Carbon Nanotubes

Introduction Applications Growth Techniques Growth Mechanism

Presented by: Shishir Rai

University of Notre Dame

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 1 + m 2, Chiral Angle with respect to the zigzag axis.

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Armchair (n,m) = (5,5) = 30

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

Chiral (n,m) = (10,5) 0 < < 30

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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

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Types of CNTs
Single Wall CNT (SWCNT) Multiple Wall CNT (MWCNT) Can be metallic or semiconducting depending on their geometry.

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CNT Properties

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CNT Properties (cont.)

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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.

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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: 10s of m long, very straight & have 5-30nm diameter. SWNT: needs metal catalyst (Ni,Co etc.). Produced in form of ropes consisting of 10s of individual nanotubes close packed in hexagonal crystals.

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Nanotubes Growth Methods

c) Chemical Vapor Deposition:
Hydrocarbon + Fe/Co/Ni catalyst
550-750C

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

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Controlled Growth by CVD

Methane + Porous Si + Fe pattern
a) a) SEM image of aligned nanotubes. SEM image of side view of towers. Self-alignment due to Van der Walls interaction. High magnification SEM image showing aligned nanotubes. Growth Process: Base growth mode.
CVD

Aligned MWNTs

a)

d)

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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

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Open-Ended Growth of Multi Walled Nanotube

Role of Hexagons, Pentagons & Heptagons

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MWNT: The possibilities

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MWNT: Lip-Lip Interaction Model

High Coordinated C atoms

Low Coordinated C atoms

H-atoms

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SWNT Growth Mechanism

Is uncatalyzed growth possible?
Simulations & Observations No! Spontaneous closure at experimental temperatures of 2000K to 3000K. Closure reduces reactivity.

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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.

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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.

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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.

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