Second harmonic generation (SHG) is forbidden for materials with inversion symmetry, such as bulk metals. Symmetry can be broken by morphological or dielectric discontinuities, yet SHG from a smooth continuous metallic surface is negligible. Using non-linear microscopy, we experimentally demonstrate enhanced SHG within an area of smooth silver film surrounded by nanocavities. Nanocavity-assisted SHG is locally enhanced by more than one order of magnitude compared to a neighboring silver surface area. Linear optical measurements and cathodoluminescence (CL) imaging substantiate these observations. We suggest that plasmonic modes launched from the edges of the nanocavities propagate onto the smooth silver film and annihilate, locally generating SHG. In addition, we show that these hotspots can be dynamically controlled in intensity and location by altering the polarization of the incoming field. Our results show that switchable nonlinear hotspots can be generated on smooth metallic films, with important applications in photocatalysis, single-molecule spectroscopy and non-linear surface imaging.

Controlling the optical field down to the nanometer scale is a key step in optoelectronic applications and light–matter interaction at the nanoscale. Bowtie structures, rods, and sharp tapers are commonly used to realize such optical properties, but their fabrication is challenging. In this context, the complementary structures, namely, holes and cavities, are less explored. Herein, a simple system of two metallic nanocavities milled in thin silver film is used to confine the electromagnetic field to an area of ≈60 nm2. The field is confined onto a flat surface area and is either enhanced or suppressed by the polarization state of incident light. The energy of this spatially confined mode is determined by the distance between the two cavities and thus any color (wavelength) at the optical regime can be achieved. As a consequence, a dynamically controlled color is generated on an optical pixel size smaller than 1 µm2. Those results are supported by both transmission spectra and a cathodoluminescence study.

Second harmonic generation (SHG) is forbidden from most bulk metals, because metals are characterized by a net zero electric-field in equilibrium. This limit breaks down when reaching nanoscale dimensions, as have been shown for metallic nano-particles and nano-cavities. Yet, nonlinear response from a three-dimensional (3D) macroscale metallic piece comprising suboptical wavelength features remains a challenge for many years. Herein, we introduce a largescale nanoporous metallic network whose building-blocks are assembled into an effective nonlinear conductive material, with a considerable conversion efficiency in a wide range of optical wavelengths. The high nonlinear response results from the network structure having a large surface area on which the inversion symmetry is broken. In addition, because of the 3D structure, hotspots can be formed also in deeper focal plans of the metallic network, and thus can give rise to coherent addition of the signal. The solid connectivity between the nanoscale building-blocks also plays a role, because it forms a robust network which may respond in a collective manner to form very intense hot-spots. Broadband responses of the metallic network are observed both by SHG and cathodoluminescence (CL). The large-scale dimension and generation of randomized hotspots make this 3D metallic network a promising candidate for applications like photocatalysis, sensing, or in optical imaging as structured illumination microscopy.

Second harmonic generation (SHG) is forbidden from most bulk metals because metals are characterized by centrosymmetric symmetry. Adsorption or desorption of molecules at the metal interface can break the symmetry and lead to SHG responses. Yet, the response is relatively low, and minute changes occurring at the interface, especially at solid/liquid interfaces, like in battery electrodes are difficult to assess. Herein, we use a plasmonic structure milled in a gold electrode to increase the overall SHG signal from the interface and gain information about small changes occurring at the interface. Using a specific homebuilt cell, we monitor changes at the liquid/electrode interface. Specifically, traces of water in dimethoxyethane (DME) have been detected following changes in the SHG responses from the plasmonic structures. We propose that by plasmonic structures this technique can be used for assessing minute changes occurring at solid/liquid interfaces such as battery electrodes.

Herein, centrosymmetric aluminum plasmonic structures composed of triangular cavities are studied and their long‐range coupling by cathodoluminescence nanoscopy are visualized. Four different plasmonic structures containing the same subunit are studied. The plasmonic modes of the individual triangular subunits are localized at the triangle sides rather than at the vertices, in agreement with other studies. Yet, upon strong interaction between the cavities, a redistribution of the electromagnetic field is observed such that it delocalizes around the cavities in the form of a contour, providing a mode enhancement and a pronounced nonlinear response as observed by second harmonic generation. Comparison between plasmonic structures made of either silver or aluminum reveals that the metal dielectric function plays an important role in the interaction between the cavities. This work provides a rationale for designing plasmonic structures with enhanced nonlinear activity.