LECTURE 15-3

Carbon nanostructures:
fullerenes and carbon nanotubes

Maj Md. Ashrafuzzaman, Ph.D

1
 Carbon Nanotubes

 Introduction
 Applications
 Growth Techniques
 Growth Mechanism
 What is a Carbon Nanotube?
CNT is a tubular form of carbon with diameter as small as 1nm.
Length: few nm to microns.

CNT is configurationally equivalent to a two dimensional graphene

sheet rolled into a tube.

A CNT is characterized by its Chiral Vector: Ch = n â1 + m â2,

  Chiral Angle with respect to the zigzag axis.
Armchair (n,m) = (5,5)
 = 30

Zig Zag (n,m) = (9,0)

 = 0

Chiral (n,m) = (10,5)

0 < < 30
 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.
CNT Properties
CNT Properties (cont.)
 CNT: Implications for electronics

 Carrier transport is 1-D.

 All chemical bonds are
satisfied  CNT Electronics not bound to use SiO2 as
an insulator.
 High mechanical and thermal stability and resistance to
electromigration  Current densities upto 109 A/cm2
can be sustained.
 Diameter controlled by chemistry, not fabrication.
 Both active devices and interconnects can be made
from semiconducting and metallic nanotubes.
 Nanotube Growth Methods

a) Arc Discharge b) Laser Abalation

 Involve condensation of C-atoms generated from evaporation of solid
carbon sources. Temperature ~ 3000-4000K, close to melting point of
graphite.
 Both produce high-quality SWNTs and MWNTs.
 MWNT: 10’s of m long, very straight & have 5-30nm diameter.
 SWNT: needs metal catalyst (Ni,Co etc.).
Produced in form of ropes consisting of 10’s of individual nanotubes close
packed in hexagonal crystals.
 Nanotubes Growth Methods
c) Chemical Vapor Deposition:
Hydrocarbon + Fe/Co/Ni catalyst 550-750°C
CNT

Steps:
 Dissociation of hydrocarbon.
 Dissolution and saturation
of C atoms in metal nanoparticle.
 Precipitation of Carbon.

Choice of catalyst material?

Base Growth Mode or Tip Growth Mode?

 Metal support interactions
 Controlled Growth by CVD
Methane + Porous Si + Fe pattern CVD
Aligned MWNTs

a) SEM image of aligned

nanotubes.
b) SEM image of side view
of towers. Self-alignment
due to Van der Walls
interaction.
c) High magnification SEM
image showing aligned
nanotubes.
d) Growth Process: Base
growth mode.
 Growth Mechanisms
 Electronic and Mechanical Properties are closely related to the
atomic structure of the tube.
 Essential to understand what controls the size, number of shells,
helicity & structure during synthesis.
 Mechanism should account for the experimental facts: metal
catalyst necessary for SWNT growth, size dependent on the
composition of catalyst, growth temperature etc.

 MWNT Growth Mechanism:

- Open or close ended?
- Lip Lip Interaction Models

 SWNT Growth Mechanism:

- Catalytic Growth Mechanism
Open-Ended Growth of Multi Walled Nanotube

 Role of Hexagons, Pentagons & Heptagons

MWNT: The possibilities
 MWNT: Lip-Lip Interaction Model

High Coordinated Low Coordinated H-atoms

C atoms C atoms
 SWNT Growth Mechanism

Is uncatalyzed growth possible?

 Simulations & Observations  No!

 Spontaneous closure at experimental temperatures of 2000K to
3000K.
 Closure reduces reactivity.
 Catalytic SWNT Growth Mechanism

 Transition metal surface decorated

fullerene nucleates SWNT growth
around periphery.

 Catalyst atom chemisorbed onto

the open edge. Catalyst keeps the
tube open by scooting around the
open edge, ensuring and pentagons
and heptagons do not form.
 Conclusion
 Their phenomenal mechanical properties, and unique
electronic properties make them both interesting
as well as potentially useful in future technologies.
 Significant improvement over current state of
electronics can be achieved if controllable growth is
achieved.
 Growth conditions play a significant role in deciding the
electronic and mechanical properties of CNTs.
 Growth Mechanisms yet to be fully established.
 References
 Topics in Applied Physics
Carbon Nanotubes: Synthesis, Structure, Properties and Applications
M.S. Dresselhaus, G. Dresselhaus, Ph. Avouris
 Carbon Nanotube Electronics
PHAEDON AVOURIS, MEMBER, IEEE, JOERG APPENZELLER, RICHARD MARTEL, AND
SHALOM J. WIND, SENIOR MEMBER, IEEE
PROCEEDINGS OF THE IEEE, VOL. 91, NO. 11, NOVEMBER 2003
 Carbon Nanotubes: Single molecule wires
Sarah Burke, Sean Collins, David Montiel, Mikhail Sergeev
 http://www.ipt.arc.nasa.gov
 Carbon Nanotubes: Introduction to Nanotechnology 2003, Mads Brandbyge.