Consequences of Surface Neutralization in Diblock Copolymer Thin Films

Two high-χ block copolymers, lamella-forming poly(styrene-block-[isoprene-random-epoxy­isoprene]) (PS-PEI78, with 78 mol % epoxidation) and lamella-forming poly(4-tri­methyl­silyl­styrene-block-d,l-lactide) (PTMSS-PLA), were used to study three combinations of interfacial neutrality involving at least one neutral interface. PS-PEI78 annealed on a nonpreferential polymer mat (SMG) produced perpendicular lamellae independent of film thickness, indicating a neutral substrate and neutral free surface. In contrast, the presence of only one neutral interface results in the formation of surface topography (“islands” and “holes”) with 0.5L 0 step heights. PS-PEI78 (neutral free surface) annealed on PS brush (PS block preferential) forms “half” islands and holes. The inverse experiment, PTMSS-PLA (with a PTMSS preferential free surface) annealed on a neutral (or near neutral) substrate surface, also generates 0.5L 0 topography. These “half” island and hole structures are stable to extended thermal annealing. PS-PEI78 exposes both blocks at the free surface in contrast to PTMSS-PLA, which exposes just one. All three combinations of interfacial neutrality are explained by the precise balancing of the wetting tendencies of the two blocks. Evolution of the 0.5L 0 motifs appears to be facilitated by a preference to form half-period thick nuclei in the initial stages of morphological development.