Block-copolymer-based plasmonic metamaterials

Block-copolymer (BCP) self-assembling provides a unique tool for realizing large-area ordered metamaterials, with desired optical properties. The benefits of using BCPs as templates for metamaterials come from two main aspects: first, BCPs show a rich range of available nano-morphologies, whose domains can be conveniently tuned in size, shape and periodicity, by changing molecular parameters; second, the chemical properties of the block polymers can lead to the selective inclusion of functionalized nanoparticles (NPs) of different materials in specific nanodomains, generating periodic arrays of NPs according to the geometry of the BCP acting as template. This approach allows finely modulating the optical properties of NPs and can be used as an intriguing and versatile tool to build useful devices for Optics & Photonics applications, with significant benefits for both fundamental and applied investigations. In this work, we investigate nanostructured thin films of polystyrene-block-poly(methyl methacrylate) BCP (PS-PMMA), characterized by an hexagonal array of PS cylinders in the PMMA matrix. The PS cylindrical domain are selectively filled by functionalized metallic (Au, Ag) NPs. The optical properties of such nano-structures are strongly affected by localized surface plasmons (LSPs) in the NPs, arising from the collective resonances of conduction electrons in the metal at a characteristic spectral range, usually in the visible range. LSPs induce high field enhancement (FE), with respect to an incident light, in proximity of the NP surface, and in particular in the gap between two close NPs (hot-spot). Moreover, LSPs increase the intensity of absorption and scattering of light by the NPs in their range of resonance.