Nanoporous Thin Films and Binary Nanoparticle Superlattices Created by Directed Self-Assembly of Block Copolymer Hybrid Materials

The design and development of well-defined, functional nanostructures via self-assembly is one of the key objectives in current nanotechnology. Block copolymer-based hybrid materials are attractive candidates for the fabrication of multifunctional nanostructures, which provide the building blocks for more complex nanoarchitectures and nanodevices. However, one of the major challenges lies in controlling the structure formation in these hybrid materials by guiding the self-assembly of the block copolymer. Here, hierarchical nanoporous structures are fabricated via guided multistep self-assembly of diblock copolymer micellar solutions onto hydrophilic solid substrates. The core of polystyrene-block-poly[4-vinylpyridine] micelles serves as a nanoreactor for the preparation of size-controlled gold nanoparticles. Deposition of thin films of the micellar solution in combination with a nonselective cosolvent (THF), on hydrophilic surfaces leads to the formation of hierarchical nanoporous structures. The micellar films exhibit two different pore diameters and a total pore density of more than 10¹⁰ holes per cm². Control over the pore diameter is achieved by adapting the molecular weight of the polystyrene-block-poly[4-vinylpyridine] diblock copolymer. Moreover, the porous morphology is used as a template for the fabrication of bimetallic nanostructured thin films. The PS-b-P4VP template is subsequently removed by oxygen plasma etching, leaving behind binary nanoparticle structures that mimic the original thin film morphology.