CARBON NANOTUBES, INORGANIC NANOWIRES

AND FUNCTIONALIZATION
Different Forms of Carbon
 A new form of carbon!
Graphite Diamond Fullerenes
SOME BASICS
 Carbon fullerenes and nanotubes
• Carbon
– graphite form: good metallic conductor
– diamond form: wide band gap semiconductor

Fullerenes
• A molecule with 60 carbon atoms C60
– with an icosahedral symmetry ( a regular icosahedron has 60 rotational (or orientation-
preserving) symmetries, and a symmetry order of 120 including transformations that combine a reflection and a
rotation. A regular dodecahedron has the same set of symmetries, since it is the dual of the icosahedron).

– buckyball or buckmister fullerene

– C-C distanance 1.44 A (~ graphite 1.42 A)
– 20 hexagonal faces + 12 pentagonal faces
 Carbon fullerenes
• Initially synthesized by Krätschmer et al. 1990
• C60, C70, C76, C78, C80

Fig 6.1
 C70

What are fullerenes?

In 1985, Robert Curl, Harry Kroto,
and Richard Smalley discovered C60 Buckminst
and C70. (Nobel prize in 1996.) er
Fullerene
C60

The American
pavilion in the
Expo'67 in
Montreal was
designed by
architect
R. Buckminster
Fuller.
Fullerene
colors

The fullerenes C60 and

C70 may be dispersed in
water…
 Carbon fullerenes synthesis
– arc discharge between graphite electrodes in
200 torr of He gas
– heat at the contact point between the
electrodes evaporates carbon
• form soot and fullerenes
• condense on the water-cooled walls of the reactor
• ~15% fullerenes: C60 (13%) + C70(2%)
– Separation by mass
• liquid (toluene) chromatography
 What Are Carbon Nanotubes?
• CNT can be described as
a sheet of graphite rolled
into a cylinder
• Constructed from
hexagonal rings of carbon
• Can have one layer or
multiple layers
• Can have caps at the
ends making them look
like pills

Information retrieved from: http://www.photon.t.u-tokyo.ac.jp/~maruyama/agallery/agallery.html

CARBON
NANOTUBES

Conducti
Resistivit
vity σ
Material y ρ (Ω·m)
(S/m)
at20 °C
at20 °C
Silver 1.59×10−8 6.30×107

Copper 1.68×10−8 5.96×107

Annealed
1.72×10−8 5.80×107
copper
Gold 2.44×10−8 4.10×107
 Properties of
nanotubes
• Carbon nanotubes are long meshed wires of carbon
• Longest tubes up to 1mm long and few nanometers thick made by IBM.

Property Carbon Nanotubes Comparatively

Size 0.6-1.8 nm in Si wires at least

diameter 50nm thick
Steel alloys have
Strength 45 Billion Pascals 2 Billion P.
Resilience Bent and straightened Metals fracture
without damage
ConductivityEstimated at 109 Cu wires burn at
A/cm2 106 A/cm2
Cost $2500/gram by BuckyUSA Gold is
in Houston $15/gram
 Discovery

They were discovered in 1991

by the Japanese electron
microscopist Sumio Iijima who
was studying the material
deposited on the cathode
during the arc-evaporation
synthesis of fullerenes.

He found that the central core

of the cathodic deposit
contained a variety of closed
graphitic structures including
nanoparticles and nanotubes,
of a type which had never
previously been observed
 Why do Carbon Nanotubes form?
Carbon Graphite (Ambient conditions)
sp2 hybridization: planar

Diamond (High temperature and pressure)

sp3 hybridization: cubic

Nanotube/Fullerene (certain growth conditions)

sp2 + sp3 character: cylindrical

Finite size of graphene layer has dangling bonds. These dangling

bonds correspond to high energy states.

Eliminates dangling bonds

Nanotube formation + Total Energy
Increases Strain Energy decreases
 Carbon Nanotubes
• This is a nanoscopic structure made of carbon atoms in the shape of
a hollow cylinder. The cylinders are typically closed at their ends by
semi-fullerene-like structures.
• There are three types of carbon nanotubes: armchair, zig-zag
and Chiral (helical) nanotubes. These differ in their symmetry.
Namely, the carbon nanotubes can be thought of as graphene
planes 'rolled up' in a cylinder (the closing ends of carbon nanotubes
cannot be obtained in this way).
• Depending on how the graphene plane is 'cut' before rolled up, the
three types of carbon nanotubes are obtained. Within a particular
type, carbon nanotubes with many different radii can be found
(depending on how large is the graphene area that is folded onto a
cylinder).
• These tubes can be extremely long (several hundreds of
nanometers and more). Some consider them as special cases of
fullerenes. When produced in materials, carbon nanotubes pack
either in bundles (one next to another within a triangular lattice) -
single-walled carbon nanotubes, or one of smaller radius inside
others of larger radii - multi-walled carbon nanotubes. Carbon
nanotubes have already found several technological applications,
including their application in high-field emission displays.
 Nanotube Classification
• MWNT
– Consist of 2 or more layers
of carbon
– Tend to form unordered
clumps
• SWNT
– Consist of just one layer of
carbon
– Greater tendency to align
into ordered bundles
– Used to test theory of
nanotube properties
 Single-wall carbon nanotube
(SWCNT)
• diameter and chiral angle 
– =30° : armchair
– = 0° : zigzag
– 0° <  < 30° : chiral Fig 6.2

Fig 6.3
 Multi-wall carbon nanotube
(MWCNT)
• Several nested coaxial single-wall tubules
(chiral tubes)
• typical dimensions:
– Outer diameter.: 2-20 nm
– Internal diameter.: 1-3 nm
– intertubular distance: 0.34 nm
– length: 1-100 m
The way to
find out how
the carbon
atoms are
arranged in a
molecule can
be done by
joining the
vector
coordinates
of the atoms.
By this way it
can be
identified
whether if the
carbon
atoms are
arranged in a
zig-zag,
armchair or
in a helical
shape.
 The A. J. Drexel Nanotechnology Institute

How to understand the structure of a

carbon nanotube

Carbon nanotubes can be

considered as graphene
sheets rolled up into
seamless cylinders

Arrows are showing two

different rolling directions
which gives rise to armchair
and zigzag nanotube
 Structure of All carbon atoms are involved in
SWNT hexagonal aromatic rings only and
are therefore in equivalent
position, except at the nanotube
tips where 6×5 = 30 atoms at
each tip are involved in
pentagonal rings (considering
that adjacent pentagons are
unlikely) – though not more, not
less, as a consequence of the
Euler’s rule that also governs
the fullerene structure.

Though carbon atoms are involved in aromatic rings, the C=C bond angles
are no longer planar as they should ideally be. This means that the
hybridization of carbon atoms are no longer pure sp2 but get some
percentage of the sp3 character, in a proportion that increases as the
tube radius of curvature decreases.
 Ways to roll a carbon
sheet

Sketch of three different SWNT structures as examples for

(a) a zig-zag-type nanotube, (b) an armchair type nanotube,
26 (c) a helical nanotube
The different types of carbon nanotubes

Armchair nanotube

Zigzag nanotube

Chiral nanotube
 Classification of Symmetries
• Zigzag nanotubes
correspond to (n,0) or
(0,m) and have a chiral
angle of 0°, armchair
nanotubes have (n,n)
and a chiral angle of
30°, while chiral
nanotubes have
general (n,m) values
and a chiral angle of
between 0° and 30°.
Structure of Carbon Nanotubes
Zig Zag

Armchair
Geometry of
NT

38
 Geometrical structure of NT
Properties depend on the orientation of the hexagonal network with
respect to the nanotube long axis, a property known as chirality.
 When
a
metal?
•Carbon nanotubes can be metallic or
semiconductor depending on
their chirality.

•If (n-m) is divisible by 3, the tube is metallic

•If (n-m) is not divisible by 3, the tube is

semiconducting.
Band-gap is determined by the diameter of the tube:
For tiny band-gap tube: Eg  1 / R
2

For large band-gap tube: E g  1 / R

nxn Single Walled Carbon
Nanotubes
 Electrical Properties
• If the nanotube structure is
armchair then the electrical
properties are metallic
• If the nanotube structure is chiral
then the electrical properties can
be either semiconducting with a
very small band gap, otherwise the
nanotube is a moderate
semiconductor
• In theory, metallic nanotubes can
carry an electrical current density
of 4×109 A/cm2 which is more than
1,000 times greater than metals
such as copper
 Thermal Properties
• All nanotubes are expected to be very good thermal
conductors along the tube, but good insulators laterally
to the tube axis.

• It is predicted that carbon nanotubes will be able to

transmit up to 6000 watts per meter per Kelvin at room
temperature; compare this to copper, a metal well-
known for its good thermal conductivity, which
transmits 385 watts per meter per K.

• The temperature stability of carbon nanotubes is

estimated to be up to 2800oC in vacuum and about
750oC in air.
 Defects
• Defects can occur in the form of atomic
vacancies. High levels of such defects
can lower the tensile strength by up to
85%.

• Because of the very small structure of

CNTs, the tensile strength of the tube is
dependent on its weakest segment in a
similar manner to a chain, where the
strength of the weakest link becomes
the maximum strength of the chain.
 One-Dimensional Transport
• Due to their nanoscale dimensions, electron transport in
carbon nanotubes will take place through quantum
effects and will only propagate along the axis of the tube.
Because of this special transport property, carbon
nanotubes are frequently referred to as “one-
dimensional.”
 Applications
• Nanotubes hold the promise of creating
novel devices, such as carbon-based
single-electron transistors, that
significantly smaller than conventional
transistors.
Nanotubes’ excellent strength to weight
ratio creates the potential to build an
elevator to space.
 Quantum Computing
• Nanotubes and other Fullerenes can be
filled with molecules that have either an
electronic or structural property which can
be used to represent the quantum bit
(Qubit) of information, and which can be
associated with other adjacent Qubits.
 Biological applications:
Functional AFM tips
Molecular-recognition AFM probe tips:
• Certain bimolecular is attached to the CNT tip
• This tip is used to study the chemical forces between
molecules – Chemical force microscopy
 Biological applications: DNA
sequencing
• Nanotube fits into the
major grove of the DNA
strand
• Apply bias voltage
across CNT, different
DNA base-pairs give
rise to different current
signals
• With multiple CNT, it is Top view and side view of the
possible to do parallel assembled CNT-DNA system
fast DNA sequencing
 Health Hazards

• According to scientists at the National

Institute of Standards and Technology,
carbon nanotubes shorter than about 200
nanometers readily enter into human lung
cells similar to the way asbestos does, and
may pose an increased risk to health.
• Carbon nanotubes along with the majority of
nanotechnology, are an unexplored matter,
and many of the possible health hazards are
still unknown.
 Challenges and future
• Future applications:
1. Already in product: CNT tipped AFM
2. Big hit: CNT field effect transistors based nano electronics.
3. Futuristic: CNT based OLED, artificial muscles…

• Challenges
1. Manufacture: Important parameters are hard to control.
2. Large quantity fabrication process still missing.
3. Manipulation of nanotubes.
TYPES OF CARBON NANOTUBES

1. Single Walled Carbon Nanotubes

2. Multi Walled Carbon Nanotubes
 SYNTHESIS OF CARBON NANOTUBES
SINGLE WALLED CARBON NANOTUBES MULTI WALLED CARBON NANOTUBES

1. Arc- Discharge process 1. Electric arc Discharge process

2. Inert Gas 2. a. Under N2 atmosphere
a. Optical Plasma Control b. Under magnetic field
b. Improvement of oxidation resistance c. Plasma Rotating arc discharge
3. Laser Vaporization 3. Chemical Vapor Deposition
4. Pyrolysis or vapor phase deposition a. Plasma enhanced CVD
5. Chemical Vapor Deposition b. Thermal Chemical CVD
a. Alcohol catalytic CVD c. Alcohol catalytic CVD
b. Aerogel supported CVD d. Aerogel supported CVD
c. Laser assisted Thermal CVD c. Laser assisted CVD
6. CoMoCat Process 6. Vapor phase growth
7. HIPCO Process - Nebulized Spray Pyrolysis
8. Flame Synthesis
9. Sonochemical Route

THERMAL SYNTHESIS - CVD, HIPCO AND FLAME

 SINGLE WALLED CARBON NANOTUBES
1. Arc-Discharge Method  By striking an arc between graphite electrodes
in 0.7 atm (500 torr) of He, Ar or CH4
 A current of 60-100 A across a potential drop of 25 V
gives high yield of CNTs.
 ‘C’ anode gets deposited as carbon nanotubes
on carbon anodes and graphitic nanoparticles.
 `H2 - gives high crystallinity CNTs.
 PLASMA ARC JETS – large quantities.
a. ARC DISCHARGE IN LIQUID NITROGEN
 Vacuum is replaced with liq.N2
 Direct current was supplied. Anode is pure carbon rod
(8 mm dia); cathode is pure carbon rod (10 mm dia).
The Dewar flash is filled with N2 and the assembly is
immersed in liq.N2
 As the distance between electrodes is 1 mm, arc
discharge occurs and a current of 80 A flows between
them.
Carbon deposits near the cathode
 Liq.N2 prevents the electrodes from contamination with
unwanted gases and also lowers the electrodes.
CNTs do not stick to the chamber wall.
b. ARC DISCHARGE IN A MAGNETIC FIELD

 Synthesis in a magnetic field gives defect free and high purity (> 95%) MWNTs.

Arc discharge is controlled by a magnetic field around the arc plasma.

c. PLASMA ROTATING ARC DISCHARGE TECHNIQUE

 The centrifugal force caused by the rotation generates turbulence and accelerates
the carbon vapor perpendicular to the anode.
 Rotation distributes the micro discharges uniformly - stable plasma.
 Increases the plasma volume and raises the temperature.
 At a rotation of 5000 RPM, 60 % yield at 1025oC (without catalyst).
 90% yield at 1150oC with an inner dia of 1-3 nm and outer di of 10 nm.
2. CHEMICAL VAPOR DEPOSITION
 Uses a carbon source in the gas phase and a plasma or a heated coil, to transfer the
energy to gaseous carbon molecule.
 Sources – CH4, CO, acetylene.
 The energy source cracks the atomic carbon.
 The carbon then diffuses towards the substrate, which is coated with a catalyst Fe, Ni or Co
and binds to it.
 Use of preferential catalyst is essential.

TWO STEPS IN CVD

1. Catalyst Preparation step.
2. Synthesis of Nanotubes.

Catalyst Preparation Step: Sputtering of transition metal onto a substrate, followed by

etching by chemicals to induce the nucleation of catalyst particles.

Thermal Annealing : Metal cluster formation on the substrate – on which nanotubes

grow.
Temperature : 650 – 900o C.
 TYPES OF CVD

1. Plasma Enhanced CVD.

2. Thermal Chemical CVD.
3. Alcohol Catalytic CVD.
4. Aerogel supported CVD.
5. Laser assisted CVD.
a. PLASMA ENHANCED CHEMICAL VAPOR DEPOSITION
 Involves a glow discharge in a
chamber or a reaction furnace thro’ a
high frequency voltage applied to By
striking an arc between graphite
electrodes
in 0.7 atm (500 torr) of He, Ar or CH4
 A current of 60-100 A across a
potential drop of 25 V
gives high yield of CNTs.
 ‘C’ anode gets deposited as carbon
nanotubes
on carbon anodes and graphitic
nanoparticles.
 `H2 - gives high crystallinity CNTs.
 PLASMA ARC JETS – large
quantities.