Polymorph‐Dependent Multi‐Level Supramolecular Self‐Assembly and Local Charge Transport of a Conjugated Polymer in Solution and Solid States

Abstract The polymorphic behavior of conjugated polymers enables tunable optoelectronic properties, but their transport mechanism remains elusive due to the inherent complexity and uncontrollability of polymorphic self‐assembly behaviors and electronic processes at various length scales, alongside the ambiguous relationship between solution and solid states. Herein, precise control of multi‐level supramolecular self‐assembly of a polymorphic conjugated polymer, N‐PDPP4T‐HD with two distinct semi‐crystalline aggregated phases ( β 1 and β 2 ) via solvent engineering is demonstrated. β 1 forms 1D worm‐like nanostructures in solution, whereas β 2 generates 2D nanoscale lamellar configuration, confirmed by experimental observation and molecular dynamic simulation. Such solution‐state features are inherited in the solid state (1D nanofibers for β 1 and 2D granular‐like structures for β 2 ). X‐ray characterizations reveal larger crystalline domains on the nanometer scale, reduced π‐stacking distance on the Ångstrom scale, and diminished paracrystallinity disorder for solid‐state β 2 . Going beyond conventional DC transistor characterizations, contact‐free ultrafast terahertz spectroscopy to unveil AC short‐range, intrinsic transport properties is employed. Longer charge carrier scattering time and thus intrinsic mobility of β 2 result in threefold higher short‐range photoconductivity than β 1 . This work establishes the “solution structure – solid structure – local transport” relation in polymorphic conjugated polymers and provides new opportunities for high‐performance plastic electronic devices.