Disclosing Topographical and Chemical Patterns in Confined Films of High-Molecular-Weight Block Copolymers under Controlled Solvothermal Annealing.

The microphase separation of high-molecular-weight block copolymers into nanostructured films is strongly dependent on the surface fields. Both, the chain mobility and the effective interaction parameters can lead to deviations from the bulk morphologies in the structures adjacent to the substrate. Resolving frustrated morphologies with domain period L 0 above 100 nm is an experimental challenge. Here, solvothermal annealing was used to assess the contribution of elevated temperatures of the vapor T v and of the substrate T s on the evolution of the microphase-separated structures in thin films symmetric of polystyrene-b-poly(2vinylpyridine) block copolymer (PS-PVP) with L 0 about 120 nm. Pronounced topographic mesh-like and stripe patterns develop on a time scale of min and are attributed to the perforated lamella (PL) and up-standing lamella phases. By setting T v /T s combinations it is possible to tune the sizes of the resulting PL patterns by almost 10%. Resolving chemical periodicity using selective metallization of the structures revealed multiplication of the topographic stripes, i.e., complex segregation of the component within the topographic pattern, presumably as a result of morphological phase transition from initial non-equilibrium spherical morphology. Reported results reveal approaches to tune the topographical and chemical periodicity of microphase separation of high-molecular-weight block copolymers under strong confinement, which is essential for exploiting these structures as functional templates.