The work presented in this thesis concerns surface energy modification and patterning of the surfaces of conjugated polymers. Goniometry and Wilhelmy Balance techniques were used to evaluate the surface energy or wettability of a polymer’s surface; infrared reflectionabsorption spectroscopy (IRAS) was used to analyse the residuals on the surface as modified by a bare elastomeric stamp poly(dimethylsiloxane) (PDMS). The stamp was found to be capable of modifying a polymer surface. Patterning of a single and/or double layer of conjugated polymers on the surface can be achieved by surface energy controlled dewetting. Modification of a conjugated polymer film can also be carried out when a sample is subjected to electrochemical doping in an aqueous electrolyte. The dynamic surface energy changes during the process were monitored in-situ using the Wilhelmy balance method. This thesis also concerns studies of conjugated polymer-based optoelectronics, including light-emitting diodes (PLEDs), that generate light by injecting charge into the active polymer layer, and solar cells (PSCs), that create electrical power by absorbing and then converting solar photons into electron/hole pairs. A phosphorescent metal complex was doped into polythiophene to fabricate PLEDs. The energy transfer from the host polymer to the guest phosphorescent metal (iridium and platinum) complex was studied using photoluminescence and electroluminescence measurements performed at room temperature and at liquid nitrogen temperature. PSCs were prepared using low-bandgap polyfluorene copolymers as an electron donor blended with several fullerene derivatives acting as electron acceptors. Energetic match is the main issue affecting efficient charge transfer at the interface between the polymers and the fullerene derivatives, and therefore the performance of the PSCs. Photoluminescence, luminescence quenching and the lowest unoccupied molecular orbital (LUMO) together with the highest occupied molecular orbital (HOMO) of the active materials in the devices were studied. A newly synthesized fullerene, that could match the low-bandgap polymers, was selected and used as electron acceptor in the PSCs. Photovoltaic properties of these PSCs were characterised, demonstrating one of the most efficient polymer:fullerene SCs that generate photocurrent at 1 μm. / On the day of the defence the status of article number III was Manuscript and article VII was Accepted.

Dans ce manuscrit est décrite l'utilisation d'interactions supramoléculaires pour diriger l'auto-assemblage de composés donneurs et accepteurs d'électrons au sein de dispositifs photovoltaïques organiques. Dans ce but, des matériaux de type oligo-3-hexylthiophène et fullerène ont été fonctionnalisés avec des groupements de reconnaissance complémentaires mélamine – acide barbiturique. La présence de élements solubilisants confère à ces composés une bonne mise en oeuvre permettant la fabrication de dispositifs photovoltaïques à hétérojonction volumique. L'effet de la composition et du post-traitement de la couche active sur la performance de ces dispositifs ont été explorés. Les études de mobilité de charge et des mécanismes de recombinaison au sein de ces matériaux indiquent que l'équilibre entre auto-association et séparation de phases est crucial pour l'efficacité en conversion photovoltaïque. / This research aims to elucidate the use of supramolecular interaction to guide the formation of well-defined nanoscale self-assembled architecture in photovoltaic solar cells as a means to improve device efficiency. Complementary molecular recognition sites based on melamine and barbituric acid were used to obtain functionalized fullerene and oligothiophene materials with superior processibility thanks to the presence of specific solubilizing groups. The efficiency of solid-state devices fabricated using the bulk heterojunction design was studied with respect to device morphology and composition. Experiments on recombination mechanism and field effect mobilities suggest that the balance between hydrogen-bonding interactions induce self-assembly and p-p interactions to promote phase segregation is crucial to the micro-structure of the active layer. The investigated of the relationship between the oligothiophene chain size and various complementary hydrogen-bonding motifs is envisaged.