Non-Native Block Copolymer Ordering via Directed Blends

Directed assembly of block copolymers seeks to control structure formation, often beyond the phases observed in the bulk equilibrium phase diagram. We discuss the use of blending strategies to direct ordering in block copolymer thin films. Structured/layered initial configurations (pathway-priming) and judicious selection of process history (pathway-engineering) are exploited to drive block copolymer thin films into non-native structures. Blends of copolymers are also responsive to chemical templates, exhibiting new morphologies as chains locally reorganize and partition into nano-domains. Finally, we show how autonomous experimentation—AI/ML accelerated search through parameter spaces—can discover new morphologies in these systems.