A general mechanism for controlling thin film structures in all-conjugated block copolymer: fullerene blends

Block copolymers have the potential to self-assemble into thermodynamically stable nanostructures that are desirable for plastic electronic materials with prolonged lifetimes. Fulfillment of this potential requires the simultaneous optimisation of the spatial organisation and phase behaviour of heterogeneous thin films at the nanoscale. We demonstrate the controlled assembly of an all-conjugated diblock copolymer blended with fullerene. The crystallinity, nanophase separated morphology, and microscopic features are characterised for blends of poly(3-hexylthiophene-block-3-(2-ethylhexyl) thiophene) (P3HT-b-P3EHT) and phenyl-C61-butyric acid methyl ester (PCBM), with PCBM fractions varying from 0-65 wt%. We find that PCBM induces the P3HT block to crystallise, causing nanophase separation of the block copolymer. Resulting nanostructures range from ordered (lamellae) to disordered, depending on the amount of PCBM. We identify the key design parameters and propose a general mechanism for controlling thin film structure and crystallinity during the processing of semicrystalline block copolymers.