Jérôme Gleize

Resolved E-symmetry zone-centre phonons in LiTaO3 and LiNbO3

E-symmetry optical phonons at the Γ point of LiNbO3 and LiTaO3 were experimentally resolved in spectra measured by infrared and Raman spectroscopy. For this purpose, congruent and nearly stoichiometric crystals of LiNbO3 and LiTaO3, and mixed LiNb1−xTaxO3, crystals were studied. The results show that some of the E modes have weak intensities in Raman or infrared spectra. Thus the complete assignment of E-symmetry modes has been achieved by comparing Raman and infrared data. In addition, this assignment has been confirmed by Raman measurements at low temperatures.

Identification of LiNbO3, LiNb3O8 and Li3NbO4 phases in thin films synthesized with different deposition techniques by means of XRD and Raman spectroscopy

Phase composition of epitaxial/textured LiNbO3 films on sapphire substrates, grown by pulsed laser deposition, atmospheric pressure metal organic chemical vapor deposition and pulsed injection metal organic chemical vapor deposition was studied by conventional x-ray diffraction techniques. Raman spectroscopy, being highly sensitive to the symmetry of materials, was used as a countercheck in the compositional analysis. The wavenumbers of Raman modes of LiNb3O8 and Li3NbO4 phases were identified from Raman spectra of synthesized powders. Asymmetry of profiles of x-ray diffraction reflections of LiNbO3 films was studied. This asymmetry may have different origins which consequently may result in misleading conclusions about phase composition of textured LiNbO3 films.

Selective removal of metal impurities from single walled carbon nanotube samples

Large scale production of high quality CNT samples is still challenging. The presence of structural defects and metallic particles in pristine single walled carbon nanotubes (SWNTs) is responsible for the alteration of both their chemical stability and their magnetic and electrical properties. The commonly used purification procedures are based on multi-step treatments that are often too aggressive towards the CNTs, leading to disappointing yields. Here, we propose an alternative process that allows preparing high-quality and high-purity SWNT samples. The proposed process merely consists of heating up SWNT powder under high chlorine partial pressure and high temperature. These thermodynamic conditions favor high chlorine diffusion to metal impurities embedded in carbon shells thus inducing an avalanche process of metal chloride formation and sublimation. The purified samples have been characterized by transmission electron microscopy, thermogravimetric analysis, magnetic measurements and Raman spectroscopy. We show that the developed process combines selective elimination of catalytic impurities and high yields. More importantly, we show that this process preserves the quality of the resulting purified nanotubes.

Residual stresses and clamped thermal expansion in LiNbO3 and LiTaO3 thin films

Residual stresses in LiNbO3 and LiTaO3 epitaxial thin films were evaluated taking into account Li nonstoichiometry by means of Raman spectroscopy and x-ray diffraction. The epitaxial films were grown on C-cut sapphire substrates by pulsed injection metal organic chemical vapour deposition. Clamping of the epitaxial films by the substrate induced a transfer from the in plane thermal expansion to the out of plane component. The temperature of the phase transition of clamped LiTaO3 films was close to that expected for a bulk sample.

Chemi- vs physisorption in the radical functionalization of single-walled carbon nanotubes under microwaves.

Summary The effect of microwaves on the functionalization of single-walled carbon nanotubes (SWNTs) by the diazonium method was studied. The usage of a new approach led to the identification of the strength of the interaction (physical or chemical) between the functional groups and the carbon nanotube surface. Moreover, the nature (chemical formula) of the adsorbed/grafted functional groups was determined. According to thermogravimetric analysis coupled with mass spectrometry and Raman spectroscopy, the optimal functionalization level was reached after 5 min of reaction. Prolonged reaction times can lead to undesired reactions such as defunctionalization, solvent addition and polymerization of the grafted functions. The strength (chemi- vs physisorption) of the bonds between the grafted functional groups and the SWNTs is discussed showing the occurrence of physical adsorption as a consequence of defunctionalization after 15 min of reaction under microwaves. Several chemical mechanisms of grafting could be identified, and it was possible to distinguish conditions leading to the desired chemical grafting from those leading to undesired reactions such as physisorption and polymerization.

Simultaneous growth of monolayer graphene on Ni–Cu bimetallic catalyst by atmospheric pressure CVD process

CVD is the most efficient way to produce wafer scale monolayer graphene. Although Ni and Cu are widely reported catalysts for monolayer graphene formation, but both Ni and Cu are requiring different extreme conditions to grow graphene in single layer. Here, we show that monolayer graphene could be grown simultaneously on polycrystalline Ni and Cu under single atmospheric pressure CVD for the first time. Our catalyst system combines carbon solubility divergence between the two catalysts to limit the exposure to the carbon source. Structure and quality of the grown graphene were characterized by HRTEM and Raman spectroscopy mapping. The growth mechanism shows that the role of grain boundaries is crucial for carbon diffusion tuning. The results show that free-standing high-quality monolayer graphene can be produced in a controlled and simple way with an affordable catalyst system.