Ultrasound-Induced Ordering in Poly(3-hexylthiophene): Role of Molecular and Process Parameters on Morphology and Charge Transport

Facile methods for controlling the microstructure of polymeric semiconductors are critical to the success of large area flexible electronics. Here we explore ultrasonic irradiation of solutions of poly(3-hexylthiophene) (P3HT) as a simple route to creating ordered molecular aggregates that result in a one to two order of magnitude improvement in field effect mobility. A detailed investigation of the ultrasound induced phenomenon, including the role of solvent, polymer regioregularity (RR) and film deposition method, is conducted. Absorption spectroscopy reveals that the development of low energy vibronic features is dependent on both the regioregularity as well as the solvent, with the latter especially influential on the intensity and shape of the band. Use of either higher regioregular polymer or ultrasonic irradiation of lower regioregular polymer solutions results in high field effect mobilities that are nearly independent of the dynamics of the film formation process. Surprisingly, no distinct correlation between thin-film morphology and macroscopic charge transport could be ascertained. The relationships between molecular and process parameters are very subtle: modulation of one effects changes in the others, which in turn impact charge transport on the macroscale. Our results provide insight into the degree of control that is required for the development of reproducible, robust materials and processes for advanced flexible electronics based on polymeric materials.