Spatially Amplified and Rigid Junction in Diblock Copolymers: Reduced Microphase Separation Size via Interface Expansion

We introduce an approach in diblock copolymer design, where modifying the junction point with rigid bulky monomer expands the cross-sectional area of the interface and leads to a decrease in the repeat period. Using living anionic polymerization, we synthesized a series of dialkynyl midfunctionalized poly(styrene-b-methyl methacrylate) (PSM-DA) and functionalized them using the thiol-alkyne click reaction with specifically selected rigid bulky monomers: PSS-(3-mercapto)propyl-heptaisobutyl substituted (PSS) and 1-adamantanethiol (ADA). This modification, though involving only a single monomer unit within the diblock copolymer structure, brought about a significant reduction in domain size, with PSS and ADA reducing it by 18% and 15%, respectively. The results indicate a method for reducing the domain sizes of block copolymers, which could lead to advancements in lithography and various nanotechnological applications.