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
