Tuning Solution‐State Aggregation for Shearing‐Induced Alignment and High Mobility Transport in Conjugated Polymers

ABSTRACT Clarifying the evolution of solution‐state aggregation of conjugated polymers into ordered thin films under external forces remains one of the key issues in developing high‐performance polymer electronics. Here, a strategy is provided to tailor the polymer aggregation and their responsiveness to solution‐shearing forces by tuning intermolecular interactions, aiming for efficient charge transport. Using a typical n‐type conjugated polymer as the model system, we systematically modulate the balance between backbone–solvent and side chain–solvent interactions to design distinct aggregate structures. In the backbone‐selective solvent of 1‐chloronaphthalene, enhanced backbone solvation at elevated temperatures leads to loosely packed, rod‐like aggregates that align efficiently under directional shear, yielding highly ordered films with electron mobilities up to 4.74 cm 2 V −1 s −1 . In contrast, in the side‐chain‐selective solvent of trimethylbenzene, polymer chains form disordered network‐like aggregates that resist alignment and produce less ordered films with mobilities of 2.20 cm 2 V −1 s −1 . Additionally, similar enhancements in charge‐transport mobility are also observed with two other representative polymers using the same strategy. This work establishes the critical role of intermolecular interaction‐driven aggregate design in dictating shearing‐induced structural evolution, offering a robust framework for the fabrication of high‐mobility conjugated polymer films.