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    Protein-Assisted Assembly of Modular 3D Plasmonic Raspberry-like Core/Satellite Nanoclusters: Correlation of Structure and Optical Properties
    (Washington, DC : Soc., 2016) Höller, Roland P. M.; Dulle, Martin; Thomä, Sabrina; Mayer, Martin; Steiner, Anja Maria; Förster, Stephan; Fery, Andreas; Kuttner, Christian; Chanana, Munish
    We present a bottom-up assembly route for a large-scale organization of plasmonic nanoparticles (NPs) into three-dimensional (3D) modular assemblies with core/satellite structure. The protein-assisted assembly of small spherical gold or silver NPs with a hydrophilic protein shell (as satellites) onto larger metal NPs (as cores) offers high modularity in sizes and composition at high satellite coverage (close to the jamming limit). The resulting dispersions of metal/metal nanoclusters exhibit high colloidal stability and therefore allow for high concentrations and a precise characterization of the nanocluster architecture in dispersion by small-angle X-ray scattering (SAXS). Strong near-field coupling between the building blocks results in distinct regimes of dominant satellite-to-satellite and core-to-satellite coupling. High robustness against satellite disorder was proved by UV/vis diffuse reflectance (integrating sphere) measurements. Generalized multiparticle Mie theory (GMMT) simulations were employed to describe the electromagnetic coupling within the nanoclusters. The close correlation of structure and optical property allows for the rational design of core/satellite nanoclusters with tailored plasmonics and well-defined near-field enhancement, with perspectives for applications such as surface-enhanced spectroscopies.
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    Mechanotunable Surface Lattice Resonances in the Visible Optical Range by Soft Lithography Templates and Directed Self-Assembly
    (Washington, DC : Soc., 2019) Gupta, Vaibhav; Probst, Patrick T.; Goßler, Fabian R.; Steiner, Anja Maria; Schubert, Jonas; Brasse, Yannic; König, Tobias A.F.; Fery, Andreas
    We demonstrate a novel colloidal self-assembly approach toward obtaining mechanically tunable, cost-efficient, and low-loss plasmonic nanostructures that show pronounced optical anisotropy upon mechanical deformation. Soft lithography and template-assisted colloidal self-assembly are used to fabricate a stretchable periodic square lattice of gold nanoparticles on macroscopic areas. We stress the impact of particle size distribution on the resulting optical properties. To this end, lattices of narrowly distributed particles (∼2% standard deviation in diameter) are compared with those composed of polydisperse ones (∼14% standard deviation). The enhanced particle quality sharpens the collective surface lattice resonances by 40% to achieve a full width at half-maximum as low as 16 nm. This high optical quality approaches the theoretical limit for this system, as revealed by electromagnetic simulations. One hundred stretching cycles demonstrate a reversible transformation from a square to a rectangular lattice, accompanied by polarization-dependent optical properties. On the basis of these findings we envisage the potential applications as strain sensors and mechanically tunable filters. © 2019 American Chemical Society.
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    Active Plasmonic Colloid-to-Film-Coupled Cavities for Tailored Light-Matter Interactions
    (Washington, DC : Soc., 2019) Goßler, Fabian R.; Steiner, Anja Maria; Stroyuk, Oleksandr; Raevskaya, Alexandra; König, Tobias A.F.
    For large-scale fabrication of optical circuits, tailored subwavelength structures are required to modulate the refractive index. Here, we introduce a colloid-to-film-coupled nanocavity whose refractive index can be tailored by various materials, shapes, and cavity volumes. With this colloidal nanocavity setup, the refractive index can be adjusted over a wide visible wavelength range. For many nanophotonic applications, specific values for the extinction coefficient are crucial to achieve optical loss and gain. We employed bottom-up self-assembly techniques to sandwich optically active ternary metal-chalcogenides between a metallic mirror and plasmonic colloids. The spectral overlap between the cavity resonance and the broadband emitter makes it possible to study the tunable radiative properties statistically. For flat cavity geometries of silver nanocubes with sub-10 nm metallic gap, we found a fluorescence enhancement factor beyond 1000 for 100 cavities and a 112 meV Rabi splitting. In addition, we used gold spheres to extend the refractive index range. By this easily scalable colloidal nanocavity setup, gain and loss building blocks are now available, thereby leading to new generation of optical devices. Copyright © 2019 American Chemical Society.