Hierarchical Structuring in Block Copolymer Nanocomposites through Two Phase-Separation Processes Operating on Different Time Scales

Tailoring the size and surface chemistry of nanoparticles allows one to control their position in a block copolymer, but this is usually limited to one-dimensional distribution across domains. Here, the hierarchical assembly of poly(ethylene oxide)-stabilized gold nanoparticles (Au-PEO) into hexagonally packed clusters inside mesostructured ultrathin films of polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) is described. A close examination of the structural evolution at different nanoparticle filling fractions and PEO ligand molecular weights suggests that the mechanism leading to this structure-within-structure is the existence of two phase separation processes operating on differe…