Unravelling the Correlation between Charge Mobility and Cocrystallization in Rod–Rod Block Copolymers for High‐Performance Field‐Effect Transistors

Cocrystallization involving two or more components aggregating into cocrystals allows the preparation of materials with markedly improved charge mobility. This approach however, is little explored in all-conjugated block copolymers (BCPs). Herein, we report the first investigation into the correlation between cocrystals and charge mobility in a series of new all-conjugated BCPs: poly(3-butylthiophene)-b-poly(3-hexylselenophene) (P3BT-b-P3HS) for high-performance field-effect transistors. These rationally synthesized rod-rod BCPs self-assemble into cocrystals with high charge mobilities. Upon one-step thermal annealing, their charge mobilities decrease slightly despite their increased crystallinities. After two-step thermal annealing, P3BT-b-P3HS (P3BT/P3HS=2:1) and (1:1) cocrystals disappear and phase separation occurs, leading to greatly decreased charge mobilities. In contrast, P3BT-b-P3HS (1:2) retains its cocrystalline structure and its charge mobility.