shift in the Raman spectrum, the
following formula can be used:

Where w is the Raman shift expressed in wave number, 0 is the


excitation wavelength, and 1 is the Raman spectrum wavelength.
Most commonly, the units chosen for expressing wave number in
Raman spectra is inverse centimeters (cm1). Since wavelength is
often expressed in units of nanometers (nm), the formula above can
scale for this units conversion explicitly, giving

PROPERTIES:The most important properties of CNTs are:-

a) Strength and elasticity:


CNTs are the strongest and stiffest materials on earth, in terms of
tensile strength and elastic modulus respectively. This strength
results from the covalent sp bonds formed between individual
carbon atoms.
The carbon atoms of a single sheet of graphite form a planar
honeycomb lattice, in which each atom is connected via a strong
chemical bond to three neighboring atoms. Because of these strong
bonds, the basal plane elastic modulus of graphite is one of the
largest of any known material. For this reason, CNTs are expected to
be the ultimate high-strength fibers. Single walled nanotubes are
stiffer than steel, and are very resistant to damage from physical
forces. Pressing on the tip of a nanotube will cause it to bend, but
without damage to the tip. When the force is removed, the nanotube
returns to its original state. This property makes CNTs very useful as
probe tips for very high-resolution scanning probe microscopy.
Quantifying these effects has been rather difficult, and an exact
numerical value has not been agreed upon.
Using atomic force microscopy, the unanchored ends of a
freestanding nanotube can be pushed out of their equilibrium
position, and the force required to push the nanotube can be
measured. The current Youngs modulus value of single walled
nanotubes is about 1 TeraPascal, but this value has been widely
disputed, and a value as high as 1.8 Tpa has been reported. Other
values significantly higher than that have also been reported. The
differences probably arise through different experimental
measurement techniques. Others have shown theoretically that the
Youngs modulus depends on the size and chirality of the single
walled nanotubes, ranging from 1.22 Tpa to 1.26 Tpa. They have
calculated a value of 1.09 Tpa for a generic nanotube. However,
when working with different multi walled nanotubes, others have
noted that the modulus measurements of multi walled nanotubes
using AFM techniques do not strongly depend on the diameter.
Instead, they argue that the modulus of the multi walled nanotubes
correlates to the amount of disorder in the nanotube walls. Not
surprisingly, when multi walled nanotubes break, the outermost
layers break first.

CNTs are not nearly as strong under compression. Because of their


hollow structure and high aspect ratio, they tend to undergo
buckling when placed under compressive, tensional or bending
stress.

b) Thermal conductivity and expansion:


All nanotubes are expected to be very good thermal conductors
along the tube, exhibiting a property known as ballistic conduction,
but good insulators laterally to the tube axis. The temperature
stability of carbon nanotubes is established to be up to 2800
degrees Celsius in vacuum and about 750 degrees Celsius in air.
CNTs have been shown to exhibit superconductivity below
20K (aprox. 253C). Research suggests that these exotic strands,
already heralded for their unparalleled strength and unique ability to
adopt the electrical properties of either semiconductors or perfect
metals, may someday also find applications as miniature heat
conduits in a host of devices and materials. The strong in-plane
graphitic carbon - carbon bonds make them exceptionally strong
and stiff against axial strains. The almost zero in-plane thermal
expansion but large inter-plane expansion of single walled
nanotubes implies strong in-plane coupling and high flexibility
against non-axial strains.
Many applications of CNTs, such as in nanoscale molecular
electronics, sensing and actuating devices, or as reinforcing additive
fibers in functional composite materials, have been proposed.
Reports of several recent experiments on the preparation and
mechanical characterization of CNT-polymer composites have also
appeared. These measurements suggest modest enhancements in
strength characteristics of CNT-embedded matrixes as compared to
bare polymer matrixes. Preliminary experiments and simulation
studies on the thermal properties of CNTs show very high thermal
conductivity. It is expected, therefore, that nanotube reinforcements
in polymeric materials may also significantly improve the thermal
and thermo mechanical properties of the composites.

c) High aspect ratio:


CNTs represent a very small, high aspect ratio conductive additive
for plastics of all types. Their high aspect ratio means that a lower
loading of CNTs is needed compared to other conductive additives to
achieve the same electrical conductivity. This low loading preserves
more of the polymer resins toughness, especially at low
temperatures, as well as maintaining other key performance

properties of the matrix resin. CNTs have proven to be an excellent


additive to impart electrical conductivity in plastics. Their high
aspect ratio, about 1000:1 imparts electrical conductivity at lower
loadings, compared to conventional additive materials such as
carbon black, chopped carbon fiber, or stainless steel fiber.

d) Electrical Conductivity:
Depending on their chiral vector, carbon nanotubes with a small
diameter are either semi-conducting or metallic.
CNTs can be highly conducting, and hence can be said to be
metallic. Their conductivity has been shown to be a function of their
chirality, the degree of twist as well as their diameter. CNTs can be
either metallic or semi-conducting in their electrical behavior.
Conductivity in MWNTs is quite complex. Some types of armchairstructured CNTs appear to conduct better than other metallic CNTs.
Furthermore, interwall reactions within multi walled nanotubes have
been found to redistribute the current over individual tubes nonuniformly. However, there is no change in current across different
parts of metallic single-walled nanotubes. The behavior of the ropes
of semi-conducting single walled nanotubes is different, in that the
transport current changes abruptly at various positions on the CNTs.
The conductivity and resistivity of ropes of single walled nanotubes
has been measured by placing electrodes at different parts of the
CNTs. The resistivity of the single walled nanotubes ropes was of the
order of 104 ohm-cm at 27C. This means that single walled
nanotube ropes are the most conductive carbon fibers known. The
current density that was possible to achieve was 10-7 A/cm2,
however in theory the single walled nanotube ropes should be able
to sustain much higher stable current densities, as high as 10-13
A/cm2. It has been reported that individual single walled nanotubes
may contain defects. Fortuitously, these defects allow the single
walled nanotubes to act as transistors. Likewise, joining CNTs
together may form transistor-like devices. A nanotube with a natural
junction (where a straight metallic section is joined to a chiral semi
conducting section) behaves as a rectifying diode that is, a halftransistor in a single molecule. It has also recently been reported
that single walled nanotubes can route electrical signals at speeds
up to 10 GHz when used as interconnects on semi-conducting
devices.

e) Electronic properties:
The electronic properties of SWNTs have been studied in a large
number of theoretical works. All models show that the
electronic properties vary in a predictable way from metallic to
semi conducting with diameter and chirality. This is due to the
very peculiar band structure of graphene and is absent in
systems that can be described with usual free electron theory.
Electron motion in graphene is equivalent to that of a neutrino or a
relativistic Dirac electron with vanishing rest mass. This
causes the appearance of a nontrivial Berrys phase under 2
rotation in wave-vector space, leading to the absence of
backscattering and in the metallic carbon nanotube resulting
in perfect conduction even in the presence of scatterers. The
energy bands in carbon nanotubes are determined by periodic
boundary conditions with a fictitious Aharonov-Bohm flux
determined uniquely by the circumferential chiral vector. A
nanotube becomes metallic when the flux vanishes and
semiconducting when the flux is nonzero. The conductivity of
graphene is essentially independent of the Fermi energy and
the electron concentration as long as variations in effective
scattering strength are neglected, and therefore graphene
should be regarded as a metal rather than a zero-gap
semiconductor. Various schemes are now being proposed and
tested for the purpose of opening the band gap in graphene.
Basically, all armchair tubes are metallic. One out of three zigzag
and chiral tubes show a small very small band gap due to the
curvature of the graphene sheet, while all other tubes are semiconducting with a band gap that scales approximately with the
inverse of the tube radius. Bandgaps of 0.4 1 eV can be expected
for SWNTs (corresponding to diameters between 0.6 and 1.6 nm).

On the left: band structure of the conduction band of graphene,


which crosses the Fermi level at the edges of the Brillouin zone.
On the right: predicted band-gap as a function of SWNT radius,
reproduced from Kane and Mele, PRL 78, 1932 (1997).
These theoretical predictions made in 1992 were actually confirmed
in 1998 by scanning tunneling spectroscopy. Numerous conductivity
experiments on SWNTs and MWNTs allowed gaining additional
informations. At low temperatures, SWNTs behave as coherent
quantum wires where the conduction occurs through discrete

electron states over large distances. Transport measurements


revealed that metallic SWNTs show extremely long coherence
lengths. MWNTs show also these effects in spite of their larger
diameter and multiple shells.

f) Mechanical properties:
Carbon nanotube is the one of the strongest materials in nature.
Carbon nanotubes (CNTs) are basically long hollow cylinders of
graphite sheets. Although a graphite sheet has a 2D symmetry,
carbon nanotubes by geometry have different properties in axial
and radial directions. It has been shown that CNTs are very strong in
the axial direction. Young's modulus on the order of 270 - 950 GPa
and tensile strength of 11 - 63 GPa were obtained.
On the other hand, there was evidence that in the radial direction
they are rather soft. The first transmission electron microscope
observation of radial elasticity suggested that even the van der
Waals forces can deform two adjacent nanotubes. Later,
nanoindentations with atomic force microscope were performed by
several groups to quantitatively measure radial elasticity of
multiwalled carbon nanotubes and tapping/contact mode atomic
force microscopy was recently performed on single-walled carbon
nanotubes. Young's modulus of on the order of several GPa showed
that CNTs are in fact very soft in the radial direction.
Radial direction elasticity of CNTs is important especially for carbon
nanotube composites where the embedded tubes are subjected to
large deformation in the transverse direction under the applied load
on the composite structure.
One of the main problems in characterizing the radial elasticity of
CNTs is the knowledge about the internal radius of the CNT; carbon
nanotubes with identical outer diameter may have different internal
diameter (or the number of walls). Recently a method using atomic
force microscope was introduced to find the exact number of layers
and hence the internal diameter of the CNT. In this way, mechanical
characterization is more accurate.

Comparison of mechanical properties


Materi
Young's
Tensile
Elongation at
al
modulus (T strength (G
break (%)

Pa)

Pa)

SWNT

~1 (from 1 to
5)

1353

16

Armchair
SWNT

0.94

126.2

23.1

Zigzag
SWNT

0.94

94.5

15.617.5

Chiral
SWNT

0.92

NA

NA

MWNTE

0.20.80.95

1163150

NA

Stainless
steel

0.1860.214

0.381.55

1550

Kevlar
29&149

0.060.18

3.63.8]

~2

APPLICATIONS:-

Carbon nanotubes (Buckytubes) have extraordinary electrical


conductivity, heat conductivity and mechanical properties. They are
probably the best electron field-emitter possible. They are polymers
of pure carbon and can be reacted and manipulated using the
tremendously rich chemistry of carbon. This provides opportunity to
modify the structure and to optimize solubility and dispersion.
Very significantly, buckytubes are molecularly perfect, which means
that they are free of property-degrading flaws in the nanotube
structure. Their material properties can therefore approach closely
the very high levels intrinsic to them.
These extraordinary characteristics give buckytubes potential in
numerous applications.

a) Structural

Clothes: waterproof tear-resistant cloth fibers

Combat jackets: MIT is working on combat jackets that use


carbon nanotubes as ultra strong fibers and to monitor the
condition of the wearer.

Concrete: In concrete, they increase the tensile strength, and


halt crack propagation.

Polyethylene: Researchers have found that adding them to


polyethylene increases the polymer's elastic modulus by 30%.

Sports equipment: Stronger and lighter tennis rackets, bike


parts, golf balls, golf clubs, golf shaft and baseball bats.

Space elevator: This will be possible only if tensile strengths


of more than about 70 GPa can be achieved. Monoatomic
oxygen in the Earth's upper atmosphere would erode carbon
nanotubes at some altitudes, so a space elevator constructed
of nanotubes would need to be protected (by some kind of
coating). Carbon nanotubes in other applications would
generally not need such surface protection.

Ultrahigh-speed flywheels: The high strength/weight ratio


enables very high speeds to be achieved.

b) ELECTROMAGNETIC

Buckypaper:
It is a thin sheet made from nanotubes that
are 250 times stronger than steel and 10 times lighter that
could be used as a heat sink for chipboards, a backlight for
LCD screens or as a faraday cage to protect electrical
devices/aero planes.

Chemical nanowires:
Carbon nanotubes additionally can
also be used to produce nanowires of other chemicals, such as
gold or zinc oxide. These nanowires in turn can be used to
cast nanotubes of other chemicals, such as gallium nitride.
These can have very different properties from CNTs for
example, gallium nitride nanotubes are hydrophilic, while CNTs
are hydrophobic, giving them possible uses in organic
chemistry that CNTs could not be used for.

Computer circuits:
A nanotube formed by joining
nanotubes of two different diameters end to end can act as a
diode, suggesting the possibility of constructing electronic
computer circuits entirely out of nanotubes. Because of their
good thermal properties, CNTs can also be used to dissipate
heat from tiny computer chips.

Conductive films:
CNTs are also introduced in developing
transparent, electrically conductive films to replace indium tin
oxide(ITO).CNT films are substantially more mechanically
robust then ITO films ,making them ideal for more reliability
touch screens and flexible displays. Printable water based inks
of carbon nanotubes are desired to enable the production of
these films to replace the ITO. Nanotube films show promise
for use in displays for cell phones, computers, PDAs, and
ATMs.

Electric motor brushes:


Conductive carbon
nanotubes have been used for several years in brushes for
commercial electric motors.. The nanotubes improve electrical
and thermal conductivity because they stretch through the
plastic matrix of the brush. This permits the carbon filler to be
reduced from 30% down to 3.6%, so that more matrixes are
present in the brush. Nanotube composite motor brushes are

better-lubricated (from the matrix), cooler-running (both from


better lubrication and superior thermal conductivity), less
brittle (more matrix, and fiber reinforcement), stronger and
more accurately moldable (more matrix). Since brushes are a
critical failure point in electric motors, and also dont need
much material, they became economical before almost any
other application.

Light bulb filament:


incandescent lamps.

Alternative to tungsten filaments in

Solar cells:
Organic photovoltaic devices (OPVs) are
fabricated from thin films of organic semiconductors, such as
polymers and small-molecule compounds, and are typically on
the order of 100 nm thick. Because polymer based OPVs can
be made using a coating process such as spin coating or inkjet
printing, they are an attractive option for inexpensively
covering large areas as well as flexible plastic surfaces. A
promising low cost alternative to silicon solar cells, there is a
large amount of research being dedicated throughout industry
and academia towards developing OPVs and increasing their
power conversion efficiency. GEs carbon nanotube diode has
a photovoltaic effect. Nanotubes can replace ITO (Indium tin
oxide) in some solar cells to act as a transparent conductive
film in solar cells to allow light to pass to the active layers and
generate photocurrent.

CNTs in dye-sensitized solar cells:Due to the simple fabrication process,


low production cost, and high efficiency, there is
significant interest in dye-sensitized solar cells (DSSCs).

Thus, improving DSSC efficiency has been the subject of


a variety of research investigations because it has the
potential to be manufactured economically enough to
compete with other solar cell technologies. Titanium
dioxide nanoparticles have been widely used as a
working electrode for DSSCs because they provide a
high efficiency, more than any other metal oxide
semiconductor investigated. Yet the highest conversion
efficiency under air mass (AM) 1.5 (100 mW/cm2)
irradiation reported for this device to date is about 11%.
Despite this initial success, the effort to further enhance
efficiency has not produced any major results. The
transport of electrons across the particle network has
been a key problem in achieving higher photo
conversion efficiency in nanostructured electrodes.
Because electrons encounter many grain boundaries
during the transit and experience a random path, the
probability of their recombination with oxidized
sensitizer is increased. Therefore, it is not adequate to
enlarge the oxide electrode surface area to increase
efficiency because photo-generated charge
recombination should be prevented. Promoting electron
transfer through film electrodes and blocking interface
states lying below the edge of the conduction band are
some of the non-CNT based strategies to enhance
efficiency that have been employed.
With recent progress in CNT development and
fabrication, there is promise to use various CNT based
nanocomposites and nanostructures to direct the flow of
photo generated electrons and assist in charge injection
and extraction. To assist the electron transport to the
collecting electrode surface in a DSSC, a popular
concept is to utilize CNT networks as support to anchor
light harvesting semiconductor particles.
"Efficiencies reaching 4.4% have already been achieved
and hopefully 10-15% efficiencies are feasible in the near-future
upon further optimization" says Kymakis. "Once this obstacle is
tackled, the lifetime issue, which is directly related to the cell
temperatures, can be explored. A working environment
combining the strengths of scientists and business leaders may
soon result in rapid commercialization of this technology."

Superconductor:
Nanotubes have been shown to be
superconducting at low temperatures.

Ultra capacitors:
Nanotubes, when bound to plates of
capacitors increase the surface area and thus increase energy
storage ability.

Displays:
One use for nanotubes that has already been
developed is as extremely fine electron guns, which could be
used as miniature cathode ray tubes in thin high-brightness
low-energy low-weight displays. This type of display would
consist of a group of many tiny CRTs, each providing the
electrons to hit the phosphor of one pixel, instead of having
one giant CRT whose electrons are aimed using electric and
magnetic fields. These displays are known as field emission
displays (FEDs).

Others:

Artificial muscles, magnets, optical ignition etc.

c) CHEMICAL

Air pollution filter:


Future applications of nanotube
membranes include filtering carbon dioxide from power plant
emissions.

Biotech container:
Nanotubes can be opened and filled
with materials such as biological molecules, raising the
possibility of applications in biotechnology.

Hydrogen storage:
Research is currently being
undertaken into the potential use of carbon nanotubes for
hydrogen storage. They have the potential to store between
4.2 and 65% hydrogen by weight. This is an important area of
research, since if they can be mass produced economically
there is potential to contain the same quantity of energy as a
50L gasoline tank in 13.2L of nanotubes. See also, Hydrogen
Economy.

Water filter:
Recently nanotube membranes have been
developed for use in filtration. This technique can purportedly
reduce desalination costs by 75%. The tubes are so thin that
small particles (like water molecules) can pass through them,
while larger particles (such as the chloride ions in salt) are
blocked.

Oscillator:

Nanotube membrane:
Liquid flows up to five orders of
magnitude faster than predicted by classical fluid dynamics.

Smooth surface:

Fastest known oscillators (> 50 GHz).

Smoother than Teflon and waterproof.

d) MECHANICAL

Oscillator: fastest known oscillators (> 50 GHz).

Liquid flow array: Liquid flows up to five orders of


magnitude faster than predicted through array.

Slick surface: slicker than Teflon and waterproof.

e) CARBON NANOTUBE INTERCONNECTS


Metallic CNTs have aroused a lot of research interest in their
applicability as Very-large-scale integration (VLSI) interconnects of
the future because of their desirable properties of high thermal
stability, high thermal conductivity and large current carrying
capacity. An isolated CNT can carry current densities in excess of
1000 MA/sq-cm without any signs of damage even at an elevated
temperature of 250 degrees C, thereby eliminating electromigration
reliability concerns that plague Cu interconnects. Recent modeling
work comparing the performance, power dissipation and
thermal/reliability aspects of CNT interconnect to scaled copper
interconnects have shown that CNT bundle interconnects can
potentially offer more advantages over copper.
f) TRANSISTORS

Smaller silicon based integrated circuits result in both a higher


speed and device density. As a result, downscaling of these devices
has been very important since their first implementation. However,
at the moment it is generally accepted that silicon devices will reach
fundamental scaling limits within a decade or so. This limit is
caused by the minimum wavelength of light used in lithographic
techniques used for integrated circuit production nowadays. For this
reason a quest for alternative, integrated circuits with smaller
dimensions has started. A major step in downscaling would be the
application of single molecules in electronic devices. Carbon
nanotubes have already shown promising results in single molecular
transistors. For successful implementation of molecular transistors
in large and complex logic systems, they must show signal
amplification. Signal amplification makes it possible to reference
separate signals along a chain of logical operations. In addition,
noise caused by thermal fluctuations and environmental
disturbances is also reduced. Three terminal nanotransistors, in
special, field-effect-transistors show amplifying behavior and have
recently been investigated for this reason.
g) Electrical circuits
Carbon nanotubes have many propertiesfrom their unique
dimensions to an unusual current conduction mechanismthat
make them ideal components of electrical circuits. Currently, there
is no reliable way to arrange carbon nanotubes into a circuit.
The major hurdles that must be jumped for carbon nanotubes to find
prominent places in circuits relate to fabrication difficulties. The
productions of electrical circuits with carbon nanotubes are very
different from the traditional IC fabrication process. The IC
fabrication process is somewhat like sculpture - films are deposited
onto a wafer and pattern-etched away. Because carbon nanotubes
are fundamentally different from films, carbon nanotube circuits can
so far not be mass produced.
Researchers sometimes resort to manipulating nanotubes one-byone with the tip of an atomic force microscope in a painstaking,
time-consuming process. Perhaps the best hope is that carbon
nanotubes can be grown through a chemical vapor deposition
process from patterned catalyst material on a wafer, which serve as

growth sites and allow designers to position one end of the


nanotube. During the deposition process, an electric field can be
applied to direct the growth of the nanotubes, which tend to grow
along the field lines from negative to positive polarity. Another way
for the self assembly of the carbon nanotube transistors consist in
using chemical or biological techniques to place the nanotubes from
solution to determinate place on a substrate.
Even if nanotubes could be precisely positioned, there remains the
problem that, to this date, engineers have been unable to control
the types of nanotubesmetallic, semiconducting, single-walled,
multi-walledproduced. A chemical engineering solution is needed
if nanotubes are to become feasible for commercial circuits.

h) OTHER APPLICATIONS

CNTs have also been implemented in nano electromechanical


systems, including mechanical memory elements.
CNTs have also been proposed as a possible gene delivery
vehicle and for use in combination in radio frequency fields to
destroy cancer cells.
Nanomix Inc was the first to put on the market an electronic
device that integrated carbon nanotubes on a silicon platform,
in may 2005. It was a hydrogen sensor. Since then nanomix
has been patenting many such sensor applications such as in
the field of Carbon-di-oxide, Nitrous Oxide, glucose, DNA
detection etc.
As a container for drug delivery: Because of the versatile
structure of the CNT, it can be used for a variety of tasks in
and around body. Often in the cancer related incidents, the
CNT is often used as a container for transporting drugs into
the body. Here drugs can actually be placed inside the
nanotubes or can be attached to the side or trailed behind.
Both of these methods are effective for the delivery and
distribution of drug inside out of the body.
CNTs can be used as light emitting semiconductors.

CONCLUSION
Rise in demand and production, and ease of accessibility of carbon
nanotubes would lead to the extensive use of carbon nanotubes in a
wide variety of applications. The use of nanotechnology for human
will become common need in 21st century. As world is suffering from
serious pollution problems, hydrogen will becoming need of 21st
century & carbon nanotubes provide better solution for hydrogen
storage.
Nanotubes market, which was growing at a moderate rate till 20062007, is expected to rise at a skyrocketing pace in the coming years.
Hence we can conclude that most of the demands of human, in this
and fore coming generation will be fulfilled by carbon nanotubes.