Lateral Order and Self-Organized Morphology of Diblock Copolymer Micellar Films

We report the lateral order and self-organized morphology of diblock copolymer polystyrene-block-poly(2-vinylpyridine), P(S-b-2VP), and micelles on silicon substrates (SiO_x/Si). These micellar films were prepared by spin coating from polymer solutions of varied concentration of polymer in toluene onto SiO_x/Si, and were investigated with grazing-incidence small-angle X-ray scattering (GISAXS) and an atomic force microscope (AFM). With progressively increased surface coverage with increasing concentration, loosely packed spherical micelles, ribbon-like nanostructures, and a second layer of spherical micelles were obtained sequentially. Quantitative analysis and simulations of the micellar packing demonstrates that the spatial ordering of the loosely packed spherical micelles altered from short-range order to hexagonal order when the micellar coverage increased from small to moderate densities of the covered surface. At large densities, anisotropic fusion between spherical micelles caused the ribbon-like nanostructures to have a short-range spatial order; the ordering quality of the second layer was governed by the rugged surface of the underlying layer because the valleys between the ribbon-like nanostructures allowed for further deposition of spherical micelles.