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Nonlinear optical materials comprise the foundation of modern photonics, offering functionalities ranging from ultrafast lasers to optical switching, harmonic and soliton generation. Optical nonlinearities are typically strong near the electronic resonances of a material and thus provide limited tuneability for practical use. Here we show that in plasmonic nanorod metamaterials, the Kerr-type nonlinearity is not limited by the nonlinear properties of the constituents. Compared with gold's nonlinearity, the measured nonlinear absorption and refraction demonstrate more than two orders of magnitude enhancement over a broad spectral range that can be engineered via geometrical parameters. Depending on the metamaterial's effective plasma frequency, either a focusing or defocusing nonlinearity is observed. The ability to obtain strong and fast optical nonlinearities in a given spectral range makes these metamaterials a flexible platform for the development of low-intensity nonlinear applications.

Hyperbolic metamaterials comprised of an array of plasmonic nanorods provide a unique platform for designing optical sensors and integrating nonlinear and active nanophotonic functionalities. In this work, the waveguiding properties and mode structure of planar anisotropic metamaterial waveguides are characterized experimentally and theoretically. While ordinary modes are the typical guided modes of the highly anisotropic waveguides, extraordinary modes, below the effective plasma frequency, exist in a hyperbolic metamaterial slab in the form of bulk plasmon-polaritons, in analogy to planar-cavity exciton-polaritons in semiconductors. They may have very low or negative group velocity with high effective refractive indices (up to 10) and have an unusual cut-off from the high-frequency side, providing deep-subwavelength (λ0/6–λ0/8 waveguide thickness) single-mode guiding. These properties, dictated by the hyperbolic anisotropy of the metamaterial, may be tuned by altering the geometrical parameters of the nanorod composite.

Hot, nonequilibrium carriers formed near the interfaces of semiconductors or metals play a crucial role in chemical catalysis and optoelectronic processes. In addition to optical illumination, an efficient way to generate hot carriers is by excitation with tunnelling electrons. Here we show that the generation of hot electrons makes the nanoscale tunnel junctions highly reactive and facilitates strongly confined chemical reactions which can in turn modulate the tunnelling processes. We designed a device containing an array of electrically-driven plasmonic nanorods with up to 1011 tunnelling junctions per square centimeter, which demonstrates hot-electron activation of oxidation and reduction reactions in the junctions, induced by the presence of O2 and H2 molecules, respectively. The kinetics of the reactions can be monitored in-situ following the radiative decay of tunnelling-induced surface plasmons. This electrically-driven plasmonic nanorod metamaterial platform can be useful for the development of nanoscale chemical and optoelectronic devices based on electron tunnelling.

Light–matter interactions can be strongly modified by the surrounding environment. Here, we report on the first experimental observation of molecular spontaneous emission inside a highly non-local metamaterial based on a plasmonic nanorod assembly. We show that the emission process is dominated not only by the topology of its local effective medium dispersion, but also by the non-local response of the composite, so that metamaterials with different geometric parameters but the same local effective medium properties exhibit different Purcell factors. A record-high enhancement of a decay rate is observed, in agreement with the developed quantitative description of the Purcell effect in a non-local medium. An engineered material non-locality introduces an additional degree of freedom into quantum electrodynamics, enabling new applications in quantum information processing, photochemistry, imaging and sensing with macroscopic composites.