Regioregularity and Intrachain Ordering: Impact on the Nanostructure and Charge Transport in Two-Dimensional Assemblies of Poly(3-hexylthiophene)

The properties of supramolecular assemblies in conjugated macromolecular systems are strongly dependent on single chain effects. We report that differences in regioregularity (RR) of side chain attachment in poly(3-hexylthiophene) (P3HT) as small as ca. 4% are sufficient to induce dramatic changes in the electronic and morphological properties of the material. Casting the electronic absorption spectra in the framework of Spano's model g reveals that the conjugation length is surprisingly sensitive to RR, with differences in free exciton bandwidth between the two P3HT samples approaching 73 meV. The enhanced main chain planarization motivates a concomitant increase in nanofibril width as well as crystallinity observed in thin films of the higher RR variant. This observation correlates well with the field effect mobilities that are attenuated by 1 to 2 orders of magnitude in the lower RR polymer film. We suggest that the increased intrachain order coupled with a reduced fraction of grain boundaries in the higher RR film is responsible for the reported differences.