Bright single photon emitters with enhanced quantum efficiency in a two-dimensional semiconductor coupled with dielectric nano-antennas.

Single photon emitters in atomically-thin semiconductors can be deterministically positioned using strain induced by underlying nano-structures. Here, we couple monolayer WSe2 to high-refractive-index gallium phosphide dielectric nano-antennas providing both optical enhancement and monolayer deformation. For single photon emitters formed on such nano-antennas, we find very low (femto-Joule) saturation pulse energies and up to 104 times brighter photoluminescence than in WSe2 placed on low-refractive-index SiO2 pillars. We show that the key to these observations is the increase on average by a factor of 5 of the quantum efficiency of the emitters coupled to the nano-antennas. This further allows us to gain new insights into their photoluminescence dynamics, revealing the roles of the dark exciton reservoir and Auger processes. We also find that the coherence time of such emitters is limited by intrinsic dephasing processes. Our work establishes dielectric nano-antennas as a platform for high-efficiency quantum light generation in monolayer semiconductors.

Anapole Excitations in Oxygen-Vacancy-Rich TiO2-x Nanoresonators: Tuning the Absorption for Photocatalysis in the Visible Spectrum.

Research on optically resonant dielectric nanostructures has accelerated the development of photonic applications, driven by their ability to strongly confine light on the nanoscale. However, as dielectric resonators are typically operated below their band gap to minimize optical losses, the usage of dielectric nanoantenna concepts for absorption enhancement has largely remained unexplored. In this work, we realize engineered nanoantennas composed of photocatalytic dielectrics and demonstrate increased light-harvesting capabilities in otherwise weakly absorptive spectral regions. In particular, we employ anapole excitations, which are known for their strong light confinement, in nanodisks of oxygen-vacancy-rich TiO2-x, a prominent photocatalyst that provides a powerful platform for exploring concepts in absorption enhancement in tunable nanostructures. The arising photocatalytic effect is monitored on the single particle level using the well-established photocatalytic silver reduction reaction on TiO2. With the freedom of changing the optical properties of TiO2 through tuning the abundance of VO states, we discuss the interplay between cavity damping and the anapole-assisted field confinement for absorption enhancement. This concept is general and can be extended to other catalytic materials with higher refractive indices.

Monitoring plasmonic hot-carrier chemical reactions at the single particle level.

Plasmon excitation in metal nanoparticles triggers the generation of highly energetic charge carriers that, when properly manipulated and exploited, can mediate chemical reactions. Single-particle techniques are key to unearthing the underlying mechanisms of hot-carrier generation, transport and injection, as well as to disentangling the role of the temperature increase and the enhanced near-field at the nanoparticle-molecule interface. Gaining nanoscopic insight into these processes and their interplay could aid in the rational design of plasmonic photocatalysts. Here, we present three different approaches to monitor hot-carrier reactivity at the single-particle level. We use a combination of dark-field microscopy and photoelectrochemistry to track a hot-hole driven reaction on a single Au nanoparticle. We image hot-electron reactivity with sub-particle spatial resolution using nanoscopy techniques. Finally, we push the limits by looking for a hot-electron induced chemical reaction that generates a fluorescent product, which should enable imaging plasmonic photocatalysis at the single-particle and single-molecule levels.

Plasmonic hot electron transport drives nano-localized chemistry.

Nanoscale localization of electromagnetic fields near metallic nanostructures underpins the fundamentals and applications of plasmonics. The unavoidable energy loss from plasmon decay, initially seen as a detriment, has now expanded the scope of plasmonic applications to exploit the generated hot carriers. However, quantitative understanding of the spatial localization of these hot carriers, akin to electromagnetic near-field maps, has been elusive. Here we spatially map hot-electron-driven reduction chemistry with 15 nm resolution as a function of time and electromagnetic field polarization for different plasmonic nanostructures. We combine experiments employing a six-electron photo-recycling process that modify the terminal group of a self-assembled monolayer on plasmonic silver nanoantennas, with theoretical predictions from first-principles calculations of non-equilibrium hot-carrier transport in these systems. The resulting localization of reactive regions, determined by hot-carrier transport from high-field regions, paves the way for improving efficiency in hot-carrier extraction science and nanoscale regio-selective surface chemistry.

Bridging the Gap between Dielectric Nanophotonics and the Visible Regime with Effectively Lossless Gallium Phosphide Antennas.

We present all-dielectric gallium phosphide (GaP) nanoantennas as an efficient nanophotonic platform for surface-enhanced second harmonic generation (SHG) and fluorescence (SEF), showing negligible losses in the visible range. Employing single GaP nanodisks, we observe an increase of more than 3 orders of magnitude in the SHG conversion signal in comparison with the bulk. This constitutes an SHG efficiency as large as 0.0002%, which is to the best of our knowledge the highest yet achieved value for a single nano-object in the optical region. Furthermore, we show that GaP dimers with 35 nm gap can enhance up to 3600 times the fluorescence emission of dyes located in the gap of the nanoantenna. This is accomplished by a fluorescence lifetime reduction of at least 22 times, accompanied by a high-intensity field confinement in the gap region. These results open new avenues for low-loss nanophotonics in the optical regime.