Tuning Metastability Of Poly(3-Hexyl Thiophene) Solutions To Enable In Situ Atomic Force Microscopy Imaging Of Surface Nucleation

Poly(3-hexyl thiophene) (P3HT), a workhorse material for the study of organic electronic devices, assembles into nanofibers (NFs) upon crystallization from solution, providing the means to tailor morphology and improve device performance. We investigate how P3HT regioregularity, molecular weight, and concentration influence the hysteresis between crystallization and melting temperatures of NFs. Hysteresis is found to increase with molecular weight and reach an asymptote for polymer chains above the chain folding threshold (M-n > 12 kg/mol). Regioregularity does not substantially affect the hysteresis above a level of 88%, while increasing polymer concentration is found to reduce hysteresis. This insight facilitates in situ high-resolution atomic force microscopy measurements that provide better understanding of the mechanism of NF crystallization on graphite. We find an interchain distance (along the a crystallographic axis) of 16.7 +/- 0.7 angstrom, and a spacing of 7.7 +/- 0.2 angstrom along the c axis, suggesting that the crystals on graphite are form I.