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Nanomaterials -carbon fullerenes and nanotubes
Lecture 3
郭修伯
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Carbon fullerenes and nanotubes
• Carbon– graphite form: good metallic conductor– diamond form: wide band gap semiconductor
• Ref:– “Science of Fullerenes and Carbon nanotubes”,
M.S. Dresselhaus, G. Dresselhaus and P.C. Eklund, Academic Press (1996)
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Carbon fullerenes
• A molecule with 60 carbon atoms C60
– with an icosahedral symmetry– buckyball or buckmister fullerene– C-C distance 1.44 A (~ graphite 1.42 A)– 20 hexagonal faces + 12 pentagonal faces– each carbon atoms: 2 single bonds (1.46 A)+ 1
double bond (1.40 A)
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Carbon fullerenes
• Initially synthesized by Krätschmer et al. 1990
• C60, C70, C76, C78, C80
Fig 6.1
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Carbon fullerenes synthesis
– arc discharge between graphite electrodes in 200 torr of He gas
– heat at the contact point between the electrodes evaporates carbon
• form soot and fullerenes
• condense on the water-cooled walls of the reactor
• ~15% fullerenes: C60 (13%) + C70(2%)
– Separation by mass• liquid (toluene) chromatography
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Carbon nanotubes
• Ref– M. Terrones, Ann. Rev.Mater. Rev. 33 (2003)
419– K. Tanaka, T. Yambe and K. Fukui, “The
Science and Technology of Carbon Nanotubes” Elsevier, 1999
– R. Saito, G. Dresselhaus and M.S. Dresselhaus, “Physical Properties of Carbon Nanotubes”, Imperial College Press, 1998
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Single-wall carbon nanotube (SWCNT)
• diameter and chiral angle =30° : armchair = 0° : zigzag– 0° < < 30° : chiral
Fig 6.2
Fig 6.3
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Multi-wall carbon nanotube (MWCNT)
• Several nested coaxial single-wall tubules (chiral tubes)
• typical dimensions:– o.d.: 2-20 nm– i.d.: 1-3 nm– intertubular distance: 0.34 nm– length: 1-100 m
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Carbon nanotube synthesis
• Initially synthesized by Iijima (1991) by arc discharge
• Arc evaporation, laser ablation, pyrolysis, PECVD, eletrochemical
• Requires an “open end”:– carbon atoms from the gas phase could land and
incorporate into the structure.
– Open end maintenance: high electric field, entropy opposing, or metal cluster
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Carbon nanotube synthesis
• Electric field in the arc-discharge promotes the growth– tubes form only where the current flows on the
larger negative electrode– typical rate: 1 mm/min (100A, 20V, 2000-
3000°C)– the high temperature may cause the tubes to
sinter (defects!!)
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Carbon nanotube formation
• Single-wall:– add a small amount of transition metal powder
(e.g. Co, Ni, or Fe)– Thess et al. (1996)
• condensation of laser-vaporized carbon catalyst mixture
• low temp: ~1200°C
• alloy cluster anneals all unfavorable structure into hexagons -> straight nanotubes
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Aligned carbon nanotubes
• CVD– on Fe nanoparticles embedded in silica– the catalyst size affects: tube diameter, tube
growth rate, vertical aligned tube density
• Plasma induced well-aligned tubes– on contoured surfaces– with a growth direction perpendicular to the
local substrate surface
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Fig 6.5
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Fig 6.5
Fig 6.6
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Carbon nanotube growth mechanism
• Atomic carbon dissolves into the metal droplet
• diffuses to and deposits at the growth substrate
• mass production– CVD (700~800°C), but poor crystallinity– CVD (2500~3000°C+argon), improved
crystallinity
• base growth? tip growth?
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Tip/base growth
• PECVD and pyrolysis:– catalytic particles are found at the tip and
explained by the tip growth model
• thermal CVD using iron as catalyst:– vertical aligned carbon nanotubes– base growth model– both tip and base growth (depend on catalyst)
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Carbon nanotubes purification
• Impurities– amorphous carbon and carbon nanoparticles
• gas phase method– remove impurities by an oxidation process
– burn off many of the nanotubes (especially smaller ones)
• liquid phase method– KMnO4 treatment: higher yield than gas phase purification, but
shorter length
• intercalation methods– reacting with CuCl2-KCl, remove impurities
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Carbon nanotube properties
• Excellent for stiff and robust structures– carbon-carbon bond in graphite
• flexible and do not break upon bending
• extremely high thermal conductivity
• applications– catalyst, storage of hydrogen and other gases,
biological cell electrodes, electron field emission tips, scanning probe tip, flow sensors