Jean-Louis Sauvajol

Production of high-density single-walled nanotube material by a simple laser-ablation method

Abstract A continuous-wave 250 W CO2-laser operating at 10.6 μm has been employed to evaporate graphite/bi-metal targets in a vertical evaporation chamber. Without the help of an additional furnace, web-like soot material has been easily produced. This contains high densities of bundles of single-walled nanotubes (SWNTs). Electron microscopy, Raman spectroscopy and neutron diffraction show the high quality of the SWNT material. The use of this simple laser-ablation system offers additional possibilities to study experimental parameters important for the formation of SWNTs leading to a better understanding of its growth mechanism.

Resonant Raman study of the structure and electronic properties of single-wall carbon nanotubes

We investigate the laser-energy dependence of the Raman profile of single-wall carbon nanotube (SWNT) samples with various distributions of diameters. We show that resonant Raman is an efficient tool for the study of the structure and electronic properties of SWNT. The tube diameter distribution is derived from the comparison between the experimental frequencies of the radial A1g breathing mode range (RBM) and the calculated RBM frequency of SWNT bundles. Metallic or semi-conducting tubes are identified in the light of calculations of allowed optical transitions. The assignments are confirmed by the observation (absence) of a Breit–Wigner–Fano-like lineshape for the tangential graphite-like modes of metallic (semiconducting) nanotubes.

Raman Modes of Index-Identified Freestanding Single-Walled Carbon Nanotubes

Using electron diffraction on freestanding single-walled carbon nanotubes, we have determined the structural indices (n,m) of tubes in the diameter range from 1.4 to 3 nm. On the same freestanding tubes, we have recorded Raman spectra of the tangential modes and the radial breathing mode. For the smaller diameters (1.4-1.7 nm), these measurements confirm previously established radial breathing mode frequency versus diameter relations and would be consistent with the theoretically predicted proportionality to the inverse diameter. However, for extending the relation to larger diameters, either a yet unexplained environmental constant has to be assumed, or the linear relation has to be abandoned.

Raman spectra of misoriented bilayer graphene

We compare the main feature of the measured Raman scattering spectra from single layer graphene with a bilayer in which the two layers are arbitrarily misoriented. The profiles of the 2D bands are very similar having only one component, contrary to the four found for commensurate Bernal bilayers. These results agree with recent theoretical calculations and point to the similarity of the electronic structures of single layer graphene and misoriented bilayer graphene. Another new aspect is that the dependance of the 2D frequency on the laser excitation energy is different in these two latter systems.

Phonons in single wall carbon nanotube bundles

Abstract We review recent and original results on the vibrational properties of single wall carbon nanotubes (SWNT). We especially focus on calculations and experiments performed on nanotube bundles. So far, the main technique for probing the dynamics has been Raman spectroscopy. Here, we discuss: (i) the relation between frequency of the A 1 g radial breathing mode and nanotube diameter, (ii) the origin of resonance and the consequences on the profile and intensity of the Raman lines, and (iii) the assignment and resonant behaviour of the Raman lines between 700 and 1000 cm −1 . Recently, inelastic neutron scattering techniques (INS) were shown to be effective tools to probe the vibrational density of states of SWNT. We review the INS results and focus on the study of low frequency excitations, especially libration-twist modes and acoustic modes. Both Raman and INS results are analysed in the light of calculations performed in a valence force field model taking into account van der Waals intertubes interactions in the bundles.

Supramolecular discrimination of carbon nanotubes according to their helicity.

Adsorption of specifically designed and geometrically constrained polyaromatic amphiphiles on single-walled carbon nanotubes (SWNTs) was found to be selective of the nanotube helicity angle. Starting from the same SWNT mixture, photoluminescence and resonant Raman spectroscopies show that a pentacenic-based amphiphile leads to the solubilization of armchair SWNTs and that a quaterrylene-based amphiphile leads to the solubilization of zigzag SWNTs. The results were predicted by the design of the two amphiphiles and are consistent with a supramolecular recognition of the nanotube graphene-type atomic structure by the aromatic part of the molecules through optimized pi-pi-stacking interactions.

Direct measurement of the absolute absorption spectrum of individual semiconducting single-wall carbon nanotubes.

The optical properties of single-wall carbon nanotubes are very promising for developing novel opto-electronic components and sensors with applications in many fields. Despite numerous studies performed using photoluminescence or Raman and Rayleigh scattering, knowledge of their optical response is still partial. Here we determine using spatial modulation spectroscopy, over a broad optical spectral range, the spectrum and amplitude of the absorption cross-section of individual semiconducting single-wall carbon nanotubes. These quantitative measurements permit determination of the oscillator strength of the different excitonic resonances and their dependencies on the excitonic transition and type of semiconducting nanotube. A non-resonant background is also identified and its cross-section comparable to the ideal graphene optical absorbance. Furthermore, investigation of the same single-wall nanotube either free standing or lying on a substrate shows large broadening of the excitonic resonances with increase of oscillator strength, as well as stark weakening of polarization-dependent antenna effects, due to nanotube-substrate interaction.

Modulated phases in NaNbO3 : Raman scattering, synchrotron x-ray diffraction, and dielectric investigations

Raman spectra of sodium niobate (NaNbO3) were obtained in all phases and revealed a significant disorder in the high-temperature U, T2 and T1 phases and ac omplicated folding of the Brillouin zone at the transitions into modulated S, R, P and N phases associated with the competitive zone-boundary soft mode s( in-phase and out-of phase octahedral tilts) along the M–T–R line. An extensive Raman study combined with x-ray diffraction (XRD) and dielectric measurements confirmed the presence of the incommensurate (INC) phase in sodium niobate. XRD experiments revealed the invar effect in the temperature interval 410–460 K corresponding to the INC phase associated with rotations of the NbO6 octahedra modulated along the b-direction. Our experiments suggest that the phase P consists of three phases: monoclinic (Pm) between 250 and 410 K, INC between 410 and 460 K, and orthorhombic (Po) between 460 and 633 K. At the low-temperature transition to the ferroelectric rhombohedral N phase all folded modes originating from the M- and T-points of the Brillouin zone abruptly disappear, Raman spectra in the N phase become much simpler and all peaks were assigned.

Reversible optical doping of graphene

The ultimate surface exposure provided by graphene monolayer makes it the ideal sensor platform but also exposes its intrinsic properties to any environmental perturbations. In this work, we demonstrate that the charge carrier density of graphene exfoliated on a SiO2/Si substrate can be finely and reversibly tuned between hole and electron doping with visible photons. This photo-induced doping happens under moderate laser power conditions but is significantly affected by the substrate cleaning method. In particular, it requires hydrophilic substrates and vanishes for suspended graphene. These findings suggest that optically gated graphene devices operating with a sub-second time scale can be envisioned and that Raman spectroscopy is not always as non-invasive as generally assumed.

Excitation energy dependence of the Raman spectrum of single-walled carbon nanotubes

We investigate the excitation energy dependence of Raman modes in the 600–1200 cm−1 range. The main features are first, two lines around 860 and 1060 cm−1 independent of the energy and second, energy-dependent couples of lines, each of them composed of one first-order mode and one substractive combination band. In each couple, the frequency of the lines is found to follow a linear, strong and opposite energy dependence.