Downsizing feature of microphase-separated structures via intramolecular crosslinking of block copolymers

A novel strategy for downsizing the feature of microphase-separated structures was developed via the intramolecular crosslinking reaction of block copolymers (BCPs) without changing the molecular weight. A series of BCPs consisting of poly[styrene-st-(p-3-butenyl styrene)] and poly(rac-lactide) (SBS–LA) was subjected to Ru-catalyzed olefin metathesis under highly diluted conditions to produce intramolecularly crosslinked BCPs (SBS(cl)–LAs). Small-angle X-ray scattering measurement and transmission electron microscopy observation of the SBS(cl)–LAs revealed feature size reduction in lamellar (LAM) and hexagonally close-packed cylinder (HEX) structures in the bulk state, which was surely due to the restricted chain dimensions of the intramolecularly crosslinked SBS block. Notably, the degree of size reduction was controllable by varying the crosslink density, with a maximum decrease of 22% in the LAM spacing. In addition, we successfully observed the downsizing of the HEX structure in the thin film state using atomic force microscopy, indicating the applicability of the present methodology to next-generation lithography technology.