Grazing-angle x-ray reflectivity ͑XRR͒ is described as an efficient, nondestructive, parameter-free means to measure the mass density of various types of amorphous carbon films down to the nanometer thickness range. It is shown how XRR can also detect layering if it is present in the films, in which case the reflectivity profile must be modeled to derive the density. The mass density can also be derived from the valence electron density via the plasmon energy, which is measured by electron energy-loss spectroscopy ͑EELS͒. We formally define an interband effective electron mass m*, which accounts for the finite band gap. Comparison of XRR and EELS densities allows us to fit an average m*ϭ0.87m for carbon systems, m being the free-electron mass. We show that, within the Drude-Lorentz model of the optical spectrum, m*ϭ͓1Ϫn(0) Ϫ2 ͔m, where n(0) is the refractive index at zero optical frequency. The fraction of sp 2 bonding is derived from the carbon K-edge EELS spectrum, and it is shown how a choice of ''magic'' incidence and collection angles in the scanning transmission electron microscope can give sp 2 fraction values that are independent of sample orientation or anisotropy. We thus give a general relationship between mass density and sp 3 content for carbon films.

A comprehensive study of the stress release and structural changes caused by postdeposition thermal annealing of tetrahedral amorphous carbon ͑ta-C͒ on Si has been carried out. Complete stress relief occurs at 600-700°C and is accompanied by minimal structural modifications, as indicated by electron energy loss spectroscopy, Raman spectroscopy, and optical gap measurements. Further annealing in vacuum converts sp 3 sites to sp 2 with a drastic change occurring after 1100°C. The field emitting behavior is substantially retained up to the complete stress relief, confirming that ta-C is a robust emitting material.

Carbon nanotubes, first identified by Iijima, require for their production a source of elemental carbon and a transfer of energy that is specific to the type of source and the growth environment. Methods developed so far involve arc discharge, and vaporization using laser, pyrolysis and chemical vapour deposition of hydrocarbons. Here, we show growth of carbon nanofibres from radio-frequency plasma-enhanced chemical vapour deposition at room temperature, which was made possible by substituting the thermal energy requirements for the growth with plasma decomposition of methane on the Ni catalyst. Electron microscopy analysis provides evidence for a 'tip' growth model, with the Ni catalyst particle attached to the tip of the nanofibre. Energy-filtered imaging shows the Ni catalyst has a surface layer rich in carbon, consistent with the formation of a eutectic Ni-C droplet as a nucleation site for the carbon nanofibres, so that the carbon diffuses across the surface. The reduced distortion of the catalyst particles at low temperatures leads to a more uniform growth of the carbon nanofibres over large areas. The lower growth temperature allows for the removal of the silicon dioxide barrier layer associated with catalytic growth, and should allow in situ growth of nanofibres on relatively large areas of temperature-sensitive substrates, such as plastics, organics and even paper.

We report a detailed study of the interaction between surface-oxidized multiwall carbon nanotubes (o-MWCNTs) and the molecular semiconductor tetrasulfonate copper phthalocyanine (TS-CuPc). Concentrated dispersions of o-MWCNT in aqueous solutions of TS-CuPc are stable toward nanotube flocculation and exhibit spontaneous nanostructuring upon rapid drying. In addition to hydrogen-bonding interactions, the compatibility between the two components is shown to result from a ground-state charge-transfer interaction with partial charge transfer from o-MWCNT to TS-CuPc molecules orientated such that the plane of the macrocycle is parallel to the nanotube surface. The electronegativity of TS-CuPc as compared to unsubsubtituted copper phthalocyanine is shown to result from the electron-withdrawing character of the sulfonate substituents, which increase the molecular ionization potential and promote cofacial molecular aggregation upon drying. Upon spin casting to form uniform thin films, the experimental evidence is consistent with an o-MWCNT scaffold decorated with phthalocyanine molecules self-assembled into extended aggregates reminiscent of 1-D linearly stacked phthalocyanine polymers. Remarkably, this self-organization occurs in a fraction of a second during the spin-coating process. To demonstrate the potential utility of this hybrid material, it is successfully incorporated into a model organic photovoltaic cell at the interface between a poly(3-hexylthiophene):[6,6]-phenyl-C61 butyric acid methyl ester bulk heterojunction layer and an indium-tin oxide-coated glass electrode to increase the light-harvesting capability of the device and facilitate hole extraction. The resulting enhancement in power conversion efficiency is rationalized in terms of the electronic, optical, and morphological properties of the nanostructured thin film.

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