Nanotubes from Carbon.

Graphene is one of the most promising materials in nanotechnology. The electronic and mechanical properties of graphene samples with high perfection of the atomic lattice are outstanding, but structural defects, which may appear during growth or processing, deteriorate the performance of graphene-based devices. However, deviations from perfection can be useful in some applications, as they make it possible to tailor the local properties of graphene and to achieve new functionalities. In this article, the present knowledge about point and line defects in graphene are reviewed. Particular emphasis is put on the unique ability of graphene to reconstruct its lattice around intrinsic defects, leading to interesting effects and potential applications. Extrinsic defects such as foreign atoms which are of equally high importance for designing graphene-based devices with dedicated properties are also discussed.

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Structural defects in graphene

Carbon nanotubes can be thought of as graphitic sheets with a hexagonal lattice that have been wrapped up into a seamless cylinder. Since their discovery in 19911, the peculiar electronic properties of these structures have attracted much attention. Their electronic conductivity, for example, has been predicted2,3,4 to depend sensitively on tube diameter and wrapping angle (a measure of the helicity of the tube lattice), with only slight differences in these parameters causing a shift from a metallic to a semiconducting state. In other words, similarly shaped molecules consisting of only one element (carbon) may have very different electronic behaviour. Although the electronic properties of multi-walled and single-walled nanotubes5,6,7,8,9,10,11,12 have been probed experimentally, it has not yet been possible to relate these observations to the corresponding structure. Here we present the results of scanning tunnelling microscopy and spectroscopy on individual single-walled nanotubes from which atomically resolved images allow us to examine electronic properties as afunction of tube diameter and wrapping angle. We observe bothmetallic and semiconducting carbon nanotubes and find thatthe electronic properties indeed depend sensitively on thewrapping angle. The bandgaps of both tube types are consistent with theoretical predictions. We also observe van Hove singularities at the onset of one-dimensional energy bands, confirming the strongly one-dimensional nature of conduction within nanotubes.

Electronic structure of atomically resolved carbon nanotubes

Single-walled carbon nanotubes (SWNTs) offer the prospect of both new fundamental science and useful (nano)technological applications1. High yields (70–90%) of SWNTs close-packed in bundles can be produced by laser ablation of carbon targets2. The electric-arc technique used to generate fullerenes and multi-walled nanotubes is cheaper and easier to implement, but previously has led to only low yields of SWNTs3,4. Here we show that this technique can generate large quantities of SWNTs with similar characteristics to those obtained by laser ablation. This suggests that the (still unknown) growth mechanism for SWNTs must be independent of the details of the technique used to make them. The ready availability of large amounts of SWNTs, meanwhile, should make them much more accessible for further study.

Large-scale production of single-walled carbon nanotubes by the electric-arc technique

Nanodiamonds have excellent mechanical and optical properties, high surface areas and tunable surface structures. They are also non-toxic, which makes them well suited to biomedical applications. Here we review the synthesis, structure, properties, surface chemistry and phase transformations of individual nanodiamonds and clusters of nanodiamonds. In particular we discuss the rational control of the mechanical, chemical, electronic and optical properties of nanodiamonds through surface doping, interior doping and the introduction of functional groups. These little gems have a wide range of potential applications in tribology, drug delivery, bioimaging and tissue engineering, and also as protein mimics and a filler material for nanocomposites.

The properties and applications of nanodiamonds

SPHERICAL particles of carbon consisting of concentric graphite-like shells ('carbon onions') can be formed by electron irradiation of graphitic carbon materials1,2. Here we report that, when such particles are heated to ∼700 °C and irradiated with electrons, their cores can be transformed to diamond. Under these conditions the spacing between layers in the carbon onions decreases from 0.31 in the outer shells (slightly less than the 0.34-nm layer spacing of graphite) to about 0.22 nm in the core, indicating considerable compression towards the particle centres. We find that this compression allows diamond to nucleate—in effect the carbon onions act as nanoscopic pressure cells for diamond formation.

Carbon onions as nanoscopic pressure cells for diamond formation

Topology related changes in the local density of states near the ends of closed carbon nanotubes are investigated using spatially resolved scanning tunneling spectroscopy and tight binding calculations. Sharp resonant valence band states are observed in the experiment at the tube ends, dominating the valence band edge and filling the band gap. Calculations show that the strength and position of these states with respect to the Fermi level depend sensitively on the relative positions of pentagons and their degree of confinement at the tube ends.

Electronic structure and localized states at carbon nanotube tips

BCN nanotubes and boron doping of carbon nanotubes

The formation, annealing and self-compression of carbon onions under electron irradiation

We propose a new microscopic mechanism to explain the unusually fast fusion process of carbon nanotubes. We identify the detailed pathway for two adjacent (5,5) nanotubes to gradually merge into a (10,10) tube, and characterize the transition states. The propagation of the fused region is energetically favorable and proceeds in a morphology reminiscent of a Y junction via a zipper mechanism, involving only Stone-Wales bond rearrangements with low activation barriers. The zipper mechanism of fusion is supported by a time series of high-resolution transmission electron microscopy observations.

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P. M. Ajayan

Papers

Carbon onions as nanoscopic pressure cells for diamond formation

Electronic structure and localized states at carbon nanotube tips

BCN nanotubes and boron doping of carbon nanotubes

The formation, annealing and self-compression of carbon onions under electron irradiation

Zipper mechanism of nanotube fusion: theory and experiment.