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...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.展开更多
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 F...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.展开更多
文摘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.
文摘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.