The wondrous world

of carbon nanotubes

March 26, 2014

Nanocarbon:
Properties and Applications

Overview

Introduction
Synthesis & Purification
Overview of applications
Single nanotube measurements
Energy storage
Molecular electronics
Conclusion and future outlook

Introduction

Carbon

Melting point: ~ 3500oC

Atomic radius: 0.077 nm
Basis in all organic componds
10 mill. carbon componds

Introduction

Nanocarbon

Fullerene
Tubes
Cones
Carbon black
Horns
Rods
Foams
Nanodiamonds

Properties

Bonding

Graphite sp2

Diamond sp3

Properties

Nanocarbon

Shenderova et al. Nanotechnology 12 (2001) 191.

Properties

Nanocarbon
6 + 6 pentagons
1 5 pentagons

12 pentagons

Properties

Fullerene
The most symmetrical large molecule
Discovered in 1985
- Nobel prize Chemistry 1996, Curl, Kroto, and Smalley

C60, also 70, 76 and 84.

- 32 facets (12 pentagons and 20
hexagons)

Epcot center,
Paris

- prototype
~1 nm

Architect: R. Buckminster Fuller

Properties

Fullerene
Symmetric shape
lubricant

Large surface area

catalyst

Properties

Fullerene
Symmetric shape
lubricant

Large surface area

catalyst

High temperature (~500oC)

High pressure

Properties

Fullerene
Symmetric shape
lubricant

Large surface area

catalyst

High temperature (~500oC)

High pressure
Hollow
caging particles

Properties

Fullerene
Chemically stable as graphite
- most reactive at pentagons

Crystal by weak van der Waals force

Superconductivity
- K3C60: 19.2 K
- RbCs2C60: 33 K

Kittel, Introduction to

Introduction: common facts

Discovered in 1991 by Iijima

Unique material properties
Nearly one-dimensional structures
Single- and multi-walled

Properties

Nanotube
Discovered 1991, Iijima

Roll-up vector:

Ch n a1 m a2

Properties

Nanotube
Discovered 1991, Iijima

Roll-up vector:

Ch n a1 m a2

Properties

Nanotube
Electrical conductanse depending on helicity

Ch n a1 m a2

If

2n m
i , then metallic
3
else semiconductor

Properties

Nanotube
Electrical conductanse depending on helicity

Ch n a1 m a2

If

Current capacity

2n m
i , then metallic
3
else semiconductor

Carbon nanotube 1 GAmps / cm2

Copper wire

1 MAmps / cm2

Heat transmission
Comparable to pure diamond (3320 W / m.K)

Temperature stability
Carbon nanotube

750 oC (in air)

Metal wires in microchips 600 1000 oC

Caging
May change electrical properties
sensor

Introduction: nanotube structure

Roll a graphene sheet in a certain direction:
Armchair structure
Zigzag structure
Chiral structure
Defects result in bends and transitions

Geometry
Rollup Vector
(n,m)
n-m=3d

Chiral Angle
tan() = 3m/
(2(n2+m2+nm))

Arm Chair (n,n), =30

Zig-zag (n,0), =0
Chiral, 0< <30

Properties

Nanotube
High aspect ratio:
Length:
typical few m

length
1000
diameter
quasi 1D solid

Diameter:
as low as 1 nm

Properties

Nanotube
High aspect ratio:
Length:
typical few m

length
1000
diameter
quasi 1D solid

Diameter:
as low as 1 nm

SWCNT 1.9 nm

Zheng et al. Nature Materials 3

Properties

Nanotubes
Carbon nanotubes are the strongest ever known
material.
Young Modulus (stiffness):

Carbon nanotubes
Carbon fibers
High strength steel

1250 GPa
425 GPa (max.)
200 GPa

Tensile strength (breaking

strength)

Carbon nanotubes
GPa

11- 63

Carbon fibers
GPa

3.5 - 6

High strength steel

~ 2 GPa

Properties

Mechanical

Carbon nanotubes are very flexible

http://www.ipt.arc.nasa.gov/gallery.html
Nanoscience Research Group
University of North Carolina (USA)
http://www.physics.unc.edu/~rsuper/research/

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 4109 A/cm2 which is more than
1,000 times greater than metals
such as copper

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: arc discharge

MWNTs and SWNTs
Batch process

Relatively cheap
Many side-products

Research Approach
Chemical vapor deposition set up
Parameters to be varied are:
Temperature , Mass Flow Rate, Hydrocarbon source,
Carrier gas, Deposition Metal

28

Synthesis: CVD
Gas phase deposition
Large scale possible
Relatively cheap
SWNTs / MWNTs
Aligned nanotubes
Patterned substrates

Synthesis: laser ablation

Catalyst / no catalyst
MWNTs / SWNTs
Yield <70%

Use of very strong laser

Expensive (energy costs)

Commonly applied

Synthesis: growth mechanism

Metal catalyst
Tip growth / extrusion growth

Purification: techniques
Removal of catalyst:
Acidic treatment (+ sonication)
Thermal oxidation
Magnetic separation (Fe)

Removal of small fullerenes

Micro filtration
Extraction with CS2

Removal of other carbonaceous impurities

Thermal oxidation
Selective functionalisation of nanotubes
Annealing

Field Effect Transistors

FETs work because of applied
voltage on gate changes the amount
of majority carriers decreasing
Source-Drain Current
SWCNT and MWCNT used
Differences will be discussed
Gold Electrodes
Holes main carriers
Positive applied voltage should
reduce current

SWCNT Transport
Properties

Current shape consistent with

FET
Bias VSD = 10 mA
G(S) conductance varies by ~5
orders of magnitude
Mobility and Hole concentration
determined to be large
Q=CVG,T (VG,T voltage to
deplete CNT of holes)
C calculated from physical
parameters of CNT
p=Q/eL

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

???

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 + xOH CNT xH 2 O xe - oxidation

Counter Electrode
reduction

Ni OH 2
oxidation

NiOOH H + e-

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

Single Electron transistor

Conclusions
Mass production is nowadays too expensive
Many different techniques can be applied for
investigation
Large scale purification is possible
FEDs and CNTFETs have proven
Positioning of molecular electronics is difficult
Energy storage is still doubtful, fundamental
investigations are needed