CARBON NANOTUBES ASSIGNMENT

Sudeb Sarkar
A4455715002
BSc. Physics 6th Semester
 INTRODUCTION TO CARBON NANOTUBES

One can think of a carbon nanotube as a sheet of graphite rolled into a tube
with bonds at the end of the sheet forming the bonds that close the tube. A single-
waited nanotube (SWNT) can have a diameter of 2 nm and a length of100 um, making
it effectively a one dimensional structure called a nanowire.

Fig 1. Some possible structures of CNT depending on how graphite sheets are rolled
(a) armchair structures; (b) zigzag structures; (c) chiral structures

There are a variety of structures of carbon nanotubes, and these various

structures have different properties. Although carbon nanotubes are not actually made
by rolling graphite sheets, it is possible to explain the different structures by
consideration of the way graphite sheets might be rolled into tubes. A nanotube can be
formed when a graphite sheet is rolled up about die axis r shown in Fig. 2. The C h
vector is called the circumferential vector, and it is at right angles to T . Three
examples of nanotube structures constructed by rolling the graphite sheet about the T
vector having different orientations in the graphite sheet are shown in Fig. 1.
 There are many ways to roll a graphene into a single-wall nanotube, some of
the resulting nanotubes enabling symmetry mirrors both parallel and perpendicular to
the nanotube axis (such as the SWNTs from Fig.1 (a) and 1 (b)) The SWNT in Fig. 1
(c) is called chiral, as chiral molecules are unable to be superimposed with their
mirror image.

Fig 2. Illustration of notations used in understanding of carbon nanotubes and the

indexing scheme used in carbon nanotubes.

Chiral / Circumferential Vector C h=n a1 +m a2

Where a 1and a 2is defined as

a 1= ( √23 , 12 ) a
Which means that the x component ( x axis as defined in the diagram) is of the length
√3 a and the y component is of the length 1 a .
2 2

Similarly

a 2=( √23 ,− 12 ) a
Here a is the C−C bond length which is approximately equal to 1.421 Å for graphite
however for nanotubes, it is more appropriate to take a=1.44 Å as the approximation.
The length of C hgives the circumference of the tube which is given by

|C h|= √3 a √ m2+ n2 +mn

Eg.

1) For armchair nanotube (m=n)|C h|=3 na

2) For m=5 and n=5 ( 5,5 )|C h|=15 a
3) For zigzag nanotubes (m=0 ¿ |C h|=√ 3 na

Diameter of nanotube is given by

|C h| √3 a √m2 +n2 +mn

d= =
π π

The condition for metallic nanotube is

2 n+m=3 q (where q is integer)

OR

n−m
is an integer
3

From these conditions we can create a diagram which gives us the positions at which
we get metallic nanotubes if that position is overlapped with the position ( 0,0 )
Fig 3. The red solid point represents metallic nanotube and a black open circle
represents semiconductor nanotubes.

The Chiral angle θ  (angle between the chiral vector and the zigzag direction) is
defined as

θ=arctan ⁡(
√3 m )
m+2 n

For armchair ( m=n )

θ=arctan
( √13 )=30 °
For zigzag ( m=0 )

θ=arctan ( 0 )=0 °

HISTORY AND DISCOVERY

Sumio Ijima is credited with discovering CNT at NEC in 1991. He was

awarded the Benjamin Franklin Medal in Physics in 2002, "for the discovery and
elucidation of the atomic structure and helical character of multi-wall and single-wall
carbon nanotubes, which have had an enormous impact on the rapidly growing
condensed matter and materials science field of nanoscale science and electronics."
1952 - Radushkevich and Lukyanovich publish a paper in the Soviet Journal of
Physical Chemistry showing hollow graphitic carbon fibers that are 50 nanometers in
diameter.

1955 - Hofer, Sterling and McCarney observe a growth of tubular carbon filaments, of
10–200 nm in diameter.

1958 - Hillert and Lange observe a growth of nanoscale tubular carbon filaments from
n-heptane decomposition on iron at about 1000 °C.

1960 - Roger Bacon grows "graphite wiskers" in an arc-discharge apparatus and use
electron microscopy to show that the structure consist of rolled up graphene sheets in
concentric cylinders.
Bollmann and Spreadborough discuss friction properties of carbon due to rolling
sheets of graphene in Nature. Electron Microscope picture clearly shows MWCNT.

1971 - M.L. Lieberman reports growth of three different graphitic like filaments;
tubular, twisted, and balloon like. TEM images and diffraction data shows that the
hollow tubes are multi-walled carbon nanotubes (MWCNT).

1976 – Morinobu Endo reported CVD (Chemical Vapor Deposition) growth of

nanometer-scale carbon fibers, and they also reported the discovery of carbon
nanofibers, including that some were shaped as hollow tubes.

1979 - Arthur C. Clarke's science fiction novel The Fountains of Paradise popularizes
the idea of a space elevator using "a continuous pseudo-one dimensional diamond
crystal".

1982 - The continuous or floating-catalyst process was patented by Japanese

researcher Morinobu Endo.

1985 – Fullerenes discovered.

1991 - Nanotubes synthesized hollow carbon molecules and determined their crystal
structure for the first time in the soot of arc discharge at NEC, by Japanese
researcher Sumio Iijima
August — Nanotubes discovered in CVD by Al Harrington and Tom Maganas of
Maganas Industries, leading to development of a method to synthesize
monomolecular thin film nanotube coatings.

HOW TO MANUFACTURE CARBON NANOTUBES

Carbon nanotubes can be made by laser evaporation, carbon arc methods, and
chemical vapour deposition.

Fig 4. Experimental arrangement for synthesizing carbon nanotubes by laser

evaporation.

A quartz tube containing argon gas and a graphite target are heated to1200 ° C .
Contained in the tube, but somewhat outside the furnace, is a water-cooled copper
collector. The graphite target contains small amounts of cobalt and nickel that act as
catalytic nucleation sites for the formation of the tubes. An intense pulsed laser beam
is incident on the target, evaporating carbon from the graphite. The argon then sweeps
the carbon atoms from the high-temperature zone to the colder copper collector on
which they condense into nanotubes. Tubes 10−20 nm in diameter and 100 μm long
can be made by this method.
 Nanotubes can also be synthesized using a carbon arc. A potential of 20−25V
is applied across carbon electrodes of 5−20 μ m diameter and separated by 1 mm at
500 torr pressure of flowing helium. Carbon atoms are ejected from the positive
electrode and form nanotubes on the negative electrode. As the tubes form, the length
of the positive electrode decreases, and a carbon deposit forms on the negative
electrode. To produce single-walled nanotubes, a small amount of cobalt, nickel, or
iron is incorporated as a catalyst in the central region of the positive electrode. If no
catalysts are used, the tubes are nested or multiwalled types (MWNT), which are
nanotubes within nanotubes. The carbon arc method can produce single-walled
nanotubes of diameters 1−5 nm with a length of1 um.

The chemical vapor deposition method involves decomposing a hydrocarbon

gas such as methane (C H 4) at 1100 ° C . As the gas decomposes, carbon atoms are
produced that then condense on a cooler substrate mat may contain various catalysts
such as iron. This method produced tubes with open ends, which does not occur when
other methods are used. This procedure allows continuous fabrication, and may be the
most favorable method for scaleup and production.

The present synthesis methods provide only small yields, and make the cost of
the tubes about $ 1500 per gram. On the other hand, large-scale production methods
based on chemical deposition have been developed for multiwalled tubes, which are
presently available for $60 per pound, and as demand increases, this price is expected
to drop significantly. The methods used to scale up the multiwalled tubes should
provide the basis for scaling up synthesis of single-walled nanotubes. Because of the
enormous application potential, it might be reasonable to hope that large-scale
synthesis methods will be developed, resulting in a decrease in the cost to the order of
$10 per pound.

APPLICATIONS OF CARBON NANOTUBES

A. TRANSISTORS

It is very feasible to design field-effect transistors (FETs) using

semiconducting carbon nanotubes, connecting two gold electrodes.
Fig 5. A schematic of a field-effect transistor made from a carbon nanotube.

When a small voltage is applied to the gate, the silicon substrate, current
flows through the nanotube between the source and the drain. The device is
switched on when current is flowing, and off when it is not It has been found mat
a small voltage applied to the gate can change the conductivity of the nanotube by
a factor of ¿ 1 x 10 s , which is comparable to silicon field-effect transistors. It has
been estimated that the switching time of these devices will be very fast, allowing
clock speeds of a terahertz, which is 104 times fester than present processors. The
gold sources and drains are deposited by lithographic methods, and the connecting
nanotube wire is less man one nanometer in diameter. This small size should
allow more switches to be packed on a chip.

B. FIELD EMISSION DEVICES

When a small electric field is applied parallel to the axis of a nanotube,
electrons are emitted at a very high rate from the ends of the tube. This is
called field emission. This effect can easily be observed by applying a small
voltage between two parallel metal electrodes, and spreading a composite
paste of nanotubes on one electrode. A sufficient number of tubes will be
perpendicular to the electrode so that election emission can be observed. One
application of this effect is the development of flat panel displays. Television
 and computer monitors use a controlled electron gun to impinge electrons on
the phosphors of the screen, which then emit light of the appropriate colors. A
thin film of nanotubes is placed over control electronics with a phosphor-
coated glass plate on top instead of electron guns.
C. HETEROJUNCTION STRUCTURES BASED ON CARBON
NANOTUBES

In 1996 theorists pointed out that ‘elbow connections’ joining tubes of

different structures could constitute nanoscale heterojunctions Thus, a connection
between a metallic tube and a semiconducting one could form a rectifying diode:
higher energy electrons from the semiconducting side of the junction could flow
‘downhill’ to the metallic side, but they could not travel the other way. Work by
Collins etal. In 1998 provided the first evidence for this kind of behaviour in
single-walled tubes. In this work, an STM tip was moved along the length of
individual tubes, and positions were found where the current transport behaviour
changed abruptly. Effectively, the tubes passed current in only one direction. This
was attributed to pentagon–heptagon defects, although no direct proof was given.
later, clear experimental evidence for the rectifying behaviour of elbow
connections was given by Cees Dekker and colleagues. The setup used was
similar to that employed to demonstrate quantum wire behaviour in individual
SWNTs.

D. MICROWAVE DEVICES

To communicate, spacecraft and satellites rely on microwave devices,

which were traditionally based on relatively inefficient thermionic electron
sources that require heating and could not be switched on instantaneously. A
microwave diode that uses a cold-cathode electron source consisting of carbon
nanotubes which operates at high frequency and at high current densities. Because
it weighs little, responds instantaneously and has no need of heating, this
miniaturizes electron source may prove valuable for microwave devices used in
telecommunications.

E. CARBON NANOTUBE BASED SENSORS

 A field-effect transistor similar to the one shown in Fig. 5 made of the
chiral semiconducting carbon nanotubes has been demonstrated to be a sensitive
detector of various gases. The transistor was placed in a 500 ml flask having
electrical feed throughs and inlet and outlet valves to allow gases to flow over the
carbon nanotubes of the FET. Two to 200 parts per million of N O2 flowing at a
rate of 700 ml /min for l 0 min caused a threefold increase in the conductance of the
carbon nanotubes.

Figure 6 shows (he current-voltage relationship before and after exposure

to N O2. These data were taken for a gate voltage of 4 V The effect occurs because
when N O2 bonds to the carbon nanotube, charge is transferred from the nanotube
to the N O2, increasing the hole concentration in the carbon nanotube and
enhancing the conductance.

Fig 6. Plot of current versus voltage for carbon nanotube field effect trasnistor before
(line a) and after (line b) exposure to N O2 gas. These data were taken for a 4 V gate
voltage.