Forming Long-Range Order of Semiconducting Polymers through Liquid-Phase Directional Molecular Assemblies

Intermolecular interactions are crucial in determining the morphology of solution-processed semiconducting polymer thin films. However, these random interactions often lead to disordered or short-range ordered structures. Achieving long-range order in these films has been a challenge due to limited control over microscopic interactions in current techniques. Here, we present a molecular-level methodology that leverages spatial matching of intermolecular dynamics among solutes, solvents, and substrates to induce a directional molecular assembly in weakly bonded polymers. Within the optimized dynamic scale of 2.5 Å between polymer side chains and self-assembled monolayers (SAMs) on nanogrooved substrates, our approach transforms random aggregates into unidirectional fibers with a remarkable increase in the anisotropic stacking ratio from 1 to 11. The Flory-Huggins-based molecular stacking model accurately predicts the transitioning order on various SAMs, validated by morphological and spectroscopic observations. The enhanced structural ordering spans over 3 orders of magnitude in length, rising from the smallest 7.3 nm random crystallites to >14 μm unidirectional fibers on submillimeter areas. Overall, this study provides insights into the control of complex intermolecular interactions and offers enhanced molecular-level controllability in solution-based processes.