The aim of this work is the study of photogenerated charge transport in hybrid films composed of π-conjugated polymers and of semiconductor nanocrystals, designed for applications in optoelectronics. Chemical synthesis provides gram-scale samples of CdSe nanocrystals, of low polydispersity and con- trolled shapes (spherical, branched). In order to enhance their conductivity, the surface ligands of CdSe nanocrystals (stearic acid, oleylamine) are exchanged by smaller molecules, namely pyridine, ethanedithiol, phenylenediamine, butylamine and benzenedithiol. Optical and electrochemical studies show that the ligand exchange modifies the nanocrystals' energy levels. Poly(3-hexylthiophene) thin films exhibit varying degrees of energetical disorder and of intermolecular coupling, depending on the processing method and on the solvent used. In hybrid films, the crystallinity of P3HT, probed by grazing incidence X-ray diffraction, is modified by the presence of nanocrystals. Time-of-Flight measurements of hybrid films show that electron and hole mobilities vary with the content of nanocrystals, with their shape, and with their ligands. Small volume fractions of nanocrystals enhance the hole mobility, and large fractions degrade it. Electron mobilities are percolation-limited: they reach a stable value for a threshold fraction of nanocrystals. The optimal fraction of nanocrystals for electron and hole mobilities is 36 vol% in hybrids made of spherical nanocrystals with their synthesis synthesis ligands. Finally, Monte Carlo simulations of photogenerated current transients in pristine poly(3-hexylthiophene) and in a hybrid sample show on one hand that the energy distribution of poly(3-hexylthiophene) rules the shape of the simulated transients, and on the other hand that nanocrystals can be described as little accessible sites of the hopping lattice.
