Lamellar and liquid crystal ordering in solvent-annealed all-conjugated block copolymers
All-conjugated block copolymers are an emerging class of polymeric materials promising for organic electronic applications, but further progress requires a better understanding of their microstructure including crystallinity and self-assembly through micro-phase segregation. Here, we demonstrate remarkable changes in the thin film structure of a model series of all-conjugated block copolymers with varying processing conditions. Under thermal annealing, poly(3-hexylthiophene)-b-poly(9′,9′-dioctylfluorene) (P3HT-b-PF) all-conjugated block copolymers exhibit crystalline features of P3HT or PF, depending on the block ratio, and poor π–π stacking. Under chloroform solvent annealing, the block copolymers exhibit lamellar ordering, as evidenced by multiple reflections in grazing incidence wide- and small-angle X-ray scattering (GIWAXS and GISAXS), including an in-plane reflection indicative of order along the π–π stacking direction for both P3HT and PF blocks. The lamellae have a characteristic domain size of 4.2 nm, and this domain size is found to be independent of block copolymer molecular weight and block ratio. This suggests that lamellar self-assembly arises due to a combination of polymer block segregation and π–π stacking of both P3HT and PF polymer blocks. Strategies for predicting the microstructure of all-conjugated block copolymers must take into account intermolecular π–π stacking and liquid crystalline interactions not typically found in flexible coil block copolymers.