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• Sciences de l'ingénieur/Matériaux
  
• Sciences de l'ingénieur/Energie électrique
  
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Photoluminescence of single-walled carbon nanotubes is monitored at the individual scale by molecule encapsulation into their hollow core. Depending on the electronic character (electron donor or acceptor) of the confined molecule, enhancement or quenching of the photoluminescence intensity is demonstrated. This behavior is assigned to a charge transfer, evidenced by the shift of the Raman G-band, and a correlated Fermi level shift shown by photoemission experiments. Our experimental results are supported by DFT calculations. A consistent picture of the physical interactions taking place in the hybrid systems and their effects on the optical and electronic properties is given. Our results indicate that the electron affinity or ionization potential of the encapsulated molecules and the diameter of the nanotube are relevant parameters to tune the light emission properties of the hybrid systems at the nanoscale.

Filling carbon nanotubes with molecules is a route for the development of electronically modified one-dimensional hybrid structures for which the interplay between the electronic structure of molecules and nanotubes is a key factor. Tuning these energy levels with external parameters is an interesting strategy for the engineering of new devices and materials. Here we show that the hybrid system composed by quaterthiophene (4T) molecules confined in single-walled carbon nanotubes, presents a piezo-Raman-resonance of the molecule vibrational pattern. This behavior manifests as a rapid pressure induced enhancement of the 4T Raman mode intensities compared to the tubes G-band Raman modes. Density functional theory calculations allow to explain the spectral behaviour through the pressure-enhanced quaterthiophene resonance evolution. By increasing pressure, the tube cross-section deformation leads to a reduction of the intermolecular distance, to the splitting of the molecular levels and then to an increase of resonance channels. Calculations and experiments converge to the 4T piezo-resonance scenario associated with the pressure-induced nanotube radial collapse observed at about 0.8 GPa. Our findings offer possibilities for the development of pressure transducers based on molecule-filled carbon nanotubes.

Dye confinement into carbon nanotube significantly affects the electronic charge density distribution of the final hybrid system. Using the electron-phonon coupling sensitivity of the Raman G-band, we quantify experimentally how charge transfer from thiophene oligomers to single walled carbon nanotube is modulated by the diameter of the nano-container and its metallic or semiconducting character. This charge transfer is shown to restore the electron-phonon coupling into defected metallic nanotubes. For sub-nanometer diameter tube, an electron transfer optically activated is observed when the excitation energy matches the HOMO-LUMO transition of the confined oligothiophene. This electron doping accounts for an important enhancement of the photoluminescence intensity up to a factor of nearly six for optimal confinement configuration. This electron transfer shifts the Fermi level, acting on the photoluminescence efficiency. Therefore, thiophene oligomer encapsulation allows modulating the electronic structure and then the optical properties of the hybrid system.

Wet acid oxidation treatment methods have been widely reported as an effective method to purify and oxidize the surface of industrial multi-walled carbon nanotubes (MWCNT). This work examines the use of a concentrated HNO3/H2SO4 mixture in an attempt to optimize the purification procedure of industrial MWCNT with diameter distribution statistics. It is shown that acid treatments of several hours are enough to purify the nanotubes. The electrical and thermal conductivities of epoxy composites containing 0.05-0.25 wt. % of acid-treated MWCNT has been studied. The electrical conductivity of the composites decreases by more than three orders, whereas the thermal conductivity of the same specimen increases very modestly as a function of the filler content.

Photo-active pi-conjugated molecules (quaterthiophene and phthalocyanine) are either encapsulated into the hollow core of single-walled carbon nanotubes or non-covalently stacked at their outer surface in order to elaborate hybrid nano-systems with new physical properties, providing practical routes to fit different requirements for potential applications. In this study, we are interested in the relationship between the structure and the opto-electronic properties. The structural properties are investigated mainly by x-ray diffraction and/or Transmission Electron Microscopy and Raman spectroscopy. We evidence that the supramolecular organizations of confined quaterthiophenes depend on the nanocontainer size whereas phthalocyanine encapsulation leads the formation of a 1D-phase for which the angle between the molecule ring and the nanotube axis is close to 32°. Confined phthalocyanine molecules display Raman spectra hardly altered with respect to the bulk phase, suggesting a rather weak interaction with the tubes. In contrast, the vibrational properties of the molecules stacked at the outer surface of tubes display important modifications. We assume a significant curvature of the phthalocyanine induced by the interaction with the tube walls and a change of the central atom position within the molecular ring, in good agreement with our DFT calculations.