Abstract
The self-assembly process and resulting structure of a series of conductive diblock copolymer thin films of Poly(3-hexylthiophene)-b-Polystyrene (P3HT-b-PS) have been studied by TEM, SAED, GIXD and AFM and additionally by first principles modeling and simulation. By varying the molecular weight of the P3HT segment, these block copolymers undergo microphase separation and self-assemble into nanostructured sphere, lamellae, nanofiber, and nanoribbon in the films. Within the diblock copolymer thin film, the convalently bonded PS blocks segregated to form amorphous domains, however, the conductive P3HT blocks were crystalline, exhibiting highly-ordered molecular packing with their alkyl side chains aligned along to the normal to the substrate and the π-π stacking direction of the thiophene rings aligned parallel to the substrate. The conductive P3HY block copolymers exhibited significant improvements in organic feild-effect transistor (OFET) performance and environmental stability as compared to P3HT homopolymers, with up to a factor of two increase in measured moblity (0.08 cm2/Vs ) for the P4 (85 wt% P3HT). Overall, this work demonstrates that the high degree of molecular order induced by bock copolymer phase separation can improve the transport properties and stability of conductive polymer critical for high-performance OFET’s.
