Methods for Carbon Nanotube Synthesis

Presentation Overview

Background

Nomenclature Carbon Nanotube Classification Applications CVD

Synthesis Techniques

Nanotube Synthesis By CVD Process Plasma Enhanced CVD Nanotube Synthesis Nanotube Synthesis By Arc Discharge in a Magnetic Field Carbon Nanotube Synthesis Using Laser Ablation of Metallic Catalyst

Nomenclature

CVD - Chemical Vapor Deposition MWNT - Multi-Walled Carbon Nanotubes SWNT - Single-Walled Carbon Nanotubes XRD - X-ray Diffraction Pyrolysis - decomposition of organic material through the application of heat and the absence of oxygen Chirality - measure of the twist of the nanotube Ablation - Removing a surface material by vaporization
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Why Carbon nanotubes so interesting ?

Technological applications
conductive

and high-strength composites energy storage and conversion devices sensors, field emission displays nanometer-sized molecular electronic devices

Basic research: most phenomena of mesoscopic physics observed in CNs

ballistic, diffusive and localized regimes in transport disorder-related effects in MWNTs strong interaction effects in SWNTs: Luttinger liquid Coulomb blockade and Kondo physics spin transport superconductivity

Allotropic forms of Carbon

Curl, Kroto, Smalley 1985

graphene

Iijima 1991
(From R. Smalleys web image gallery)

What Are Carbon Nanotubes?

CNT can be described as a sheet of graphite rolled into a cylinder Constructed from hexagonal rings of carbon Can have one layer or multiple layers Can have caps at the ends making them look like pills

Information retrieved from: http://www.photon.t.u-tokyo.ac.jp/~maruyama/agallery/agallery.html

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.

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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Nanotube Classification
Chirality - twist of the nanotube Described as the vector R (n, m) Armchair vector, R vector, angle = 0, armchair nanotube 0 < < 30, chiral nanotube > 30, zigzag nanotube

Information and image retrieved from: http://www.pa.msu.edu/cmp/csc/ntproperties/

Nanotube Classification
(10, 10) (10, 5)

Information retrieved from: http://www.photon.t.u-tokyo.ac.jp/~maruyama/agallery/agallery.html

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Nanotube Classification

MWNT

Consist of 2 or more layers of carbon Tend to form unordered clumps

SWNT

Consist of just one layer of carbon Greater tendency to align into ordered bundles Used to test theory of nanotube properties

Images retrieved from: http://www.photon.t.u-tokyo.ac.jp/~maruyama/agallery/agallery.html

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Introduction: common facts

Discovered in 1991 by Iijima Unique material properties Nearly one-dimensional structures Single- and multi-walled

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Introduction: nanotube structure

Roll a graphene sheet in a certain direction:

Armchair structure
Zigzag structure Chiral structure Defects result in bends and transitions
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Introduction: special properties

Difference in chemical reactivity for end caps and side wall High axial mechanical strength Special electrical properties:

Metallic Semi conducting

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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

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

MWNTs and SWNTs Batch process

Relatively cheap Many side-products

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Synthesis: laser ablation

Catalyst / no catalyst MWNTs / SWNTs Yield <70%

Use of very strong laser

Expensive (energy costs)

Commonly applied
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Purification

Contaminants:
Catalyst particles Carbon clusters Smaller fullerenes: C60 / C70

Impossibilities:
Completely retain nanotube structure Single-step purification

Only possible on very small scale:

Isolation of either semi-conducting SWNTs

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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

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Chemical Vapor Deposition

1.

2. 3.

4.

Gas enters chamber at room temperature (cooler than the reaction temperature) Gas is heated as it approaches the substrate Gases then react with the substrate or undergo chemical reaction in the Reaction Zone before reacting with the substrate forming the deposited material Gaseous products are then removed from the reaction chamber
Information and photo retrieved from: http://www.sandia.gov/1100/CVDwww/cvdinfo.htm21

Nanotube Synthesis By CVD Process

Schematic from: Andrews, Jacques, Qian, and Rantell, Mulitwall Carbon Nanotubes: Synthesis and Application

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Nanotube Synthesis By CVD Process

Source of carbon atoms usually comes from an organic compound Mixed with a metal catalyst and inert gas Atomized and sprayed into reactor with temperatures ranging from 600C to 1200C Pyrolysis of organic compound deposits carbon (as soot) and carbon nanotubes on reactor wall (usually a tube constructed from quartz)
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Sources of Carbon

Typical Organic/Catalyst Mixtures

Xylene/ferrocene (Andrews et al.) Toluene, benzene, xylene, mesitylene, and n-hexane/ferrocene (Vivekchand et al.) Ethylene and ethanol/Fe, Co, and Mo alloys (K. Mizuno et al.)

Typical Carrier Gases

Argon Hydrogen

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Plasma Enhanced CVD Nanotube Synthesis

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Plasma Enhanced CVD Nanotube Synthesis

Alumina substrate (Al2O3) is coated with ferric nitrate [Fe(NO3)3 6H2O] (the catalyst) Methane and hydrogen are introduced to the vacuum chamber (total pressure of 15 torr) The chamber is then heated to 850C-900C with a input microwave power of 600W Nanotubes are grown from the substrate material

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Plasma Enhanced CVD Nanotube Synthesis

Methane moves toward the catalyst on the substrate Heat of the reactor decomposes methane at the catalyst surface Catalyst is at a slightly cooler temperature so carbon is supersaturated in the catalyst film so carbon precipitates out Carbon forms nanotubes at the surface of the catalyst film
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Nanotube Synthesis By Arc Discharge in a Magnetic Field

Image courtesy of: K. Anazawa, K. Shimotani, C. Manabe, H. Watanabe, and M. Shimizu. High-puritymagnetic field28

Nanotube Synthesis By Arc Discharge in a Magnetic Field

Electrodes are composed of high purity graphite (>99.999%) ~70 A at ~18V dc is applied to the electrodes Magnets are placed around electrodes which help align nanotubes during formation Carbon nanotubes are formed at atmospheric pressures from the electrodes

Information courtesy of: K. Anazawa, K. Shimotani, C. Manabe, H. Watanabe, and M. Shimizu. High-puritymagnetic field 29

Carbon Nanotube Synthesis Using Laser Ablation of Metallic Catalyst

A well mixed acetylene-air mixture is burned inside a tube furnace A laser is used to vaporize a metal target (either Fe or Ni) The post-flame exhaust gas is mixed with the metallic vapor and allowed to cool During cooling, carbon nanotubes are formed
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Applications

Electronic Devices

Nanotube TVs Nano-wiring

High Strength Composites

100 times as strong as steel and 1/6 the weight

Conductive Composites Medical Applications

Encase drug into nanotube capsule for more predictable time release

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Overview of potential applications

< AFM Tip

> Molecular electronics

Transistor > FED devices:
Displays

< Others
Composites

< Energy storage:

Li-intercalation Hydrogen storage Supercaps

Biomedical
Catalyst support Conductive materials

???

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Overview of potential applications

< AFM Tip

> Molecular electronics

Transistor > FED devices:
Displays

< Others
Composites

< Energy storage:

Li-intercalation Hydrogen storage Supercaps

Biomedical
Catalyst support Conductive materials

???

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Overview of potential applications

< AFM Tip

> Molecular electronics

Transistor > FED devices:
Displays

< Others
Composites

< Energy storage:

Li-intercalation Hydrogen storage Supercaps

Biomedical
Catalyst support Conductive materials

???

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Energy Storage

Experiments & Modelling Electrochemical Storage of Lithium Electrochemical Storage of Hydrogen Gas Phase Intercalation of Hydrogen Supercapacitors

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References

R. Andrews, D. Jacques, D. Quan, and T. Rantell. Multiwall Carbon Nanotubes: Synthesis and Application. Accounts of Chemical Research. Vol. 35, No. 12, 2002 Chemical Vapor Deposition. http://www.sandia.gov/1100/CVDwww/cvdinfo.htm A Carbon Nanotube Page. http://www.personal.rdg.ac.uk/~scsharip/tubes.htm Physical Properties of Carbon Nanotubes. http://www.pa.msu.edu/cmp/csc/ntproperties/ S.R.C. Vivekchand, L.M. Cele, F.L. Deepak, A.R. Raju, and A. Govindaraj. Carbon nanotubes by nebulized spray pyrolysis. Chemical Physics Letters. 386 (2004) 313-318
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References

K. Mizuno, K. Hata, T. Saito, S. Ohshima, M. Yumura, and S. Iijima. Selective Matching of Catalyst Element and Carbon Source in SingleWalled Carbon Nanotube Synthesis on Silicon Substrates. Journal of Physical Chemistry B, Vol. 109, No. 7, 2005 K. Anazawa, K. Shimotani, C. Manabe, H. Watanabe, and M. Shimizu. Applied Physics Letters. Vol. 81, No. 4, 22 July 2002 R.L. Vander Wal, G.M. Berger, and T.M. Ticich. Carbon nanotube synthesis in a flame using laser ablation for in situ catalyst generation. Applied Physics A: Materials Science & Processing. 77, 885-889, 2003 L.C. Qin, D. Zhou, A.R. Krauss, and D.M. Gruen. Growing carbon nanotubes by microwave plasma-enhanced chemical vapor deposition. Applied Physics Letters. Vol. 72, No. 26, 29 June 1998

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