We explore the preparation and use of graphene dispersions and graphene-nanoparticles composites viawet routes in order to create organized thin films (for passivation, adhesion and design of SERS substrates, seeFig.) At large concentrations, the liquid crystal ordering is an opportunity to spontaneously organize the materials.At lower concentrations, a special care has to be taken during the deposition of the thinnest films.In this work, we have focused on the design and the characterization of thin layers made of graphene oxide andgold nanoparticles (GO/AuNps) for their Surface Enhanced Raman Spectroscopy (SERS) properties. The objectivehere is to establish the main rules that control (during the deposition) the structure of the films and their resultingSERS properties. We have used various techniques such as dip-coating, spin coating with varying parameters, aswell as surface functionalization before deposition. The thin films have been characterized by AFM and theirperformance have been tested with Raman spectroscopy.

Graphene oxide dispersions are easily obtained in water. Due to the high aspect ratio of the flakes, liquid crystalsthen forms a nematic phase at moderate concentrations [1,2], which allows to design various composites withnanoparticles. Preparing organized materials and thin films from these dispersions however requires a good controlof the liquid crystal ordering during the deposition and the drying of the films.Here we have focused on mechanical instabilities that are frequently observed in thin graphene liquid crystallayers, when they are submitted to weak constraints. We have shown how to create and stabilize large-sizedperiodic textures (millimeter scale, see fig.1). The patterns have been characterized under optical and electronicmicroscopies. They result from the peculiar elastic and rheological properties of the graphene oxide liquid crystals.Our results also clarify why long-standing hypotheses on the presence of exotic phases [1] at large concentrationsare present in the literature.

Dye encapsulation into host single-walled carbon nanotubes is an easy way to create hybrid nano-systems with tunable opto-electronic properties. In this work, we will discuss the supramolecular organization inside the nanotube, the optical properties and the charge transfer as the function of the type of molecules, diameter and metallic or semiconducting character of the host nanotube. A significant electron transfer from encapsulated dyes to the carbon material is reported, whose magnitude strongly depends on the nanotube diameter, in good agreement with DFT calculations, and on the metallic or semiconducting character. Experiments also suggest a photo-activated electron transfer for small diameter (~9 Å) semiconducting and metallic tubes. Dye encapsulation is shown to significantly alter electron-phonon coupling into metallic nanotubes as revealed by the value of the coupling factor extracted from the Fano equation. The charge transfer is consistent with an important enhancement of the photoluminescence intensity up to a factor of nearly six for optimal confinement configuration. This charge transfer shifts the Fermi level, acting on the photoluminescence efficiency and the electron-phonon-coupling.

The aim of the present work is to study by means of thermodynamic measurements, i.e. isotherms of adsorption and desorption of water and Infrared (IR) spectroscopy, the effect of the interlayer cations on the mechanism of adsorption-desorption of water in the case of a montmorillonite exchanged with alkaline-earth metals. For the first time, the net isosteric heat of water adsorption and desorption is determined from isotherms recorded at three temperatures. The net isosteric heat is a very useful parameter for getting more insights into the sorption mechanism since it provides information about the sorption energy evolution which can be complementary to that obtained from structural or gravimetric measurements. The homoionic montmorillonite samples are prepared from purification and cationic exchanged in aqueous solution of the raw material, i.e the reference SWy-2 Wyoming material. XRD at the dry state and elemental chemical analysis confirm that the treatment does not deteriorate the clay structure and yield the expected homoionic composition. The adsorption and desorption isotherms measured at various temperatures show that the nature of the interlayer, i.e. exchangeable, cation changes the adsorbed/desorbed amount of water molecules for a given water relative pressure. The total amount of water adsorbed at = 0.5 follows the cation sequence Ca>Mg>Ba. Although the adsorption isosteric heat also follows the cation sequence Ca>Mg>Ba, that of desorption obeys a slightly different sequence Ca~Mg>Ba. This discrepancy between the adsorption and desorption heat is due to the higher irreversibility of water sorption process in the Ca exchanged montmorillonite. Finally, analysis of the IR spectra recorded at room temperature and under a primary vacuum reveals that the amount of adsorbed water follows the same sequence as that of the isosteric heat of adsorption and shows the coexistence of liquid-like and solid-like water confined in the interlayer space.

The main hurdle preventing the widespread useof single-walled carbon nanotubes remains the lack ofmethods with which to produce formulations of pristine,unshortened, unfunctionalized, individualized single-walledcarbon nanotubes, thus preserving their extraordinary properties.In particular, sonication leads to shortening, which isdetrimental to percolation properties (electrical, thermal,mechanical, etc.). Using reductive dissolution and transfer intodegassed water, open-ended, water-filled nanotubes can bedispersed as individualized nanotubes in water−dimethylsulfoxide mixtures, avoiding the use of sonication andsurfactant. Closed nanotubes, however, aggregate immediately upon contact with water. Photoluminescence andabsorption spectroscopy both point out a very high degree of individualization while retaining lengths of several microns.The resulting transparent conducting films are 1 order of magnitude more conductive than surfactant-based blanks atequal transmittance.

Since 2008, epitaxial graphene growth has been developed in terms of homogeneity and scale by using a 1 ATM argon pressure at high temperature (>1650°C). Until now, it still remains challenging to obtain films with different and controlled characteristics such as the thickness or the doping by tuning the growth parameters. Here, we optimized the epitaxial growth of monolayer graphene (1LG) on 4H-SiC (0001) under a low argon pressure of 10 mbar. This intermediate pressure allows growing a continued 1LG in a short process ~1h30.First, we discuss the initial growth stages from buffer layer to 1LG as a function of annealing temperature (same heating rate). The combined Raman spectroscopy and atomic force microscopy analyses show that a buffer layer, fully covering the Si-face of SiC, forms as the first step of growth. Subsequently, 1LG starts to grow at step edges and continue to cover the buffer layer on terraces with a step-flow growth mechanism. Eventually, reproducible syntheses of 1LG films were achieved by this temperature-controlled growth process. Then, we investigate the structural and electronic properties of the 1LG films. The integrated intensity of G-band in Raman spectra normalized with respect to a HOPG reference, AG/AG-HOPG, of each spectrum in Raman map of our continued graphene film is very close to the experimental value reported for a 1LG, demonstrating the good homogeneity. Atomically resolved scanning tunnellingmicroscopy (STM) evidences a (6x6) superstructure, indicative of 1LG covering a reconstructed interface layer[7]. Regarding the transport measurement, quantum Hall plateau values observed in our graphene layers confirmed both continuity and thickness of the1LG film. Moreover, we estimated a hole concentration of p~10^10 - 10^11 /(cm^2) at 1.7 K in helium atmosphere. We ascribe this unusual doping type to an atmosphere contamination effect since we regain the typical n-doped graphene under vacuum by transport measurement and STM analysis.