CCVD synthesis of carbon nanotubes from (Mg,Co,Mo)O catalysts: influence of the proportions of cobalt and molybdenum

Carbon nanotubes have been synthesised by catalytic chemical vapour deposition of a H2–CH4 mixture (18 mol% CH4) over (Mg,Co,Mo)O catalysts. The total amount of cobalt and molybdenum has been kept constant at 1 cat% and the proportion of molybdenum with respect to cobalt has been varied from x(Mo) = 0.25–1.0. This variation has important effects on both the yield and the nature (number of walls, straight walls or bamboo-like structures) of the carbon nanotubes. It also has an influence on the purity of the samples (amount of encapsulated metal particles, presence or not of amorphous carbon deposits). For x = 0.25, the nanotubes were mainly double- and triple-walled (inner diameter less than 3 nm); samples prepared from catalysts with higher molybdenum ratios contained larger multi-walled carbon nanotubes (inner diameter up to 9 nm), having up to 13 concentric walls. It is proposed that different growth mechanisms may occur depending on the initial composition of the catalyst

Local optical field variation in the neighborhood of a semiconductor micrograting

The local optical field of a semiconductor micrograting (GaAs, 10x10 micro m) is recorded in the middle field region using an optical scanning probe in collection mode at constant height. The recorded image shows the micro-grating with high contrast and a displaced diffraction image. The finite penetration depth of the light leads to a reduced edge resolution in the direction to the illuminating beam direction while the edge contrast in perpendicular direction remains high (~100nm). We use the discrete dipole model to calculate the local optical field to show how the displacement of the diffraction image increases with increasing distance from the surface.Comment: 12 pages, 3 figure

Ultraviolet photon absorption in single- and double-wall carbon nanotubes and peapods: Heating-induced phonon line broadening, wall coupling, and transformation

Ultraviolet photon absorption has been used to heat single- and double-wall carbon nanotubes and peapods in vacuum. By increasing the laser intensity up to 500 mW, a downshift and a broadening of the optical phonons are observed corresponding to a temperature of 1000°C. The UV Raman measurements are free of blackbody radiation. We find that the linewidth changes for the G+ and G− bands differ considerably in single-wall carbon nanotubes. This gives evidence that the phonon decay process is different in axial and radial tube directions. We observe the same intrinsic linewidths of graphite (highly oriented pyrolytic graphite) for the G band in single- and double-wall carbon nanotubes. With increasing temperature, the interaction between the walls is modified for double-wall carbon nanotubes. Ultraviolet photon induced transformations of peapods are found to be different on silica and diamond substrates

High specific surface area carbon nanotubes from catalytic chemical vapor deposition process

A carbon nanotube specimen with a carbon content of 83 wt.% (95 vol.%) and a specific surface area equal to 790 m2/g (corresponding to 948 m2/g of carbon) is prepared by a catalytic chemical vapor deposition method. The nanotubes, 90% of which are single- and double-walled, are individual rather than in bundles. High-resolution electron microscopy shows a diameter distribution in the range 0.8–5 nm and Raman spectroscopy shows a high proportion of tubular carbon. Both techniques reveal a maximum in the inner wall diameter distribution close to 1.2 nm

Narrow diameter double-wall carbon nanotubes: synthesis, electron microscopy and inelastic light scattering

Double-wall carbon nanotubes are themolecular analogues to coaxial cables. Narrow diameter double-walled carbon nanotubes (DWNTs) have been obtained by catalytic chemical vapour deposition process with high yield and characterized by scanning and transmission electron microscopy. We examine the inelastic light scattering spectrum of mostly DWNTs with internal tubes of subnanometre diameter. We observe particularly narrow radial breathing modes corresponding to the internal tubes of diameter less than 0.7 nm of double-walled tubes. The D band is found to be strongly helicity dependent and the tangential modes in narrow diameter DWNTs are found to be often down-shifted

Discontinuous Tangential Stress in Double Wall Carbon Nanotubes

We have examined the stability of double wall carbon nanotubes under hydrostatic pressures up to 10 GPa. The tangential optical phonon mode observed by inelastic light scattering is sensitive to the inplane stress and splits into a contribution associated with the external and internal tube. While the pressure coefficient from the external tube is the same as in single wall carbon nanotubes, the pressure coefficient from the internal tube is found to be 45% smaller. The phonon band from the external tube broadens considerably with applied pressure in contrast with the phonon band of the internal tube which stays constant. These pressure dependent phonon shifts of the external and internal tubes and the contrasting phonon line broadening are explained by the elastic continuum shell model which takes into account both the continuous radial and discontinuous tangential stress component

Spectroscopic detection of carbon nanotube interaction with amphiphilic molecules in epoxy resin composites

Incorporation of carbon nanotubes into epoxy resin composites has the effect of increasing electrical conductivity at low percolation levels. An amphiphilic molecule such as palmitic acid has been used to increase the surface contact area and improve the dispersion of the carbon nanotube bundles in the prepolymer. The chemical environment of the dispersed nanotubes has been probed using vibrational Raman spectroscopy. Spectroscopic Raman maps, on sample surfaces (60x60 µm2) with ratios of nanotubes to palmitic acid varying from 1:2 to 2:1 by weight, have been recorded to test the uniformity of the dispersion. Substantial spatial inhomogeneities have been observed in the G-band shift and an additional spectral band at 1450 cm-1. The 1450 cm-1 band has been attributed to the CH3 group of the amphiphilic molecules adsorbed onto the nanotube surface. The maps are correlated with the measured electrical conductivity values. The highest conductivity has been observed for the best dispersed nanotubes and nanotubes with the highest degree of interaction

Raman G and D band in strongly photoexcited carbon nanotubes

We observe clear differences in the spectral shift of the Raman D and G bands when heating double wall carbon nanotubes through intense photon irradiation and by varying the temperature in a thermostat. These spectral differences are attributed to modifications of the defect induced double-resonance Raman process, and are consistent with Stokes–anti-Stokes anomalies observed for single and double wall carbon nanotubes, not present in graphite. We find that the Raman intensity for double wall carbon nanotubes increases superlinearly in the red spectral region and sublinearly in the UV spectral region

Raman G band in double-wall carbon nanotubes combining p doping and high pressure

We use sulfuric acid as pressure medium to extrapolate the G-band position of the inner and outer tubes of double-wall carbon nanotubes. Keeping the G-band position of the inner and outer tubes constant, we can determine the fraction of double-wall and single-wall tubes in samples containing a mixture of the two. A-band-related electronic interwall interaction at 1560 cm−1 is observed, which is associated with the outer tube walls. This band is observed to shift with pressure at the same rate as the G band of outer tubes and is not suppressed with chemical doping. Differences in the interwall interaction is discussed for double-wall carbon nanotubes grown by the catalytic chemical-vapor method and double-wall carbon nanotubes obtained through transformation of peapods

Charge transfer between carbon nanotubes and sulfuric acid as determined by Raman spectroscopy

The spontaneous interaction between sulfuric acid and carbon nanotubes is studied using Raman spectroscopy. We are able to determine the charge transfer without any additional parameter using the spectral signature of inner and outer walls of double-wall carbon nanotubes. While for the outer wall both the lattice contraction and the nonadiabatic effects contribute to the phonon shift, only the lattice contraction contributes for the inner nanotube. For the outer nanotube, we are able to separate these two contributions of the Raman G-band shift as a function of the charge transfer. We have carried out density functional theory calculations on graphene to see how different chemical species (HSO4-, H2SO4, H+) affect the electronic band structure and electron-phonon coupling. The Raman G band shift for the outer nanotube, Δω as a function of hole harge transfer per carbon atom, fC, is found to be Δω (cm−1) = (350 ± 20)fC + (101 ± 8)√fC