A Physicochemical Approach Toward Extending Conjugation and the Ordering of Solution-Processable Semiconducting Polymers

Poly(3-hexylthiophene)s (P3HTs) were synthesized with a well-controlled molecular weight (Mw) and degree of regioregularity; additionally, π-conjugated P3HT structures in both solutions and films were systematically investigated. Conjugated P3HT phases in spin-cast films significantly changed from ordered nanorods, -fibrils, and -ribbons to less-ordered granules, depending on the conformation of the P3HT chains in solutions. The chain conformations could be physicochemically adjusted by modifying chain lengths (from 5 to 45 kDa), solvents, and ultrasonication. Highly extended conformations of the P3HT in ultrasound-treated solutions yielded longer degree of conjugation both the intra- and intermolecularly. When toluene was used as a marginal solvent, ultrasonicated 0.1 wt % 29 kDa P3HT solutions could be used to yield highly ordered aggregates in spin-cast films, including nanoribbons or nanosheets, with field-effect mobility (μFET) up to ∼0.1 cm(2) V(-1) s(-1) being measured for organic field-effect transistors (OFETs). However, ultrasonicated chloroform systems with good P3HT solubility (for P3HT Mw ≥ 20 kDa) yielded featureless conducting layers even at 0.4 wt % P3HT content. However, these film-based OFETs yielded μFET values up to 0.04 cm(2) V(-1) s(-1), which were much greater than 0.004 cm(2) V(-1) s(-1) for the nonultrasonicated systems.