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Carbon Nanotubes -1-

Contents

Abstract

Introduction

History

Properties
Structure
Strength
Kinetic
Thermal
Electrical
Defects
Conductance & Mobility

Synthesis
Arc Discharge
Laser Ablation
Chemical Vapor Deposition (CVD)

Device Fabrication
Fire em and wire em
CVD growth of nanotubes
Locating the nanotubes
Electrical Measurements

Application
Structural
Electromagnetic
Chemical
Mechanical
In electrical circuits
As fiber and film

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Conclusion

Reference

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Abstract

Carbon nanotubes (CNTs) are a recently discovered allotrope of carbon. They take the form
of cylindrical carbon molecules and have novel properties that make them potentially useful in
a wide variety of applications in nanotechnology, electronics, optics, and other fields of
materials science. They exhibit extraordinary strength and unique electrical properties, and are
efficient conductors of heat. Inorganic nanotubes have also been synthesized.

A nanotube is a member of the fullerene structural family, which also includes buckyballs.
Whereas buckyballs are spherical in shape, a nanotube is cylindrical, with at least one end
typically capped with a hemisphere of the buckyball structure. Their name is derived from
their size, since the diameter of a nanotube is on the order of a few nanometers (approximately
50,000 times smaller than the width of a human hair), while they can be up to several
millimeters in length. There are two main types of nanotubes: single-walled nanotubes
(SWNTs) and multi-walled nanotubes (MWNTs).

Manufacturing a nanotube is dependent on applied quantum chemistry, specifically, orbital


hybridization. Nanotubes are composed entirely of sp2 bonds, similar to those of graphite. This
bonding structure, 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 sp2 bonds
for sp3 bonds, giving great possibility for producing strong, unlimited-length wires through
high-pressure nanotube linking

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Introduction

What is a CARBON NANOTUBE?

Carbon nanotubes are wires of pure carbon with nanometer diameters and lengths of many
microns. A single-walled carbon nanotube (SWNT) may be thought of as a single atomic
layer thick sheet of graphite (called graphene) rolled into a seamless cylinder. Multi-walled
carbon nanotubes (MWNT) consist of several concentric nanotube shells.

Understanding the electronic properties of the graphene sheet helps to understand the
electronic properties of carbon nanotubes. Graphene is a zero-gap semiconductor; for most
directions in the graphene sheet, there is a bandgap, and electrons are not free to flow along
those directions unless they are given extra energy. However, in certain special directions
graphene is metallic, and electrons flow easily along those directions. This property is not
obvious in bulk graphite, since there is always a conducting metallic path which can connect
any two points, and hence graphite conducts electricity.

However, when graphene is rolled up to make the nanotube, a special direction is selected, the
direction along the axis of the nanotube. Sometimes this is a metallic direction, and
sometimes it is semiconducting, so some nanotubes are metals, and others are
semiconductors. Since both metals and semiconductors can be made from the same all-carbon
system, nanotubes are ideal candidates for molecular electronics technologies.

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Three nanotubes of different chiralities.

In addition to their interesting electronic structure, nanotubes have a number of other useful
properties. Nanotubes are incredibly stiff and tough mechanically - the world's strongest
fibers. Nanotubes conduct heat as well as diamond at room temperature. Nanotubes are very
sharp, and thus can be used as probe tips for scanning-probe microscopes, and field-emission
electron sources for lamps and displays.

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History

The current huge interest in carbon nanotubes is a direct consequence of the synthesis of
buckminsterfullerene, C60, and other fullerenes, in 1985. The discovery that carbon could form
stable, ordered structures other than graphite and diamond stimulated researchers worldwide
to search for other new forms of carbon. The search was given new impetus when it was
shown in 1990 that C60 could be produced in a simple arc-evaporation apparatus readily
available in all laboratories. It was using such an evaporator that the Japanese scientist Sumio
Iijima discovered fullerene-related carbon nanotubes in 1991. The tubes contained at least two
layers, often many more, and ranged in outer diameter from about 3 nm to 30 nm. They were
invariably closed at both ends.

A transmission electron micrograph of some multiwalled nanotubes is shown in the figure


(left). In 1993, a new class of carbon nanotube was discovered, with just a single layer. These
single-walled nanotubes are generally narrower than the multiwalled tubes, with diameters
typically in the range 1-2 nm, and tend to be curved rather than straight. The image on the
right shows some typical single-walled tubes It was soon established that these new fibres had

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a range of exceptional properties (see below), and this sparked off an explosion of research
into carbon nanotubes. It is important to note, however, that nanoscale tubes of carbon,
produced catalytically, had been known for many years before Iijimas discovery. The main
reason why these early tubes did not excite wide interest is that they were structurally rather
imperfect, so did not have particularly interesting properties. Recent research has focused on
improving the quality of catalytically-produced nanotubes.

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Properties

The strength of the sp carbon-carbon bonds gives carbon nanotubes amazing mechanical
properties. The stiffness of a material is measured in terms of its Young's modulus, the rate of
change of stress with applied strain. The Young's modulus of the best nanotubes can be as
high as 1000 GPa which is approximately 5x higher than steel. The tensile strength, or
breaking strain of nanotubes can be up to 63 GPa, around 50x higher than steel. These
properties, coupled with the lightness of carbon nanotubes, gives them great potential in
applications such as aerospace. It has even been suggested that nanotubes could be used in the
space elevator, an Earth-to-space cable. The electronic properties of carbon nanotubes are
also extraordinary. Especially notable is the fact that nanotubes can be metallic or
semiconducting depending on their structure. Thus, some nanotubes have conductivities
higher than that of copper, while others behave more like silicon. There is great interest in the
possibility of constructing nanoscale electronic devices from nanotubes, and some progress is
being made in this area. However, in order to construct a useful device we would need to
arrange many thousands of nanotubes in a defined pattern, and we do not yet have the degree
of control necessary to achieve this. There are several areas of technology where carbon
nanotubes are already being used. These include flat-panel displays, scanning probe
microscopes and sensing devices. The unique properties of carbon nanotubes will undoubtedly
lead to many more applications.

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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 in the diagram below.

The first two of these, known as armchair (top left) and zig-zag (middle left) have a high
degree of symmetry. 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 shown at the bottom left.

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The structure of a nanotube can be specified by a vector, (n,m), which defines how the
graphene sheet is rolled up. This can be understood with reference to figure on the right. To
produce a nanotube with the indices (6,3), say, the sheet is rolled up so that the atom labelled
(0,0) is superimposed on the one labelled (6,3). It can be seen from the figure that m = 0 for all
zig-zag tubes, while n = m for all armchair tubes.

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Strength

Carbon nanotubes are one of the strongest materials known to humans, both in terms of tensile
strength and elastic modulus. This strength results from the covalent sp2 bonds formed
between the individual carbon atoms. In 2000, an MWNT was tested to have a tensile strength
of 63 GPa. In comparison, high-carbon steel has a tensile strength of approximately 1.2 GPa.
CNTs also have very high elastic modulus, on the order of 1 TPa. Since carbon nanotubes
have a low density for a solid of 1.3-1.4 g/cm, its specific strength is the best of known
materials.

Under excessive tensile strain, the tubes will undergo plastic deformation, which means the
deformation is permanent. This deformation begins at strains of approximately 5% [Qian et al,
2002] and can increase the maximum strain the tube undergoes before fracture by releasing
strain energy.

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, torsional or
bending stress.

Kinetic

Multiwalled carbon nanotubes, multiple concentric nanotubes precisely nested within one
another, exhibit a striking telescoping property whereby an inner nanotube core may slide,
almost without friction, within its outer nanotube shell thus creating an atomically perfect
linear or rotational bearing. This is one of the first true examples of molecular
nanotechnology, the precise positioning of atoms to create useful machines. Already this
property has been utilized to create the world's smallest rotational motor and a nanorheostat.
Future applications such as a gigahertz mechanical oscillator are envisioned.

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Electrical

Because of the symmetry and unique electronic structure of graphene, the structure of a
nanotube strongly affects its electrical properties. For a given (n,m) nanotube, if 2n + m=3q
(where q is an integer), then the nanotube is metallic, otherwise the nanotube is a
semiconductor. Thus all armchair (n=m) nanotubes are metallic, and nanotubes (5,0), (6,4),
(9,1), etc. are semiconducting. In theory, metallic nanotubes can have an electrical current
density more than 1,000 times greater than metals such as silver and copper.

Thermal

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.

Defects

As with any material, the existence of defects affects the material properties. Defects can
occur in the form of atomic vacancies. High levels of such defects can lower the tensile
strength by up to 85%. Another well-known form of defect that occurs in carbon nanotubes is
known as the Stone Wales defect, which creates a pentagon and heptagon pair by
rearrangement of the bonds. Because of the almost one-dimensional structure of CNTs, the
tensile strength of the tube is dependent on the weakest segment of it in a similar manner to a
chain, where a defect in a single link diminishes the strength of the entire chain.

The tube's electrical properties are also affected by the presence of defects. A common result
is the lowered conductivity through the defective region of the tube. Some defect formation in
armchair-type tubes (which are metallic) can cause the region surrounding that defect to
become semiconducting. Furthermore single monoatomic vacancies induce magnetic
properties.

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The tube's thermal properties are heavily affected by defects. Such defects lead to phonon
scattering, which in turn increases the relaxation rate of the phonons. This reduces the mean
free path, and reduces the thermal conductivity of nanotube structures.

Conductance and Mobility

Recently, much of our research has focused on semiconducting nanotubes, because of their
utility for devices. Since the conductance of the semiconducting nanotube can be changed by
the voltage on a third electrode (the gate), the nanotube acts like a switch. This type of switch
is called a field-effect transistor (FET), and forms the basis of most computer chips used
today. We are very interested in determining how well nanotubes perform as field-effect
transistors, in order to gauge their prospects for future electronics applications.

The first question one might ask is: How well do semiconducting nanotubes conduct? The
figure below shows the conductance of a very long nanotube (about 1/3 of a millimeter long)
as a function of gate voltage. The highest conductance observed is 1.6 micro-Siemens, which
corresponds to a resistance of around 600 kilo-Ohms. How does this compare to other
materials? In order to compare, we need to consider the conductivity, conductance x
length/area. This takes into account the fact that we expect a long, thin wire to have lower
conductance than a short, fat wire. The conductivity of the nanotube is around 2.6 micro-
Ohm-centimeters. This is comparable to good metals like copper (1.6 micro-Ohm-
centimeters), which is very surprising. This means that this nanotube switch can be tuned
from insulating, to conducting as well as copper, simply by changing the gate voltage!

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The top panel shows an SEM image of a long


semiconducting carbon nanotube spanning between two gold
electrodes (scale bar is 100 micrometers). The bottom graph
shows the conductance of this nanotube as a function of the
voltage applied to the back gate (silicon substrate) at
temperatures of 300, 200, and 100 Kelvins.

The above analysis also hints that conductivity isn't the best number to use when comparing
one semiconductor to another, since the conductivity changes with charge density (in this case
with gate voltage). It's fine for metals, like copper, where the charge density is very high and
doesn't change much. The number that's used to indicate how well one semiconductor
conducts compared to another is mobility. Mobility is the conductance divided by the density
of charge carriers, so it can be used to compare the conductance of semiconductor samples
with different amounts of charge to carry the current.

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We know the charge density in our nanotube devices, because we know the capacitance C
between the nanotube and the gate electrode that is producing the charge. The charge Q is
proportional to the capacitance and to the amount of gate voltage V we have applied: Q = CV.
So we know everything we need to find the mobility. The mobility of one of our long
nanotube transistors is shown below.

Mobility as a function of gate voltage for a semiconducting carbon


nanotube. At low gate voltage (low charge carrier density) the mobility
exceeds that of InSb (77,000 cm2/Vs), the previous highest-known
mobility at room temperature.

The mobility is higher than 100,000 cm2/Vs at room temperature, higher than any other known
semiconductor. (The previous record, for InSb, was 77,000 cm2/Vs, set in 1955.) The
mobility is a function of the gate voltage, and is higher when the gate voltage is low, i.e. when

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there are fewer charges in the devices. We don't know why this is yet, but we are studying
this. The mobility is also rather independent of temperature, suggesting that the thermal
vibrations of the lattice, called phonons, don't play much of a role in scattering the electrons.

Why is the mobility so high? Part of the reason is that graphite itself is a good conductor of
electricity. The mobility of charges in graphite is around 20,000 cm2/Vs at room temperature.
Graphite also has other excellent properties - it's strong, lightweight, and an excellent
conductor of heat. But graphite isn't a semiconductor - it doesn't have a bandgap - so it can't
be used to make semiconductor devices like transistors. The nanotube can be thought of as a
way to engineer a bandgap in graphite so we can use it for semiconductor devices (see
Introduction to Carbon Nanotubes above). The mobility in nanotubes turns out to be even
higher than in graphite. Part of the reason for this may lie in the one-dimensional nature of the
nanotube - it's harder to scatter electrons in one-dimension, because they can only go forward
or backward, not to the sides.

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Synthesis

Techniques have been developed to produce nanotubes in sizeable quantities, including arc
discharge, laser ablation, high pressure carbon monoxide (HiPco), and chemical vapor
deposition (CVD). Most of these processes take place in vacuum or with process gases. CVD
growth of CNTs can take place in vacuum or at atmospheric pressure. Large quantities of
nanotubes can be synthesized by these methods; advances in catalysis and continuous growth
processes are making CNTs more commercially viable. The arc-evaporation method, which
produces the best quality nanotubes, involves passing a current of about 50 amps between two
graphite electrodes in an atmosphere of helium. This causes the graphite to vaporise, some of
it condensing on the walls of the reaction vessel and some of it on the cathode. It is the deposit
on the cathode which contains the carbon nanotubes. Single-walled nanotubes are produced
when Co and Ni or some other metal is added to the anode. It has been known since the 1950s,
if not earlier, that carbon nanotubes can also be made by passing a carbon-containing gas,
such as a hydrocarbon, over a catalyst. The catalyst consists of nano-sized particles of metal,
usually Fe, Co or Ni. These particles catalyse the breakdown of the gaseous molecules into
carbon, and a tube then begins to grow with a metal particle at the tip. It was shown in 1996
that single-walled nanotubes can also be produced catalytically. The perfection of carbon
nanotubes produced in this way has generally been poorer than those made by arc-
evaporation, but great improvements in the technique have been made in recent years. The big
advantage of catalytic synthesis over arc-evaporation is that it can be scaled up for volume
production. The third important method for making carbon nanotubes involves using a
powerful laser to vaporise a metal-graphite target. This can be used to produce single-walled
tubes with high yield.

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Arc discharge

Nanotubes were observed in 1991 in the carbon soot of graphite electrodes during an arc
discharge that was intended to produce fullerenes. During this process, 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 perhaps the most
widely used method of nanotube synthesis.

Laser ablation

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.

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Chemical vapor deposition (CVD)

Nanotubes being grown by plasma enhanced chemical vapor deposition

The catalytic vapor phase deposition of carbon was first reported in 1959, but it was not until
1993 that carbon nanotubes could be formed by this process.

During 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 (or
masked) 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, 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, where it forms the nanotubes. The catalyst particles generally stay at the tips of
the growing nanotube during the growth process, although in some cases they remain at the
nanotube base, depending on the adhesion between the catalyst particle and the substrate.

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 (i.e., perpendicular to the substrate), a
morphology that has been of interest to researchers interested in the electron emission from
nanotubes. Without the plasma, the resulting nanotubes are often randomly oriented,
resembling a bowl of spaghetti. Under certain reaction conditions, even in the absence of a

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plasma, closely spaced nanotubes will maintain a vertical growth direction resulting in a dense
array of tubes resembling a carpet or forest.

Of the various means for nanotube synthesis, CVD shows the most promise for industrial
scale deposition in terms of its price/unit ratio. There are additional advantages to the CVD
synthesis of nanotubes. Unlike the above methods, CVD is capable of growing nanotubes
directly on a desired substrate, whereas the nanotubes must be collected in the other growth
techniques. The growth sites are controllable by careful deposition of the catalyst.
Additionally, no other growth methods have been developed to produce vertically aligned
nanotubes. Natural, incidental, and controlled flame environments

Fullerenes and carbon nanotubes are not necessarily products of high-tech laboratories; they
are commonly formed in such mundane places as ordinary flames, produced by burning
methane, ethylene, and benzene, and they have been found in soot from both indoor and
outdoor air. However, these naturally occurring varieties can be highly irregular in size and
quality because the environment in which they are produced is often highly uncontrolled.
Thus, although they can be used in some applications, they can lack in the high degree of
uniformity necessary to meet many needs of both research and industry. Recent efforts have
focused on producing more uniform carbon nanotubes in controlled flame environments.

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Device Fabrication

Find 'em and wire 'em

This is a technique for synthesizing carbon nanotubes directly on silicon substrates, locating
individual nanotubes, and electrically contacting nanotubes with metallic electrodes. The
general idea is to "find 'em and wire 'em", as opposed to attempting to self-assemble
nanotubes in place, or deposit nanotubes or wires at random and hope to contact some
nanotubes. The great advantage of the find 'em and wire 'em technique is that customized
devices can be made. Some examples are below.

Atomic force microscope (AFM) image of Scanning electron microscope (SEM) image
crossed nanotubes (green) contacted by Au of a long nanotube transistor fabricated at
electrodes (yellow) using the "find 'em and Maryland using the "find 'em and wire 'em"
wire 'em" technique. In this work, performed technique. The nanotube is the thin
at UC Berkeley, the nanotubes were horizontal white line connecting the two gold
deposited onto the chip from solution, and leads (thicker vertical lines). Here the
located using the AFM. nanotubes were grown by chemical vapor
deposition directly on the substrate, and
located using the SEM.

The disadvantages of the find 'em and wire 'em scheme are that only a limited number of
devices can be made, and the technique is not "scalable" - that is, making twice as many

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devices takes twice as much time. If nanotubes are to find electronic applications in industry,
scalable fabrication techniques will be needed.

CVD growth of nanotubes

Chemical Vapor Deposition (CVD) can be used to prepare carbon nanotubes. The basic
ingredients needed for CVD growth of nanotubes are a small catalyst particle (typically iron
or iron/molybdenum) and a hot environment of carbon-containing gas (we use CH4 and
C2H4). The metal particle catalyzes the decomposition of the carbon-containing gases, and the
carbon dissolves in the catalyst particle. Once the catalyst particle is supersaturated with
carbon, it extrudes out the excess carbon in the form of a tube. One catalyst particle of a few
nanometers in diameter can produce a nanotube millimeters in length, about 1 million times
the size of the particle.

Nanotubes grown by the CVD process on a silicon dioxide


covered silicon chip. The thin white lines are the
nanotubes. The nanotubes here form a continuous
conducting network, and thus are too dense to use for device
fabrication.

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Typically silicon chips (pieces of flat silicon wafer from the semiconductor industry) are used
as the substrate material, with a layer of silicon dioxide (glass) grown on top of the silicon as
an insulator. The catalyst can be obtained in several ways; the easiest is to dip the silicon chip
into a solution of ferric nitrate in isopropanol, and then dip the chip into hexane to cause the
ferric nitrate to come out of solution. This deposits nanocrystals of ferric nitrate on the chip,
which can be reduced to iron with hydrogen in the growth furnace.

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Locating the nanotubes

Once the nanotubes are grown on the substrates, they need to be located. To do this, first a
pattern of alignment marks on the substrate is deposited, using a conventional lithography
technique. A method for locating nanotubes is to use an atomic force microscope (AFM). The
AFM uses a tiny needle on the end of a diving-board-like cantilever to tap on a surface as it
scans over that surface. It senses the amplitude of the tapping and uses that to follow the
height variations in the surface, making a topographical map of the area. The AFM is very
sensitive, so it is able to image the nanometer-diameter nanotubes lying on the flat substrate.
However, AFM is very time consuming, taking 5 minutes or so to image a 10 x 10 micron
square image.

Another technique is to image nanotubes using the scanning electron microscope (SEM). This
imaging technique relies on the fact that the nanotubes are conducting, and the substrate on
which they are lying is insulating. The SEM images by scanning a high-energy beam of
electrons over the sample. Secondary electrons generated by the energetic beam are collected
and amplified to produce the image signal. When the SEM beam hits an insulator, some
electrons stick in the insulator and it becomes negatively charged. When the beam scans over
the nanotube, the electrons are free to spread out along the nanotube, and thus the area around
the nanotube is less negatively charged. The less negatively charged area allows more
electrons from the substrate to escape and be detected, producing a signal when the beam
scans across the nanotube. Examples of SEM and AFM images of nanotubes are seen below.

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Fig: Comparison of field-emission scanning electron microscope (FESEM) and


atomic force microscope (AFM) images of nanotubes (two narrow lines) and Cr/Au
alignment markers (squares and geometric shapes). The FESEM (a) images the
conducting alignment marks and nanotubes, but is insensitive to the surface
contamination visible in the AFM image (b). The FESEM image was acquired
approximately 100 times faster than the AFM scan.

Once the nanotubes are located, they may be contacted electrically using electron-beam
lithography (EBL). A thin layer of resist (a polymer) is spun onto the chip, and the SEM is
used again, but this time the energetic electron beam is used to write a pattern in the resist
where we want the electrodes to be. The resist which has been exposed to the beam is then
washed away in a solvent, and metal (such as gold) is evaporated into the holes in the resist,
forming wires which contact the nanotubes. The excess metal which is on top of the resist is
lifted off of the chip using a second solvent which dissolves the remaining resist. The
electrodes for both the crossed nanotube device and the long nanotube device shown above
were fabricated using EBL.

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Electrical measurements

The wires on the chip are much bigger than the nanotube, but still fairly small - typically the
largest parts of the wires on the chip are one or two tenths of a millimeter across. We make
contact to the wires on the chip under a microscope, either by using a wire bonder which can
attach larger wires to the chip to connect it to a rigid chip holder, or by using a probe station,
which has sharp needles that can be used to temporarily make contact to the wires on the
chip.

Once electrical contacts are made to the nanotubes, we can test their electrical properties. The
simplest nanotube device has just two electrode, one at each end of the nanotube. There is
actually a third electrode, called the gate, which is the silicon substrate underneath the
nanotube. This electrode is not in electrical contact with the nanotube, since it is separated
from the nanotube by an insulator (typically silicon dioxide). However, the capacitor formed
by the nanotube and the gate can be charged by applying a voltage between nanotube and
gate. This way we can change the amount of charge on the nanotube.

When we change the gate voltage (changing the amount of charge on the nanotube) and
measure the conductance between the two contacts on the nanotube (conductance is the
inverse of resistance) we see one of two types of behavior. Either the conductance stays
constant as we change the gate voltage, or it drops dramatically as we make the gate voltage
more positive (see below). We identify the first type of behavior with the metallic nanotubes -
changing the charge on a metal does not change its conductance. The second type of behavior
we associate with the semiconducting nanotubes - unless they are "doped", semiconductors
don't have any charges which can carry current. The gate voltage allows us to add charge to
the nanotube and make it conduct. Negative gate voltage adds "holes" (positive charges
corresponding to the absence of an electron) to the nanotube, and it conducts better. Around

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zero gate voltage there are no holes, and the nanotube stops conducting. (The nanotube
should conduct again at a positive enough voltage which would add negatively charged
electrons to the nanotube, but it doesn't for reasons related to a barrier at the metal-nanotube
interface.)

Conductance as a function of gate voltage for (a) a metallic nanotube, and


(b) a semiconducting nanotube.

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Applications

The strength and flexibility of carbon nanotubes makes them of potential use in controlling
other nanoscale structures, which suggests they will have an important role in nanotechnology
engineering. The highest tensile strength an individual MWNT has been tested to be is
63 GPa. Bulk nanotube materials may never achieve a tensile strength similar to that of
individual tubes, but such composites may nevertheless yield strengths sufficient for many
applications. Carbon nanotubes have already been used as composite fibers in polymers and
concrete to improve the mechanical, thermal and electrical properties of the bulk product.

Structural

clothes: waterproof tear-resistant cloth fibers


combat jackets: MIT is working on combat jackets that use carbon nanotubes as
ultrastrong 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.

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Carbon Nanotubes - 29 -

Electromagnetic

artificial muscles
buckypaper - 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/aeroplanes.
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. The longest
electricity conducting circuit is a fraction of an inch long.(Source: June 2006 National
Geographic).
conductive films: A 2005 paper in Science notes that drawing transparent high strength
swathes of SWNT is a functional production technique (Zhang et. al., vol. 309, p.
1215). Additionally, Eikos Inc. of Franklin, Massachusetts is developing transparent,
electrically conductive films of carbon nanotubes to replace indium tin oxide (ITO) in
LCDs, touch screens, and photovoltaic devices. Carbon nanotube films are substantially
more mechanically robust than ITO films, making them ideal for high reliability touch
screens and flexible displays. Nanotube films show promise for use in displays for
computers, cell phones, PDAs, and ATMs.
electric motor brushes: Conductive carbon nanotubes have been used for several years
in brushes for commercial electric motors. They replace traditional carbon black, which

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Carbon Nanotubes - 30 -

is mostly impure spherical carbon fullerenes. 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 matrix is
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 don't need much material, they became economical before almost any
other application.
light bulb filament: alternative to tungsten filaments in incandescent lamps.
magnets: MWNTs coated with magnetite
optical ignition: A layer of 29% iron enriched SWNT is placed on top of a layer of
explosive material such as PETN, and can be ignited with a regular camera flash.
solar cells: GE's carbon nanotube diode has a photovoltaic effect. Nanotubes can
replace ITO 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.
superconductor: Nanotubes have been shown to be superconducting at low
temperatures.
ultracapacitors: MIT is researching the use of nanotubes bound to the charge plates of
capacitors in order to dramatically increase the surface area and therefore 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).
transistor: developed at Delft, IBM, and NEC.

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Carbon Nanotubes - 31 -

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.
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.

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.

In 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 production 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.

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Carbon Nanotubes - 32 -

Researchers sometimes resort to manipulating nanotubes one-by-one 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.

As fiber and film

One application for nanotubes that is currently being researched is high tensile strength fibers.
Two methods are currently being tested for the manufacture of such fibers. A French team has
developed a liquid spun system that involves pulling a fiber of nanotubes from a bath which
yields a product that is approximately 60% nanotubes. The other method, which is simpler but
produces weaker fibers uses traditional melt-drawn polymer fiber techniques with nanotubes
mixed in the polymer. After drawing, the fibers can have the polymer component burned out
of them leaving only the nanotube or they can be left as they are.

Ray Baughman's group from the NanoTech Institute at University of Texas at Dallas produced
the current toughest material known as of mid-2003 by spinning fibers of single wall carbon
nanotubes with polyvinyl alcohol. Beating the previous contender, spider silk, by a factor of
four, the fibers require 600 J/g to break In comparison, the bullet-resistant fiber Kevlar is 27

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Carbon Nanotubes - 33 -

33 J/g. In mid-2005, Baughman and co-workers from Australia's Commonwealth Scientific


and Industrial Research Organization developed a method for producing transparent carbon
nanotube sheets 1/1000th the thickness of a human hair capable of supporting 50,000 times
their own mass. In August 2005, Ray Baughman's team managed to develop a fast method to
manufacture up to seven meters per minute of nanotube tape. Once washed with ethanol, the
ribbon is only 50 nanometers thick; a square kilometer of the material would only weigh
30 kilograms.

In 2004, Alan Windle's group of scientists at the Cambridge-MIT Institute developed a way to
make carbon nanotube fiber continuously at the speed of several centimetres per second just
as nanotubes are produced. One thread of carbon nanotubes was more than 100 metres long.
The resulting fibers are electrically conductive and as strong as ordinary textile threads.

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Carbon Nanotubes - 34 -

Conclusion

Carbon nanotubes are the next step in miniaturizing electronic circuits, replacing silicon
transistors and diodes, which are fast reaching the theoretical limits of size and speed of
operation. Using CNTs, nanochips can be made with entire circuits on it. Ideal diodes can be
made from CNTs, resulting in highly efficient electronic circuits. Further, CNTs have a
number of other uses other than in the electronic industry, as seen here.

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Carbon Nanotubes - 35 -

Reference

http://www.pa.msu.edu/cmp/csc/ntproperties
http://en.wikipedia.org/wiki/Nanotubes
http://www.rdg.ac.uk/%7Escsharip/tubes.htm

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