Expanding the Scope of Thiophene Based Semiconductors: Perfluoroalkylated Materials and Fused Thienoacenes

Thiophene based semiconductors with new molecular and macromolecular structures were explored for applications in field effect transistors. Perfluoroalkylation was studied both as a means for controlling the self-assembly properties of polythiophenes, as well as modifying the molecular orbital energies of a series of oligothiophenes. End-perfluoroalkylation of poly(3-hexylthiophene) resulted in interesting self-assembly of the polymer into a bilayer vesicle. Similar fluorophilic assembly may be useful for controlling blend morphologies in heterojunction based devices. On the other hand, perfluoroalkylation of small molecule thiophene semiconductors leads to low lying LUMO levels, and can be used to promote electron injection for n-type transistor devices. This strategy was employed in combination with a pi-electron deficient benzothiadiazole to afford a new n-type semiconductor with an exceptionally low LUMO. Monoperfluoroalkylated oligothiophenes were also synthesized and studied in field effect transistors for the first time. In addition, two new fused thienoacene compounds were synthesized and their crystal structures were analyzed. The fused compounds showed exceptional pi-pi stacking and assembled into well defined one-dimensional microcrystals from the vapor phase. Field effect transistors were fabricated employing the new thienoacenes, showing p-type conductivity with equivalent charge carrier mobilities.