Forming Long-range Order of Semiconducting Polymers through Liquid-phase Directional Molecular Assemblies

Abstract

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 directional molecular assembly in weakly bonded polymers. Within the optimized dynamic scale of 2.5 \r{A} 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 morphologic and spectroscopic observations. The enhanced structural ordering spans over 3 orders of magnitude in length, raising from the smallest 7.3 nm random crystallites to >14 um unidirectional fibers on sub-millimeter areas. Overall, this study provides insights into the control of complex intermolecular interactions and offers enhanced molecular-level controllability in solution-based processes.