Role of Multivalent Interactions in Dynamic-Template-Directed Assembly of Conjugated Polymers

Dynamic-template-directed assembly is a promising method to enhance molecular ordering and electronic properties of solution-coated polymer semiconductor thin films over a large area. In this work, we establish that multicomponent dynamic templates of complementary chemistries can promote polymer crystallization through cooperative multivalent interactions. We investigate this phenomenon using a combination of templating substrates including a fluoropolymer, a hydrogen-bonded liquid, and an ionic liquid (IL). Template-dependent multiscale morphology is studied by a comprehensive set of characterization techniques to understand how introducing diverse chemical moieties modulates polymer assembly. Our results clearly confirm synergistic effects between components of complementary chemistries constituting the dynamic template. The relative degree of crystallinity is improved by 50–150% for films deposited on multicomponent dynamic templates compared to their neat constituents. In addition, macroscopic alignm...