Vertical Orientation of Nanodomains on Versatile Substrates through Self‐Neutralization Induced by Star‐Shaped Block Copolymers

Vertical orientation of lamellar and cylindrical nanodomains of block copolymers on substrates is one of the most promising means for developing nanopatterns of next‐generation microelectronics and storage media. However, parallel orientation of lamellar and cylindrical nanodomains is generally preferred due to different affinity between two block segments in a block copolymer toward the substrate and/or air. Thus, vertical orientation of the nanodomains is only obtained under various pre‐ or post‐treatments such as surface neutralization by random copolymers, solvent annealing, and electric or magnetic field. Here, a novel self‐neutralization concept is introduced by designing molecular architecture of a block copolymer. Star‐shaped 18 arm poly(methyl methacrylate)‐block‐polystyrene copolymers ((PMMA‐b‐PS)₁₈) exhibiting lamellar and PMMA cylindrical nanodomains are synthesized. When a thin film of (PMMA‐b‐PS)₁₈ is spin‐coated on a substrate, vertically aligned lamellar and cylindrical nanodomains are obtained without any pre‐ or post‐treatment, although thermal annealing for a short time (less than 30 min) is required to improve the spatial array of vertically aligned nanodomains. This result is attributed to the star‐shaped molecular architecture that overcomes the difference in the surface affinity between PS and PMMA chains. Moreover, vertical orientations are observed on versatile substrates, for instance, semiconductor (Si, SiO_x), metal (Au), PS or PMMA‐brushed substrate, and a flexible polymer sheet of polyethylene naphthalate.