Direct grazing-angle X-ray scattering evidence of the order-disorder transition and interdigitation of side chains in a conjugated polymer poly(3-hexylthiophene) (P3HT) is presented. The free methyl ends of the side chains exhibit closest packing, as in n-alkane crystallization, and cause a structural mismatch due to the difference between their packing density and the areal density of the attached ends. This mismatch is resolved by increases in the tilt angle of the side chains and local interdigitation. In situ X-ray scattering and electrical measurements show that the structural transition and interdigitation of these side chains strongly affect its surface morphology as well as the charge transport properties of the resulting P3HT-based organic field-effect transistor. Since most conjugated polymers have side chains, the results of this study provide a deeper understanding of the effects of side chains on the structural and electrical properties of conjugated backbones. These results also provide a new perspective on the formation of a metastable polymorph consisting of interdigitated P3HT.
Keywords: conjugated polymers; crystal polymorphs; order−disorder transition; organic electronics; side chains.