Showing papers by "Cinzia Casiraghi published in 2005"

Raman spectroscopy of hydrogenated amorphous carbons

Abstract: We present a comprehensive multiwavelength Raman investigation of a variety of hydrogenated amorphous carbons $(a\text{\ensuremath{-}}\mathrm{C}:\mathrm{H})$, ranging from polymeric $a\text{\ensuremath{-}}\mathrm{C}:\mathrm{H}$ to diamond-like $a\text{\ensuremath{-}}\mathrm{C}:\mathrm{H}$ and ta-C:H, which allows us to derive values for their bonding, density, band gap, hydrogen content, and mechanical properties. The Raman spectra of $a\text{\ensuremath{-}}\mathrm{C}:\mathrm{Hs}$ show two different trends. In one case, the $G$ peak width increases with $G$ peak dispersion. In the second case, the opposite trend is found. In the first case, the Raman parameters vary with optical, structural, and mechanical properties in the same way as in hydrogen-free carbon films. In the second case, typical of polymeric $a\text{\ensuremath{-}}\mathrm{C}:\mathrm{H}$, the $G$ peak width correlates with the density, while the $G$ peak dispersion varies with the optical gap and hydrogen content. This allows a unified picture of bonding and disorder of all carbon films. UV Raman is particularly useful for $a\text{\ensuremath{-}}\mathrm{C}:\mathrm{Hs}$, as it gives clear measurements in the $D$ and $G$ peaks spectral region even for highly hydrogenated samples, for which the visible Raman spectra are overshadowed by photoluminescence. On the other hand, the slope of the photoluminescence background in visible Raman spectra can be used to estimate the H content. UV Raman measurements also allow the detection of $\mathrm{C}\mathrm{H}$ stretching vibrations.

Born-Oppenheimer breakdown in graphene

Abstract: The Born-Oppenheimer approximation (BO) has proven effective for the accurate determination of chemical reactions, molecular dynamics and phonon frequencies in a wide range of metallic systems. Graphene, recently discovered in the free state, is a zero band-gap semiconductor, which becomes a metal if the Fermi energy is tuned applying a gate-voltage Vg. Graphene electrons near the Fermi energy have twodimensional massless dispersions, described by Dirac cones. Here we show that a change in Vg induces a stiffening of the Raman G peak (i.e. the zone-center E2g optical phonon), which cannot be described within BO. Indeed, the E2g vibrations cause rigid oscillations of the Dirac-cones in the reciprocal space. If the electrons followed adiabatically the Dirac-cone oscillations, no change in the phonon frequency would be observed. Instead, since the electron-momentum relaxation near the Fermi level is much slower than the phonon motion, the electrons do not follow the Dirac-cone displacements. This invalidates BO and results in the observed phonon stiffening. This spectacular failure of BO is quite significant since BO has been the fundamental paradigm to determine crystal vibrations from the early days of quantum mechanics.

The ultrasmoothness of diamond-like carbon surfaces.

Abstract: The ultrasmoothness of diamond-like carbon coatings is explained by an atomistic/continuum multiscale model. At the atomic scale, carbon ion impacts induce downhill currents in the top layer of a growing film. At the continuum scale, these currents cause a rapid smoothing of initially rough substrates by erosion of hills into neighboring hollows. The predicted surface evolution is in excellent agreement with atomic force microscopy measurements. This mechanism is general, as shown by similar simulations for amorphous silicon. It explains the recently reported smoothing of multilayers and amorphous transition metal oxide films and underlines the general importance of impact-induced downhill currents for ion deposition, polishing, and nanopattering.

Effects of catalyst film thickness on plasma-enhanced carbon nanotube growth

Abstract: A systematic study is presented of the influence of catalyst film thickness on carbon nanostructures grown by plasma-enhanced chemical-vapor deposition from acetylene and ammonia mixtures We show that reducing the Fe∕Co catalyst film thickness below 3nm causes a transition from larger diameter (>40nm), bamboolike carbon nanofibers to small diameter (∼5nm) multiwalled nanotubes with two to five walls This is accompanied by a more than 50 times faster growth rate and a faster catalyst poisoning Thin Ni catalyst films only trigger such a growth transition when pretreated with an ammonia plasma We observe a limited correlation between this growth transition and the coarsening of the catalyst film before deposition For a growth temperature of ⩽550°C, all catalysts showed mainly a tip growth regime and a similar activity on untreated silicon, oxidized silicon, and silicon nitride support