Recent advances in the ability to synthesize metallic nanoparticles with tailored geometries have led to a revolution in the field of plasmonics. However, studies of the important complementary system, an inverted nanostructure, have so far been limited to two-dimensional sphere-segment voids or holes. Here we reveal the localized surface plasmon resonances (LSPRs) of nanovoids that are topologically enclosed in three-dimensions: an "anti-nanoparticle". We combine this topology with the favorable plasmonic properties of aluminum to observe strongly localized field enhancements with LSPR energies in the extreme UV range, well beyond those accessible with noble metals or yet achieved with aluminum. We demonstrate the resonance tunability by tailoring the shape and size of the nanovoids, which are truncated octahedra in the 10-20 nm range. This system is pristine: the nanovoid cavity is free from any oxide or supporting substrate that would affect the LSPRs. We exploit this to infer LSPRs of pure, sub-20-nm Al nanoparticles, which have yet to be synthesized. Access to this extreme UV range will allow applications in LSPR-enhanced UV photoemission spectroscopy and photoionization.
Keywords: aluminum; electron energy-loss spectroscopy; electron-driven discrete-dipole approximation; nanovoids; plasmonics.