Complex three-point junctions of single-walled carbon nanotubes are proposed as building blocks of nanoscale electronic devices. Both T- and Y-junctions, made up of tubes with differing diameters and chiralities, are studied as prototypes. All the proposed complex junctions have been found to be local minima of the total energy on relaxation with a generalized tight-binding molecular dynamics scheme.

Using ab initio and parametrized techniques, we determine the equilibrium structure of an ordered “bundle” of (10,10) carbon nanotubes. Because of small intertube interaction and lattice frustration, we predict a very soft libration mode to occur at v ≈ 12 cm−1. This mode is predicted to disappear above the orientational melting temperature which marks the onset of free tube rotations about their axis. We discuss the effect of the weak intertube coupling and orientational disorder on the electronic structure near the Fermi level.

The electronic structures of different morphologies of carbon nanotubes are investigated within either tight-binding or ab initio frameworks. After a brief description of the electronic properties of the “perfect” rolled-up graphene sheet, nanotubes containing pentagon-heptagon pairs, tips (hemispherical caps), sp3-like lines responsible for polygonization, multishell and solid-state packings (bundles) are studied in order to point out the influence of such defects on the electronic states of the “perfect” cylinders. Most of the time, a structural optimization was performed on the atomic topology, prior to the calculation of the electronic properties. Connections with experimental facts are indicated as frequently as possible.

Scanning tunneling microscopy and spectroscopy have been used to characterize the atomic structure and tunneling density of states of individual single wall carbon nanotubes (SWNT's) and ropes containing many SWNT's. Analysis of atomically resolved SWNT images shows that the nanotubes consist of a wide range of diameters and helicities with no one structure clearly dominant. Tunneling spectroscopy measurements made simultaneously on atomically resolved SWNT's exhibit semiconducting and metallic behavior that depend predictably on helicity and diameter. In addition the band gaps of the semiconducting tubes were also found to depend inversely on diameter. These results are compared to theoretical predictions, and the implications of these studies as well as important future directions are discussed.

The recent application of tunneling probes in electronic structure studies of carbon nanotubes has proven both powerful and challenging. Using scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS), local electronic properties in ordered aggregates of carbon nanotubes (multiwalled nanotubes and ropes of single walled nanotubes) have been probed. In this report, we present evidence for interlayer (concentric tube) interactions in multiwalled tubes and tube-tube interactions in singlewalled nanotube ropes. The spatially resolved, local electronic structure, as determined by the local density of electronic states, is shown to clearly reflect tube-tube interactions in both of these aggregate forms.

A resonant Raman study of single-wall carbon nanotubes (SWNT) using several laser lines between 0.94 and 3.05 eV is presented. A detailed lineshape analysis shows that the bands associated with the nanotube radial breathing mode are composed of a sum of individual peaks whose relative intensities depend strongly on the laser energy, in agreement with prior work. On the other hand, the shape of the Raman bands associated with the tangential C–C stretching motions in the 1500–1600 cm−1 range does not depend significantly on the laser energy for laser excitation energies in the ranges 0.94–1.59 eV and 2.41–3.05 eV. However, new C–C stretching modes are observed in the spectra collected using laser excitations with energies close to 1.9 eV. The new results are discussed in terms of the difference between the 1D electronic density of states for the semiconducting and metallic carbon nanotubes.

High temperature heat treatment of single wall carbon nanotube bundles in flowing H2 was used to produce a significant fraction (∼40%) of diameter-doubled, or coalesced tubes with a mean diameter corresponding to that of ∼(20, 20) tubes. At three laser excitation wavelengths (514.5, 647, and 1064 nm), a reduction in the Raman scattering intensity of the strong radial and tangential modes was observed in the H2-treated sample, consistent with the reduced fraction of tubes in the sample after coalescence. However, using 488 nm excitation, little or no change is observed in the Raman spectrum after the H2 treatment, suggesting that this excitation wavelength couples only to chiral symmetry tubes. Using the 647 nm excitation, the effect of H2 treatment on the tangential band is quite unique, and a significant change in the shape of the tangential band was observed. Our lineshape analysis, and other results reported in this issue, suggest that this unique change of shape is due to lost scattering intensity from metallic tubes partially compensated by tangential mode scattering from the coalesced tubes. The normally prominent radial breathing mode band, which would be expected at ∼90 cm−1 for ∼(20, 20) tubes was not observed, indicating that these larger diameter tubes do not exhibit strong resonant scattering, at least at any of the wavelengths used in this study.

The optical properties of inorganic fullerene-like and nanotube MS2 (M = Mo, W) material are studied through absorption and resonance Raman, and compared to those of the corresponding bulk material. The absorption measurements show that the semiconductivity is preserved. Nevertheless, the positions of the excitons are altered in comparison to the bulk. The Raman spectra of the nanoparticles show a close correspondence to that of the bulk. However, the first-order peaks are broadened and, under resonance conditions, new peaks are observed. The new peaks are assigned to disorder-induced zone edge phonons.

Micro-Raman spectroscopy is used to monitor the cooling-induced compressive deformation of carbon nanotubes embedded in an epoxy matrix. Young's modulus of single- and multiwall nanotubes may then be derived from a concentric cylinder model for thermal stresses, using the D*-band shift for each tube type. The resulting values of the elastic moduli are in very good agreement with predicted theoretical values, and with the published experimental data set of Treacy et al., Nature (London) 381, 678 (1996).

We have subjected single-walled carbon nanotube materials (SWNTM's) to a variety of organic functionalization reactions. These reactions include radioactive photolabeling studies using diradical and nitrene sources, and treatment with dichlorocarbene and Birch reduction conditions. All of the reactions provide evidence for chemical attachment to the SWNTM's, but because of the impure nature of the staring materials, we are unable to ascertain the site of reaction. In the case of dichlorocarbene we are able to show the presence of chlorine in the SWNT bundles, but as a result of the large amount of amorphous carbon that is attached to the tube walls, we cannot distinguish between attachment of dichlorocarbene to the walls of the SWNT's and reaction with the amorphous carbon.

We discuss the oxidation of carbon nanotubes and how it is affected by structure and geometry. While graphite is known to oxidize primarily at defects to create etch pits, nanotubes have additional structural features such as high curvature, helicity, and contain five and seven membered rings which modify the initiation and propagation of oxidation. Oxidation does not necessarily start at the tip of the tubes, and there are pronounced differential oxidation rates between layers which depend on the helicity of the individual shells.

The preparation and structural characterization of carbon nanoclusters of different morphologies produced by three different methods and under a variety of conditions is reported. In a comparative manner, the growth phenomena and structural properties of carbon nanoclusters are investigated as synthesized by (a) the high temperature (˜3000 °C) and high carbon-content process of the conventional arc-discharge, (b) the high temperature but low carbon-content process of the modified arc-discharge, and finally (c) the relatively low temperature (˜500 °C) process of Ni catalytic disproportionation of carbon monoxide.

Carbon nanotube reinforced aluminum (Al) composites were produced by hot-press and hot-extrusion methods. The interfacial structure between the carbon nanotube and Al was examined using a transmission electron microscope (TEM), and the mechanical properties were measured by a tensile test. TEM observations have shown that the nanotubes in the composites are not damaged during the composite preparation and that no reaction products at the nanotube/Al interface are visible after annealing for 24 h at 983 K. The strength of the composites is only slightly affected by the annealing time at 873 K, while that of the pure Al produced in a similar powder metallurgy process significantly decreases with time. These studies are considered to yield experimental information valuable for producing high performance composites.

Morphology of carbide grain in WC–12 wt.% Co–0.5 wt.% VC was examined by HREM and EDS with a special interest in the segregation of V at the WC/Co interfaces. A small addition of VC in WC-Co is effective to suppress the grain growth of carbide grains. HREM observation revealed that the WC/Co interfaces are faceted and consist of mainly two kinds of habit planes, (1010) and (0001), respectively. EDS analyses clearly showed the segregation of doped V along the interfaces. In addition, the concentration of segregated V is higher at the (0001) type habit plane than (1010) one. The retardation of the grain growth of carbide grains in the VC-doped WC-Co is closely related to the formation of the faceted WC/Co interface.

A technique for preparing electrically conductive coatings of Cu3BiS3 powder in polyacrylic acid matrix is presented. Bi2S3 powder obtained by chemical precipitation was introduced into a freshly prepared CuS chemical deposition bath. After the initial nucleation period, CuS started to deposit on the Bi2S3 surface. The as-obtained CuS–Bi2S3 powder was mixed with polyacrylic acid aqueous solution, and the resulting mixture was used as a paste to form a screen-printed composite coating. Up to 200 °C the film behaves like a simple CuS film; the sheet resistance is around 100 and the crystallized phase in the composite is CuS (Covellite). When the temperature is equal or higher than 250 °C, atomic diffusion at the CuS–Bi2S3 interface is promoted, leading to the formation of the ternary compound Cu3BiS3 (Wittichenite) in the composite film. The formation of the compound depends on the temperature, relative abundance of the Bi2S3 and CuS components in the CuS–Bi2S3 pigment, as well as on the annealing atmosphere.

The oxidation of tin layers deposited onto alumina substrates is investigated with the aim to identify the different steps of the process and obtain information on the sample homogeneity, phase segregation, and degree of oxidation. It is shown that at least three phases coexist at 450 °C, Sn, SnO, and SnO2, and remarkable inhomogeneities, already visible at an optical inspection, are found in the thin film. A micro-Raman mapping of the layer shows that these inhomogeneities are related to the presence of different Sn oxidation states, as evidenced by the inhomogeneous distribution of SnO and SnOx Raman bands. The thin film becomes homogeneous after annealing treatments above 550 °C, where only the SnO2 cassiterite phase is detected.

Highly conductive biaxially textured RuO2 thin films were deposited on technically important SiO2/Si substrates by pulsed laser deposition, where yttria-stabilized zirconia (YSZ) produced by ion-beam-assisted-deposition (IBAD) was used as a template to enhance the biaxial texture of RuO2 on SiO2/Si. The biaxially oriented RuO2 had a room-temperature resistivity of 37 μΔ-cm and residual resistivity ratio above 2. We then deposited Ba0.5Sr0.5TiO3 thin films on RuO2/IBAD-YSZ/SiO2/Si. The Ba0.5Sr0.5TiO3 had a pure (111) orientation normal to the substrate surface and a dielectric constant above 360 at 100 kHz.

Tantalum carbide nanorods and nanoparticles have been synthesized using a vapor-solid reaction path starting with CVD grown carbon nanotube precursors. Their structures were studied using XRD, TEM, and HRSEM. Superconducting properties were characterized using a SQUID magnetometer. For reactions at lower temperatures, carbide nanorods, which replicate the ∼14 nm diameter of the precursor carbon nanotubes, are observed. For higher temperature reactions, coarsened carbide nanoparticles (100–250 nm) are observed which have spherical or cubic-faceted morphologies. A morphological Rayleigh instability is postulated as initiating the transition from nanorod to nanoparticle morphologies. Stoichiometric bulk TaC crystallizes in the rock salt structure and has a superconducting transition temperature of 9.7 K. In TaC nanorods and nanoparticles, the superconducting properties correlate with the lattice parameter. Nanoparticles with a little higher lattice parameter than the ideal one show higher Tc and higher fields at which the superconductivity disappears than stoichiometric bulk TaC.

An infiltration and growth (IG) process which enables the fabrication of three-dimensional (3D) components of REBa2Cu3O7 (RE = Y, Gd, Sm, Nd, etc.) (RE-123) superconductors with a highly textured microstructure is described. The advantages of the process in comparison with conventional melt processing are discussed. The process has been demonstrated to yield highly favorable microstructures in the case Y-123 processed in air, as well as in the case of Gd-123 processed in reduced oxygen partial pressure.

Thin films of nanostructured silicon (ns-Si:H) were deposited by plasma-enhanced chemical vapor deposition in the presence of silicon nanoparticles at 100 °C substrate temperature using a silane and hydrogen gas mixture under continuous wave (cw) plasma conditions. The nanostructure of the films has been demonstrated by diverse ways: transmission electron microscopy, Raman spectroscopy, and x-ray diffraction, which have shown the presence of ordered silicon clusters (1–2 nm) embedded in an amorphous silicon matrix. Because of the presence of these ordered domains, the films crystallize faster than standard hydrogenated amorphous silicon samples, as evidenced by electrical measurements during the thermal annealing.