Carbon

Nanotubes
By
Shaweta Mutneja
M.Tech Nanotechnology
A1202810007
 What are Carbon
Nanotubes ?
Carbon nanotubes are fullerene-
related structures which consist of
graphene cylinders closed at either
end with caps containing pentagonal
rings
 Caps

* Typical high resolution TEM image of a

nanotube cap
 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
 Types of CNTs
 Single Wall CNT (SWCNT)
 Multiple Wall CNT (MWCNT)
 Can be metallic or semiconducting
depending on their geometry.
Nanotubes are formed by
rolling up a graphene
sheet into a cylinder and
capping each end with
half of a fullerene
molecule. Shown here is a
(5, 5) armchair nanotube
(top), a (9, 0) zigzag
nanotube (middle) and a
(10, 5) chiral nanotube.
The diameter of the
nanotubes depends on
the values of n and m.
 Hexagonal Lattice
(Definition of
Vectors) Chiral vector
y
a1 C h = na1 + ma 2
(4,-5) a2
3 3
x a1 = ( acc , acc )
2 2
T 3 3
a 2 = ( acc ,− acc )
2 2
O a1 = a 2 = 3acc ≡ a
Ch θ 3 1
a1 = ( , )a
2 2
(6,3) 3 1
a 2 = ( ,− ) a
2 2
 Wrapping
(10,0) SWNT
(zigzag)
(0,0)
Ch = (10,0)

y
a1
a2
x
 Wrapping
(10,0) SWNT
(Animation)
(0,0)
Ch = (10,0)

y
a1
a2
x
 Wrapping
(10,10) SWNT
(armchair)
(0,0)

Ch = (10,10)
y
a1
a2
x
 Wrapping
(10,10) SWNT
(Animation)
(0,0)

Ch = (10,10)
y
a1
a2
x
 Wrapping
(10,5) SWNT
(chiral)
(0,0)

Ch = (10,5)

y
a1
a2
x
 Wrapping
(10,5) SWNT
(Animation)
(0,0)

Ch = (10,5)

y
a1
a2
x
 Hexagonal Lattice
(n,m) nanotubes

(0,0) (1,0) (2,0) (3,0) (4,0) (5,0) (6,0) (7,0) (8,0) (9,0) (10,0) (11,0)
Zigzag
(1,1) (2,1) (3,1) (4,1) (5,1) (6,1) (7,1) (8,1) (9,1) (10,1)

(2,2) (3,2) (4,2) (5,2) (6,2) (7,2) (8,2) (9,2) (10,2)

(3,3) (4,3) (5,3) (6,3) (7,3) (8,3) (9,3)

(4,4) (5,4) (6,4) (7,4) (8,4) (9,4)

(5,5) (6,5) (7,5) (8,5)

y (6,6) (8,6)
a1
(7,6)

(7,7)
a2 Armchair
x

n - m = 3q (q: integer): metallic

n - m ≠ 3q (q: integer): semiconductor
 Synthesis: overview
 Commonly applied techniques:
 Chemical Vapor Deposition (CVD)
 Arc-Discharge
 Laser ablation

 Techniques differ in:

 Type of nanotubes (SWNT / MWNT / Aligned)
 Catalyst used
 Yield
 Purity
 Synthesis: CVD
•Gas phase deposition
•Large scale possible
•Relatively cheap

•SWNTs / MWNTs
•Aligned nanotubes
•Patterned substrates
 Synthesis: arc
discharge
 MWNTs and SWNTs • Relatively cheap
 Batch process • Many side-products
 Synthesis: laser
ablation
• Catalyst / no catalyst
• MWNTs / SWNTs
• Yield <70%

• Use of very strong laser

• Expensive (energy costs)
• Commonly applied
 Arc discharge Chemical vapor Laser ablation
method deposition (vaporization)

Connect two graphite rods to Place substrate in oven, heat Blast graphite with intense
a power supply, place them to 600 C, and slowly add a laser pulses; use the laser
millimeters apart, and throw carbon-bearing gas such as pulses rather than electricity
switch. At 100 amps, carbon methane. As gas to generate carbon gas from
vaporizes in a hot plasma. decomposes it frees up which the NTs form; try
carbon atoms, which various conditions until hit
recombine in the form of NTs on one that produces
prodigious amounts of
SWNTs

Can produce SWNT and Easiest to scale to industrial Primarily SWNTs, with a
MWNTs with few structural production; long length large diameter range that
defects can be controlled by varying
the reaction temperature

Tubes tend to be short with NTs are usually MWNTs and By far the most costly,
random sizes and directions often riddled with defects because requires expensive
lasers
 Overview of potential
applications
< AFM Tip
> Molecular electronics
•Transistor

> FED devices:

•Displays < Others
• Composites
< Energy storage: • Biomedical
•Li-intercalation • Catalyst support
•Hydrogen storage • Conductive materials
•Supercaps • ???
 Overview of potential
applications
< AFM Tip
> Molecular electronics
•Transistor

> FED devices:

•Displays < Others
• Composites
< Energy storage: • Biomedical
•Li-intercalation • Catalyst support
•Hydrogen storage • Conductive materials
•Supercaps • ???
 Energy Storage
Experiments & Modelling
 Electrochemical Storage of Lithium

 Electrochemical Storage of Hydrogen

 Gas Phase Intercalation of Hydrogen

 Supercapacitors
 Energy Storage
3-electrode cell
Work Electrode
reduction
CNT + xH 2O + xe - ‡
ˆˆˆˆˆ†
ˆˆˆˆˆ
oxidation
CNT + xH +
+ xOH -

Counter Electrode
Ni ( OH ) 2 ←
reduction
 → NiOOH + H +
+ e -
oxidation
Lithium Electrochemical
Model
 Lithium Electro
Chemical

•Equilibrium saturation
20 min
composition for graphite:
LiC6
10 min

•Purified SWNT bundles: 0 min

Li1.7 C6

•Ball-milled SWNTs:
Li2.7 C6
 Lithium Electro
Chemical
Etching
•Two types: lengths of 4 and

Voltage [V]
0.5 μm
•Good Crev (Li2.1 C6)
•Smaller hysteresis

Cut SWNTs have better

properties concerning Li
intercalation
 Hydrogen
Electrochemical
Lennard Jones Potential

 σ H-H 12  σ H-H  6 

U LJ ( r ) = 4ε H-H   −  
 r   r  
 Hydrogen
Electrochemical
storage model

Model of Hydrogen Storage at

room temperature for different
diameters of SWNTs
 Hydrogen
Electrochemical
Charging & Discharging
Charge  Discharge Cycle
 Hydrogen
Electrochemical
 Many contrasting conclusions:
 Positive Ranging from: 0.4 – 2.3 wt% H
 Negative: No systematic relationship
between purity and storage  storage
not due to SWNTs
 More investigations on the
mechanism of storage are needed in
order to explain this wide range of
results
Gas Phase Intercalation
of Hydrogen model
 Gas Phase Intercalation
of Hydrogen
 Contrast in results is very high: range
from 0-67 wt%
 Reasonable range: 2-10 wt%
 More modelling needed
 To compare models they have to use
the same parameters
 Super Capacitor
Electrochemical double layer
E l e c t r o d E e l e ( c+ t ) r o d e ( - )

S e p a r a t o r
 Molecular electronics
 FEDs
•CNTFETs
•SETs
 Field Emitting Devices

Single Emitter

Film Emitter
 Field Emitting Devices

Single Emitter

Film Emitter
 Field Emitting Devices

Single Emitter

Film Emitter
 Patterned Film Field
Emitters

•Etching and
lithography
•Conventional CVD
•Soft lithography
Transistor Principle in
CNTFETs

 Transistor

CNTFET 
Doping of CNTs
Single Electron
transistor
 Future Uses of CNTs
 Nano-Electronics
 Nanotubes can be conducting or
insulating depending on their properties
 Diameter, length, chirality/twist,
and number of walls
 Joining multiple nanotubes together to
make nanoscale diodes
 Max Current Density: 10^13 A/cm^2
 The Space Elevator
 The Idea
 To create a tether from earth to some object
in a geosynchronous orbit. Objects can then
crawl up the tether into space.
 Saves time and money

 The Problem
 62,000-miles (100,000-kilometers)
 20+ tons
 The Space Elevator

Pictures from
http://www.space.com/businesstechnology/technology/space_elevator_020327-1.html
 The Space Elevator
 The Solution: Carbon Nanotubes
 10x the tensile strengh (30GPa)
 1 atm = 101.325kPA
 10-30% fracture strain

 Further Obstacles
 Production of Nanofibers
 Record length 4cm
 Investment Capital: $10 billion