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 highpressure 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 graphite-like 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 Hanns-Peter 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 two-dimensional 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 atomic-resolution 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 E-k 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 five-membered 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. Arc-discharge 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 nanotube-device architectures for practical applications

This method has a yield of around 70% and produces primarily singlewalled 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 Nickelcatalyzed 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 well-dispersed 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 apparatus.

diagram

of

plasma

CVD

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 multiwalled 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 NH3 gas at a temperature of 750 to 1050o 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 SWNTs40 and between 70 and 100 nm for MWNTs.

Method

Who

How

Typical yield SWNT

Chemical Arc discharge Laser ablation method vapour (vaporization) deposition Ebbesen andEndo, ShinshuSmalley, Rice, 199514 Ajayan, NEC, JapanUniversity, 1992 15 Nagano, Japan 53 Connect twoPlace substrate inBlast graphite with graphite rods to aoven, heat tointense laser pulses; o power supply,600 C, and slowlyuse the laser pulses place them a fewadd a carbon-rather than electricity millimeters apart,bearing gas suchto generate carbon and throw theas methane. Asgas from which the switch. At 100gas decomposes itNTs form; try various amps, carbonfrees up carbonconditions until hit on vaporizes andatoms, whichone that produces forms hot plasma. recombine in theprodigious amounts form of NTs of SWNTs 30 to 90% 20 to 100 % Up to 70% Short tubes withLong tubes withLong bundles of diameters of 0.6 -diameters rangingtubes (5-20 microns),

Method

Chemical Arc discharge method vapour deposition 1.4 nm from 0.6-4 nm

Laser ablation (vaporization)

M-WNT

Pro

Con

with individual diameter from 1-2 nm. 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 MWNT approximately 10 synthesis is possible. nm Can easily produceEasiest to scale upPrimarily SWNTs, with SWNT, MWNTs.to industrialgood diameter SWNTs have fewproduction; longcontrol and few structural defects;length, simpledefects. The reaction MWNTs withoutprocess, SWNTproduct is quite pure. catalyst, not toodiameter expensive, opencontrollable, quite air synthesispure possible 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 highenergy 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 interplane 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 armchair-structured 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 half-transistor 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 semi-conducting 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)
SWNT Armchair SWNT Zigzag SWNT Chiral SWNT MWNTE Stainless steel Kevlar 29&149 ~1 (from 1 to 5)

Pa)
1353 16

0.94

126.2

23.1

0.94

94.5

15.617.5

0.92

NA

NA

0.20.80.95

1163150

NA

0.1860.214

0.381.55

1550

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: Fastest known oscillators (> 50 GHz).

Nanotube membrane: Liquid flows up to five orders of magnitude faster than predicted by classical fluid dynamics. Smooth surface: 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-by-one with the tip of an atomic force microscope in a painstaking, timeconsuming 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, multiwalledproduced. 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.