Carbon: (fullerenes, nanotubes, diamond UNCD) Structure Synthesis Properties Graphene fabrication & structure electronic properties potential

l for applications

http://www.pa.msu.edu/cmp/csc/nanotube.html

Allotropes of Carbon

Fullerenes Nobel Prize 1996

http://nobelprize.org/nobel_prizes/chemistry/laureates/1996/index.html

Discovery of Fullerenes

Allotropes of Carbon

"Environmental Applications of Carbon-Based Nanomaterials", Environmental Science & Technology, 42, 5843 (2008)

Carbon: Electronic structure

C*: 1s2, 2s2, 2p2

sp3

sp2

C: 1s2, 2s2, 2px1, 2py1, 2pz0

C*: 1s2, 2s1, 2px1, 2py1, 2pz1

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Carbon orbitals

sp3 (diamond) sp2 (graphene)

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Fullerenes C60
f - faces e -edges v - vertices

f +v = e+2
Diameter of C60 is 0.71 nm

Functionalization of C60:

Superconductivity in M3C60
K3C60 superconducting at 18K (discovered in 1991) Cs3R60 superconducting at 33K (discovered in 2008)
Ganin et al. Nature Materials 7 (2008) 367

Nanotube Classification

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Carbon Nanotube Chirality & Diameter

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CNT Chirality vs Physical Properties

Chirality (n,m) If n-m=0,3,6,9 metallic

S-M junction

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Structure verification by STM and Raman

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Carbon Nanotube Properties

Raman spectroscopy of SWNT

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CNT Growth: Arc Discharge

Fullerenes deposited as soot SWNT in soot if anode contains metal catalyst (Fe, Co, Ni-Co, etc.) MWNT deposited on cathode under hydrogen gas (0.34 nm layer spacing)
Yoshinori Ando, Xinluo Zhao, Toshiki Sugai, and Mukul Kumar, Materials Today, 2004, p. 22-49.

L. C. Qin, Nature (2000) 408, 50

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CNT Growth: Laser Ablation

YAG or CO2 laser aimed at carbon target containing catalytic metals SWNT diameter depends on furnace temperature and catalyst

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CNT Growth: Chemical Vapor Deposition

A nickel cap is on the tip of each nanotube (except arrow)

Hydrocarbon vapor passed through a tube furnace. 17 SWNTs or MWNTs depends on size and temperature of catalyst (Fe, Ni with NH3). Low-temperature (600-900C) yields MWNTs, higher temperature (900-1200C) favors SWNTs.

CNT Growth: Chemical Vapor Deposition

Ni-catalyzed CNT root growth recorded in 810-3 mbar C2H2 at 615 C, Hofmann, et al., Nano Lett., 7 (3), 602 -608, 2007

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CNT Growth: SWNT vs MWNT

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CNT Growth Problems

Problems with CNT production Mixture of metallic and semiconducting Alignment and positioning A breakthrough? ST-cut single crystal quartz substrates ethanol/methanol as carbon source Cu nanoparticles as catalysts Results 1.55 to 1.78 nm diameter SWNT 95% semiconducting CNT aligned
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CNT: State of the Art Aligned SWNT

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CNT in Scanning Probe Microscopy

600 nm deep trenches; 250 nm wide

conventional AFM tip

CNT AFM tip

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CNT Electronic Properties

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CNT Functionalization
Teflon-coated CNT

a) Plasma discharge chemical vapor deposition of acetylene and ammonia on nickel catalyst islands gives 50 nm diameter carbon nanotubes with a height of 2 m. (b) Hexafluoropropylene oxide gas thermally decomposes to form CF2 radicals which polymerize into PTFE on the nanotube forest substrate. (c) The surface roughness templated by the nanotube forest and the low surface energy imparted by the PTFE coating produce a superhydrophobic surface.

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"Superhydrophobic Carbon Nanotube Forests," Nano Letters, 3, 1701-1705 (2003)

Functionalized CNTs in Medical Applications

Biological systems are highly transparent to 700-1100 nm near-infrared (NIR) light Single-walled carbon nanotubes (SWNTs) strongly absorb NIR light Folate (vitamin B9) phospholipid functionalized SWNTs taken up by tumors with folate receptors Selective cancer cell destruction can occur by NIR local heating, without harming receptor-free normal cells Functionalized carbon nanotubes (green) taken up by cancer cells with folate receptors (top) and normal cells (bottom). Magnification 20x.
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Functionalized CNTs

Immobilization of Rh nanocatalyst on CNT

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CNT Applications
Samsung Field Emission Display CNT as Field Emitters in Displays

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CNT-Based Radio
NEMS Mechanical Resonant Frequency ~ 300 MHz still

vibrating

K. Jensen, J. Weldon, H. Garcia, and A. Zettl, Nano Letters 7 (11), 3508-3511 (2007)

Radio transmissions tuned to the nanotube's resonance frequency force the charged nanotube to vibrate. Field emission of electrons from the tip of thenanotube is used to detect the vibrations and also amplify and demodulate the signal. A current measuring device, such as a sensitive speaker, monitors the output of the radio.
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CNTs in Composites

SEM image of fractured polycarbonate composite loaded at 1 wt% with Zyvex processed SWNTs. The nanotubes remain embedded in the matrix even after fracture.

With a tensile strength eight times that of stainless steel and with a thermal conductivity five times that of copper, CNTs are obvious choices for creating a new class of composite materials.
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CNT Ropes

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M. Zhang, K.R. Atkinson, and R. H. Baughman, Science, 19 November 2004, 1358-1361.

Application of CNTs

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Nanocrystalline Diamond Ultra Nanocrystalline Diamond (UNCD)

UNCD Growth by PECVD Good conductor Hard material Resistant to wear Low thermal expansion

Field emitter tips coated by UNCD

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Nanocrystalline Diamond
UNCD coated AFM tips (commercially available)

http://www.thindiamond.com

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