Résumé
Opto-electronic properties of single-walled carbon nanotubes can be significantly modified by chromophore confinement into their hollow core. This study deals with quaterthiophene derivatives encapsulated into nanotubes displaying different diameter distributions. We report a significant electron transfer from the confined molecules to the nanotubes in our hybrid systems, evidenced by photoluminescence and Raman investigations. This charge transfer leads to an important enhancement of the photoluminescence intensity by a factor of nearly five depending on the tube diameter. Energy shifts observed on both absorption and emission on the hybrid system also depend on the nanotube diameters and are interpreted in terms of local structure of the confined molecules. The Raman G-band of hybrid systems exhibits a drop in intensity and significant shifts whose magnitude and direction strongly depend on the nanotube diameter. These behaviors are consistent with a weak electron transfer from the molecule to the tube, in good agreement with the PL analysis. In addition, close to the molecule resonance, the magnitude of the G-band shifts are modified and the intensity loss is amplified, strongly suggesting a photo-induced electron transfer. Finally, the Breit-Wigner-Fano lineshape (characteristic of electron-phonon coupling) of the Raman G-band is strongly reduced for defective metallic nanotubes. After molecule functionalization, this peculiar profile is recovered, suggesting a back donation of electrons to the nanotube. Thus, confinement species into nanotubes allow moving the Fermi level and consequently to monitor their opto-electronic properties.