Strategies for controlling the planar arrangement of block copolymer micelles and inorganic nanoclusters

We report several strategies for varying the diameter, the center-to-center spacing, and the areal density of block copolymer micelles, or inorganic nanoclusters synthesized in the cores of the micelles, on planar substrates. The amphiphilic block copolymer, poly(styrene-b-acrylic acid) (PS/PAA), forms micelles in toluene solution that can be spin-coated onto a substrate to create quasi-hexagonal arrays of spherical PAA domains within a PS matrix. The carboxylic acid groups within the PAA domains can be utilized in a nanoreactor synthesis scheme to create inorganic nanocluster arrays, or the PAA domains can be cavitated to expose the carboxylic acid groups to the surface for possible covalent coupling reactions. The strategies we use to vary the planar arrangements include variation of the molecular weight of PS/PAA, variation of the amount of metal loaded into the micellar solution, addition of PS homopolymer into the micellar solution, and the mixing of different micellar solutions. Through these routes, we demonstrate varying the diameter of the inorganic nanoclusters from 4.7 to 16 nm and the areal density from 8 x 10(10) to 6.5 x 10(9) nanoclusters cm(-2). We are also able to create arrays of nanoclusters containing more than one inorganic species, with each nanocluster containing either one or all of the inorganic species, depending on the sequence of processing conditions employed. We characterize these arrays using energy-dispersive X-ray analysis on a scanning transmission electron microscope.