Regioregularity-Driven Morphological Transition of Poly(3hexylthiophene)-Based Block Copolymers

Abstract

Conjugated polymer-based block copolymers (BCPs) offer great potential to provide beneficial nanostructures for efficient organic optoelectronics. However, their complicated self-assembly behavior, which is attributed to the strong crystallization of conjugated blocks, is still not well understood due to the lack of a model BCP system. Herein, we develop a series of novel conjugated polymer-based BCPs, poly(3-hexylthiophene)-block-poly(2-vinylpyridine) (P3HT-b-P2VP), in which the regioregularity (RR) of the P3HT block was varied from 95 to 73%. The tunable RR content allows for precise regulation of P3HT crystallization with minimal influence on the microphase-separation force between the P3HT and P2VP blocks. When RR is high (i.e., 95 or 8S%), structure formation is controlled by crystallization of P3HT, and the ultimate structure is characterized by nanoscale P3HT fibrils in an amorphous matrix. In contrast, as RR decreases to 78 and 73%, P3HT crystallization is suppressed. The self-assembly is controlled by the enthalpic interaction between P3HT and P2VP blocks, much like typical BCPs having two flexible blocks, and thermal annealing drives the formation of well-ordered lamellar or cylindrical phases. This morphological behavior is consistent with a Monte Carlo simulation based on a newly developed coarse-grained model. Significantly, this novel class of RR-controlled P3HT-based BCPs provides a simple method to tune bulk and thin film morphology for a variety of applications in nanostructured organic electronics.