Theoretical Investigation of X-Ray Absorption near Edge Spectroscopy (XANES) Angular Dependence of Aligned Carbon Nanotubes Grown by DC HF CVD Process

Carbon nanotubes (CNTs) grown on plain substrates SiO2/Si(100) by a direct current and hot filaments catalytic chemical vapor deposition process have been studied by synchrotron X-ray absorption near edge spectroscopy (XANES) technique to theoretically investigate the angular-dependence of carbone (C) K-edge π* and σ* transitions. Experimental XANES spectra show that π* resonance increases with the incidence angle from normal to grazing incidence angle while σ* resonance decreases. This has been explained by the sine-square and cosine-square dependencies of π* and σ* intensities, respectively. These results were confirmed by theoretical XANES curves of highly oriented pyrolytic graphite (HOPG) and CNTs plotted versus incidence angle. It has been shown that π* and σ* transitions strongly depend on the nature of polarized light (linearly or circularly). At the linear polarized light, π* resonance is a preference as well as at right-circular polarized. At the left-circular polarized light, σ* resonance is a preference. The π* intensities are high at parallel orientation and the σ* intensities are low at normal orientation. The smallest π* intensity is noticed at normal orientation, where the π* orbitals are supposed to be lying parallel to the surface plane for perfectly aligned HOPG or CNTs. This explains the incomplete extinction of π* intensity. We noticed at parallel orientation a region where any π* and σ* transitions did not expect because of the lack of polarization light.

Curvature, Hybridization and Contamination of Carbon Nanostructures Analysis Using Electron Microscopy and XANES Spectroscopy

The ability to control the nanoscale shape of carbon nanostructures during wide-scale synthesis process is an essential goal in research for Nanotechnology applications. This paper reports a significant progress toward that goal. Variant CVD has been used for the synthesis of the samples studied. Curvature, hybridization and contamination are analyzed using Electron Microscopies and XANES spectroscopy. The investigations of the results show that four types of samples are obtained. They are carbon nanotubes (CNTs), carbon nanofibers (CNFs), carbon nanowalls (CNWs) and carbon nanoparticles (CNPs). Almost all of them have catalyst nanoparticles (metal) on top in top growth model or on base in base growth model and encapsulated or adsorbed in sidewalls. The orientation of tubular carbon nanomaterials depends on operating parameters. They are classified in three groups: the poorly oriented, the medium oriented and the highly oriented. Their contamination (radicals, atoms and molecules) and hybridization are intrinsically related to the curvature of their graphene layers. XANES spectroscopy allows quantitative characterization of nanomaterials.

Alignment of Vertically Grown Carbon Nanostructures Studied by X-Ray Absorption Spectroscopy

X-Ray Absorption Spectroscopy (XAS) on the carbon K edge of carbon nanostructures (nanotubes, nanofibers, nanowalls) is reported here. They are grown on plain SiO2 (8 nm thick)/Si(100) substrates by a Plasma and Hot Filaments-enhanced Catalytic Chemical Vapor Deposition (PE HF CCVD) process. The morphology and the nature of these carbon nanostructures are characterized by SEM, TEM and Raman spectroscopy. According to conditions of catalyst preparation and DC HF CCVD process, carbon nanotubes (CNTs), carbon nanofibers (CNFs), carbon nanowalls (CNWs), carbon nanoparticles (CNPs) with different orientation of the graphene plans or shells can be prepared. From the angular dependence of the incident light and geometrical morphology of the nanostructures, wide variations of the C K-edge intensity of the transitions to the empty π* and σ* states occur. A full lineshape analysis of the XAS spectra has been carried out using a home-made software, allowing estimating the relative proportion of π* and σ* transitions. A geometrical model of the angular dependence with the incidence angle of the light and the morphology of the carbon nanostructures is derived. With normalization to the HOPG (Highly Oriented Pyrolytic Graphite graphite) reference case, a degree of alignment can be extracted which is representative of the localized orientation of the graphitic carbon π bonds, accounting not only for the overall orientation, but also for local defects like impurities incorporation, structural defects ... This degree of alignment shows good agreement with SEM observations. Thus CNTs films display degrees of alignment around 50%, depending on the occurrence of defects in the course of the growth, whereas no special alignment can be detected with CNFs and CNPs, and a weak one (about 20%) is detected on CNWs.