Irreversible Physisorption of PS‑b‑PMMA Copolymers on Substrates for Balanced Interfacial Interactions as a Versatile Surface Modification

We present a direct approach to fabricating the perfect neutral layer for block copolymer (BCP) self-assembled thin films. An irreversible physisorption of polystyrene-b-poly­(methyl methacrylate) (PS-b-PMMA) itself onto the bottom substrates, though extremely thin, offers such a compositional randomness for the substrates, directing the balanced interfacial interactions toward both blocks of the top-layer PS-b-PMMA. Owing to the neutral property from the skin layers, the chemically identical BCP self-assembles into perpendicular microdomains on the adsorbed layer composed of itself, as identified in symmetric PS-b-PMMA films. Intriguingly, the compositional randomness turns out to be valid when the correlation length (ξ) of the BCP layer adsorbed on the substrates is shorter than equilibrium lamellar spacing (L₀) of the BCP. Our strategy provides its versatility applicable to various substrates without any necessity of specific random copolymer brushes or mats, enabling the design of a neutral platform for PS-b-PMMA films.