Directed Self-Assembly of Block Copolymer Micelles onto Topographically Patterned Surface.

We report a facile method to control directed self-assembly (DSA) of spherical micelles of block copolymers (BCPs) by topographically patterned surface. A cylinder-forming polystyrene-block-poly(2-vinylpyridine) copolymer [Mn,PS = 175 kg/mol, Mn,P2VP = 70 kg/mol, and polydipersity index (PDI) = 1.08] was phase-separated on a thin film of poly(vinyl alcohol) (PVA) by solvent annealing. By additional treatment with ethanol as a preferential solvent for P2VP block, the surface of BCP thin film was reconstructed to produce nanopores. Nanoporous structures in BCP thin films were transferred to the underlying hydrophilic PVA film by reactive ion etching (RIE). Then spherical BCP micelles were quickly self-assembled within the nanopores in the PVA layer due to topographical contrast and surface energy difference during spin-coating. Consequently, the site-selective array of BCP micelles was utilized as templates to achieve heterogeneous organization of nanoparticles and organic fluorescent dyes over a large area. In addition, it was observed that those heterogeneous assemblies showed a remarkable decrease in fluorescence intensity of organic dyes.

Core-Corona Functionalization of Diblock Copolymer Micelles by Heterogeneous Metal Nanoparticles for Dual Modality in Chemical Reactions.

Nanoscale assemblies composed of different types of nanoparticles (NPs) can reveal interesting aspects about material properties beyond the functions of individual constituent NPs. This research direction may also represent current challenges in nanoscience toward practical applications. With respect to the assembling method, synthetic or biological nanostructures can be utilized to organize heterogeneous NPs in specific sites via chemical or physical interactions. However, those assembling methods often encounter uncontrollable particle aggregation or phase separation. In this study, we anticipated that the self-segregating properties of block copolymer micelles could be particularly useful for organizing heterogeneous NPs, because the presence of chemically distinct domains such as the core and the corona can facilitate the selective placement of constituent NPs in separate domains. Here, we simultaneously functionalized the core and the corona of micelles by Au NPs and Ag NPs, which exhibited plasmonic and catalytic functions, respectively. Our primary question is whether these plasmonic and catalytic functions can be combined in the assembled structures to engineer the kinetics of a model chemical reaction. To test this hypothesis, the catalytic reduction of 4-nitrophenol was selected to evaluate the collective properties of the micellar assemblies in a chemical reaction.