Film instability induced evolution of hierarchical structures in annealed ultrathin films of an asymmetric block copolymer on polar substrates

With an atomic-force microscope and a grazing-incidence small-angle X-ray scattering we studied ex situ the evolution of hierarchical structures in isothermally annealed ultrathin films of asymmetric polystyrene-block-poly(methyl methacrylate) P(S-b-MMA) that dewetted on polar substrates via a mechanism involving nucleation and growth. Film instability causes the surface to acquire an undulating thickness through incommensurability, producing not only the relief structures on a micrometer scale but also mesophase-separated domains on a nanometer scale. The dewetted morphologies strongly influence the ordering behavior of the nanoscale domains. The noncylindrical nanostructures become stable at the curved edges of the relief microstructures in the destabilized P(S-b-MMA) films, for which a preferential wetting of the PS block with the free surface is prohibited. Additionally, the shape of relief structures as result of film instability correlates with the formation of mesophase-separated nanodomains. At early stages of film instability, the formation of parallel-oriented PMMA cylindrical nanodomains increases the deformation energy and it further persists to force the shape of relief structures between irregular holes to have a facet-wedge shape. However, those relief structures are expected to be not at equilibrium. At high temperatures, the relief structures between irregular holes progressively developed to form hemispherical-cap drops accompanied by a transformation of cylindrical into noncylindrical nanodomains at curved surfaces.