Unraveling the Solution‐State Supramolecular Structures of Donor–Acceptor Polymers and their Influence on Solid‐State Morphology and Charge‐Transport Properties

Abstract Polymer self‐assembly in solution prior to film fabrication makes solution‐state structures critical for their solid‐state packing and optoelectronic properties. However, unraveling the solution‐state supramolecular structures is challenging, not to mention establishing a clear relationship between the solution‐state structure and the charge‐transport properties in field‐effect transistors. Here, for the first time, it is revealed that the thin‐film morphology of a conjugated polymer inherits the features of its solution‐state supramolecular structures. A “solution‐state supramolecular structure control” strategy is proposed to increase the electron mobility of a benzodifurandione‐based oligo( p‐ phenylene vinylene) (BDOPV)‐based polymer. It is shown that the solution‐state structures of the BDOPV‐based conjugated polymer can be tuned such that it forms a 1D rod‐like structure in good solvent and a 2D lamellar structure in poor solvent. By tuning the solution‐state structure, films with high crystallinity and good interdomain connectivity are obtained. The electron mobility significantly increases from the original value of 1.8 to 3.2 cm 2 V −1 s −1 . This work demonstrates that “solution‐state supramolecular structure” control is critical for understanding and optimization of the thin‐film morphology and charge‐transport properties of conjugated polymers.