FULLERENE &

CARBON NANOTUBES
Introduction
Kind of Carbon Nanotubes
Properties
Synthesis
Applications
 INTRODUCTION

Carbon: Two forms Diamond

Graphite

Structure of Diamond: Tetrahedral Structure- All C atoms are sp3

hybridized
 Hardest material
 Insulator

Structure of Graphite: Hexagonal Structure- All C atoms are sp2

hybridized

 Soft material
 Electrical conductor
 Graphite sheets can form various Cage-like structures
- Fullerene:C60(Buckminsterfullerene)
- Carbon nanotubes (CNT)

The properties of each material change as the arrangement of atoms changes. When
carbon atoms form tiny tubes, called carbon nanotubes, the tubes are twice as strong
as steel but weigh six times less!
 C60 : BUCKMINSTERFULLERENE

 Structure consists of - FCC arrangement of 60 C atoms

- 12 pentagons & 20 hexagons

 Lattice parameter = 14.2 Å

 Diameter = 7 Å

 Produced by electric arc discharge method

 C60 most stable follows Isolated Pentagon Rule (IPR)

 C70 stable follows IPR Rule

 Fullerenes with less than 60 atoms highly unstable

(IPR Rule not followed)
 CABON NANOTUBES
Carbon nanotubes were discovered in 1991
by Sumiyo Iijima, a Japanese scientist
working at the NEC Corporation.

 Thought off as graphite sheet rolled into a cylinder

- surface consists of regular hexagons with carbon atoms at the vertices
- They may be open or closed (capped by one half of C60 molecule)

Other examples are nanotubes of boron nitride (BN), silica, transition metal
oxides (e,g. VOx and hydrogen titanates), sulfides (WS2, MoS2) and halides.
 Types of a Carbon nanotube
Single-walled carbon nanotube – Multi-walled carbon nanotube –
Tube with only one wall Tube with two or more walls

Typically, Length ~ few microns The length-to-diameter ratio of a

Diameter ~1-2nm (SWCNT) carbon nanotube can be as large
~2-50nm (MWCNT) as 1000,000:1
(Very high aspect ratio)
Top view showing the tips of
different nanotubes

Front view showing the

hexagonal structure in
different nanotubes
 STRUCTURES OF CARBON NANOTUBES

 Different structures depend on : Diameter & Chirality

 Chiral vector(Ch):
Ch = n a 1 + m a 2
where, a1 & a2 are the unit vectors, n & m are integers
 Chiral angle ():
Sin  = √3m / 2√n2 + m2 + nm

 Structures of CNT’s can be characterized by (n, m) indices

Graphite layer with atoms labeled using (n,m) notation

Construction of the unit cell for a (6,3) nanotube
 THREE TYPES OF CARBON NANOTUBE STRUCTURES
A single-walled carbon nanotube is characterized by a set of two integers (n, m) called
the chirality vector
 Armchair nanotubes When n = m, e.g. (3,3)
and  = 30o

 Zig-Zag nanotubes When n or m = 0, e.g. (9,0)

and  = 0o

 Chiral nanotubes All nanotubes with 0o <  < 30o e.g. (10,5)

Diameter (D) of the tube:

D = ( 3√d / ) √n2 + m2 + nm

where d= 0.142nm, the distance between two carbon atoms in the

graphite plane

or, D2=((n2 + m2 + nm)1/2)0.0783

Unit cells for: (a) (5,5) armchair nanotube.
(b) (9,0) zig-zag nanotube
 SEM images of Carbon nanotubes

SWCNTs MWCNTs

Typically, Length ~ few microns

Diameter ~1-2nm (SWCNT)
~2-50nm (MWCNT)
TEM image of Single-wall Carbon nanotubes
TEM image of Multi-wall Carbon nanotubes
Why are Carbon Nanotubes technologically important?

Carbon nanotubes would inherit several important properties of ‘intra-

plane’ graphite. This imparts a very unique combination of properties on
this material

Unique Properties of Fullerene & Carbon nanotubes:

 High mechanical strength & flexibility

 High thermal & chemical stability

 High electrical conductivity

 Very high aspect ratio

 UNIQUE PROPERTIES OF CARBON NANOTUBES
MECHANICAL PROPERTIES:

•Stronger High Young’s Modulus (1.8TPa) Carbon Nanotubes are a hundred times
stronger than steel at one-sixth of its
Tensile Strength of Engineering Materials weight.

Gpa, log scale

• CNTs have Flexibility
•Twisted, flattened & bent without breaking
•Compressed without fracture
ELECTRICAL PROPERTIES:

Graphene Sheet
ELECTRICAL PROPERTIES:

•MWCNT’s Metallic
•SWCNT’s Semi-conducting or Metallic
ELECTRICAL PROPERTIES:

Bandgap increases as tube diameter decreases

ELECTRICAL PROPERTIES:

•All armchair nanotubes are Metallic

•All zig-zag and Chiral nanotubes can be either semiconducting or Metallic

When (n-m)/3 is an integer (for example when n is 8 and m is 2), then

the nanotube has metallic properties(Eg = 0eV);

if (n-m)/3 is not an integer, the corresponding nanotube behaves like it

is a semiconductor(Eg = 0.5eV).

•Resistivity of CNT’s ~10-6m

•Maximum current density ~ 1013A/m2, (100 times more than copper)

Their ability to carry current and heat along the axial direction is extraordinary, and therefore has
the potential to replace copper wires as conductors.

The ability to create tubes of either metallic or semiconductor nature is of great practical importance.
Today's computer chips use silicon (which is a semiconductor) along with copper (which is a metal) to build
circuits. Scientists and engineers envision all carbon-based electronics using semiconducting and metallic
carbon nanotubes of different values of n and m.
PHYSICAL PROPERTIES:
• High Strength to Weight ratio~1.8 g/cm2
(100 times that of steel, and twice that of carbon fibers)
-good for light weight applications.
• highly resistant to chemical attack.
• Difficult to oxidize, the oxidation temp is 100 oC higher than that of carbon fibers

THERMAL PROPERTIES:

•High thermal conductivity (1750-5800 W/mK), which increases with decrease in

diameter.

MAGNETIC PROPERTIES:

•Diamagnetic Large –ve susceptibility

OPTICAL PROPERTIES:

•Non linear optical properties dependent on diameter & chirality

Unique Properties of Fullerene & Carbon nanotubes:

•High aspect ratio structures with diameters in nanometers, lengths in microns

•High mechanical strength (tensile strength 200GPa) and modulus (Young’s modulus 1TPa)

•High electrical conductivity (10-6 ohm m typically), and for well crystallised nanotubes ballistic
transport is observed

•High thermal conductivity (1750-5800 W/mK)

•Being covalently bonded, as electrical conductors they do not suffer from electromigration or
atomic diffusion and thus can carry high current densities (107 -109 A/cm2 )

•Single wall nanotubes can be metallic or semi-conducting

•Chemically inert, not attacked by strong acids or alkali

•Collectively, nanotubes can exhibit extremely high surface area

 Synthesis of Carbon nanotubes

Various Methods

 Arc Discharge
 Pulsed Laser Vaporization (Laser Ablation)
 Chemical Vapor Deposition
 Arc Discharge Method
Schematic of Arc Discharge Apparatus
He

He

•Two graphite rods are taken as cathode and anode

•Carbon atoms are evaporated from the anode, by a plasma of

Helium gas that is produced when high currents is passed through
opposing carbon anode and cathode

•Carbon clusters, Fullerene molecules, Carbon Nanotubes,

amorphous carbon etc, get deposited on cathode rod
 •Pure anodic graphite rod MWCNT’s
•Anode doped with Ni, Co, Fe SWCNT’s

• Typically, Voltage = 20-40V

Gap b/w the rods =1mm or less

•CNT’s are obtained by controlling two growth condition

- Pressure of gas in the discharge chamber
- Arcing current

Structure of CNTs depends on: current I, voltage V, He gas pressure,

anode material, distance between the electrodes
 CNTs deposited at different He gas pressures

• (a) 20 Torr
• (b) 100 Torr
• (c) 500 Torr

The arc discharge techniques produces an ensemble of carbonaceous material

which contain carbon nanotubes (30 %), amorphous carbon and carbon particles
(usually closed-caged ones).
 Pulsed Laser Vaporization
Laser ablation
Another method to grow SWNTs using laser ablation was demonstrated in
1996 by Smalley's group. The synthesis of carbon nanotubes is carried out
in a horizontal quartz tube under a flow of inert gas at controlled pressure. In
this set-up the quartz tube is heated to ~1200°C by a tube furnace. Laser
pulses enter the tube and strike a target consisting of a graphite doped with
metal catalyst such as Co or Ni. SWNTs condense from the laser vaporization
plume and are deposited on a collector outside the furnace zone.
 Pulsed Laser Vaporization

 The material deposited on water cooled collector consists of amorphous carbon,

SWCNT, MWCNT, and other carbon cage like structures.
 Laser Vaporization
This method uses laser pulses to ablate (or evaporate) a carbon target

The target is placed in a tube-furnace whose

- Temperature = 1200oC
- Pressure = 500 Torr

When pure graphite is used MWCNT’s

When graphite containing Co, Ni, Fe is used SWCNT’s

 SWCNT diameter depends on tube furnace temperature and catalyst used

Yield of Carbon nanotubes produced by laser ablation method is 70%

Purification of samples is done by heat teatment at 1000oC to remove C60 and

other amorphous carbon deposits
Synthesis methods of growing Carbon Nanotubes

Physical Vapor
Deposition
(PVD)

•High temperature

• Low Temperature Process

• Controlled Synthesis
Plasma Enhanced CVD • High Productivity, large
scale deposition
Microwave Plasma Enhanced CVD

• Low Temperature Process

• High Productivity, large
scale deposition
• vertically alligned CNTs
 Chemical Vapor Deposition (CVD)

Alternative approach for large scale production of CNT’s

Produces pure and well aligned Carbon nanotubes at low

temperature of 500-900°C

Various types of CVD processes are

• Hot filament CVD (HFCVD)
• RF Plasma-enhanced CVD (PECVD)
• Microwave Plasma-enhanced CVD (MPECVD)

CNT production Catalytic cracking of hydrocarbon

Catalyst Fe, Co, Ni
Produces nucleation sites for the
nucleation and growth of CNT’s
Source of Carbon containing species
- Benzene (C6H6)
- Ethylene (C2H4)
- Methane (CH4)
- Carbon mono oxide (CO)

Etching species Normally H2 & NH3 are used

 Plasma Enhanced Chemical Vapor
Deposition (PECVD)

A quartz tube about 2.5 cm in diameter serves as the growth reactor and is inserted
inside a tube furnace (a tube furnace is a standard heating device for conducting
syntheses and purifications). The nanotube is grown on a silicon wafer that is placed
at a central location inside the quartz tube. A thin layer of iron or nickel or cobalt is
first deposited onto the silicon wafer to serve as a catalyst to grow the nanotubes.
Plasma of Etching gas transforms the continuous catalyst thin film in spherical
nanoparticles (of different sizes (10~100 nm). A hydrocarbon such as methane (high
purity form of natural gas) or ethane or acetylene is then passed through the reactor
tube which is heated to 750-900ºC by the furnace. This will lead to growth of vertically
aligned carbon nanotubes.
Process steps for the growth of carbon nanotubes:

Cleaned Si substrates Si

Deposition of thin films of catalyst (Fe) by Metal(

PVD (Thermal evaporation or Fe)
Sputtering)
Si

Pretreatment of metal(Fe) coated Metal particles

substrates by plasma of H2 or NH3 for
approx. 30 min.

Tip Growth
Introduction of hydrocarbon gas(C2H2)
to initiate the synthesis of carbon
nanotubes
Base Growth
SEM Photograph of Pretreated Fe Film

Deposition Parameters:
Microwave Power = 500W
Pretreatment Time = 15 min
Pressure in the Chamber = 5 Torr

Particle Size is approx. 100-200nm

Two Growth Modes of Carbon nanotubes

 Tip growth mode

 Base growth mode

Weak adhesive forces Tip growth mode

b/w Catalyst & substrate

Strong adhesive forces Base growth mode

b/w Catalyst & substrate
Nucleation and growth model of carbon nanotubes
Carbon species

In these chemical vapor deposition processes, the catalyst decomposes the hydrocarbon
gas to produce carbon and hydrogen. The carbon dissolves into the particle and
precipitates out from its circumference as the carbon nanotube. Thus, the catalyst acts as
a ‘template’ from which the carbon nanotube is formed, and by controlling the catalyst
size and reaction time, one can easily tailor the nanotube diameter and length
respectively to suit.
 Low- and high-resolution SEM images of the typical arrays of vertically-aligned
CNTs grown in PECVD process with a glow discharge.

SEM Images of carbon nanotubes grown by the NanoGrowth LT process at temperatures

below 350°C (LH) and 370°C (RH)
Hot Filament (Thermal) assisted PECVD

-Reaction gases are introduced into the

chamber containing a hot filament
-Filament Temp = 1200oC
-Contaminated CNT’s
RF-DC assisted PECVD

Schematic of the RF-DC

plasma CVD

- RF power is fed to two electrodes

placed in the chamber
- Plasma of reaction species is produced
- Low Growth rate
- Contamination problem due to electrodes
 Microwave Plasma Enhanced CVD
(MPECVD)

MPECVD: Experimental
Set-Up

ADVANTAGES OF MPECVD METHOD

 Scalability
 Low temperature process
 Electrode-less process, so no contamination problem
 Growth rate is high
 Control over nanotube diameter is achieved by
adjusting the size of catalyst used
 A wide range of gases, catalysts, substrate, temp,
and pressures are possible for extreme versatility
 Growth & yield are controlled by controlling the
catalyst, flow rate of gases, deposition temp & time
Sample deposited in the presence of H2 & Acetylene
gas plasma:

SEM Photograph of Sample 1 TEM Photograph of Sample

Deposition Parameters:
Microwave Power = 500W
Deposition Time = 10 min
Pressure in the Chamber = 5 Torr
Diameter of CNTs is approx. 50-100nm
vertically aligned CNTs over SiO2 /Si Substrate

Length of CNTs is approx. 10µm

Diameter of CNTs is approx. 50-100nm
APPLICATIONS OF CARBON NANOTUBES
 Field emitters

 Hydrogen storage

 STM & AFM probe tips

 Nanotube sensors

 Catalysis

 Nano-Electronics

 Light Emitting Devices

 Photovoltaic Devices
 Carbon Nanotubes
Applications
Current and Future Applications

Filled Nanotubes:

• protection and storage of substances

• filling with radioactive substances
• developing new magnetic devices
 Current and Future Applications

AFM probe tips

 CNT on tip of an AFM

 finer tip = higher resolution

Single-walled carbon nanotubes have been attached to the tip of an AFM probe to
make the tip “sharper”. This allows much higher resolution imaging of the surface
under investigation; a single atom has been imaged on a surface using nanotube-
enhanced AFM probes. Also, the flexibility of the nanotube prevents damage to the
sample surface and the probe tip if the probe tip happens to “crash” into the surface.
 Current and Future Applications

Nanotube in Field Emission Display Devices:

Carbon nanotubes very good Field emitters

Used as Electron Guns

• Sharp Nanotube Points Make Them Ideal as Electron Guns

• One application of Electron Guns is in Field Emission
Displays
– Electrons Emitted from Source Exciting a Phosphor
When a nanotube is put into an electric field, it will emit electrons from the end of the nanotubes. If those electrons
are allowed to bombard a phosphor screen then an image can be created.
Using transparent electrodes and addressable array, pixels of field-emitting CNTs can be switched to
excite red, green, blue phosphor and hence create a full color image.
 Brightness of CNT based Field emission
displays is higher compared to conventional
displays
Requirement:
Well controlled Vertically Aligned
Carbon nanotubes on patterned structure

Nevertheless, the achievement of vertically well-aligned CNTs arrays for applicable

field emission devices has not been facile and degradation of CNT field emitters by
residual gases including oxygen is one of the problems to be overcome for high
performance field emission displays (FEDs)
 Current and Future Applications
Nanoelectronics:
Carbon Nanotubes
One of the most significant applications is nanotube transistors.
Use of semiconducting nanotubes as compact, more efficient alternatives to conventional
Si transistors.
 Current and Future Applications

Carbon Nanotube based Light Emitting Devices:

Carbon Nanotube based Photovoltaic Devices:

Solar Light
Chemical sensors:
 CNTs sensitive to gas and pressure:
change of their electronic properties

Semiconducting carbon nanotubes display a large change in conductance (i.e., ability to

store charge) in the presence of certain gases (e.g., NO2 and NH3).

Compared to conventional sensors, carbon nanotubes provide the advantages of a smaller

size, an increased sensitivity, and a faster response.

In the future, nanotube sensors could be used for security and environmental applications.
Drug delivery with Buckyballs (Fullerene):

Fullerenes can be loaded with medicine

An antibody will only attach to a specific
(green) and attached to an antibody (pink)
antigen that is the right shape.
which will seek out the disease antigen.

Scientists are also testing fullerenes for drug delivery. Many drug molecules can be attached to a
fullerene. The medicine loaded fullerene can then be attached to an antibody. Antibodies are Y-
shaped proteins that can recognize and attach to things in the body called antigens. Viruses, bacteria
and diseases in the body each have unique antigens. The antibody finds the disease in the body then
the attached fullerene delivers the appropriate medicine. Just like with magnetic nanoparticles,
medicine can be sent only to place where it is needed, leaving healthy cells alone