Surface scattering contribution to the plasmon width in embedded Ag nanospheres

Nanometer-sized metal particles exhibit broadening of the localized surface plasmon resonance (LSPR) in comparison to its value predicted by the classical Mie theory. Using our model for the LSPR dependence on non-local surface screening and size quantization, we quantitatively relate the observed plasmon width to the nanoparticle radius $R$ and the permittivity of the surrounding medium $\epsilon_m$. For Ag nanospheres larger than 8 nm only the non-local dynamical effects occurring at the surface are important and, up to a diameter of 25 nm, dominate over the bulk scattering mechanism. Qualitatively, the LSPR width is inversely proportional to the particle size and has a nonmonotonic dependence on the permittivity of the host medium, exhibiting for Ag a maximum at $\epsilon_m\approx2.5$. Our calculated LSPR width is compared with recent experimental data.Comment: 11 pages, 4 figures. Accepted for publication in Optics Expres

Diffuse Surface Scattering in the Plasmonic Resonances of Ultra-Low Electron Density Nanospheres

Localized surface plasmon resonances (LSPRs) have recently been identified in extremely diluted electron systems obtained by doping semiconductor quantum dots. Here we investigate the role that different surface effects, namely electronic spill-out and diffuse surface scattering, play in the optical properties of these ultra-low electron density nanosystems. Diffuse scattering originates from imperfections or roughness at a microscopic scale on the surface. Using an electromagnetic theory that describes this mechanism in conjunction with a dielectric function including the quantum size effect, we find that the LSPRs show an oscillatory behavior both in position and width for large particles and a strong blueshift in energy and an increased width for smaller radii, consistent with recent experimental results for photodoped ZnO nanocrystals. We thus show that the commonly ignored process of diffuse surface scattering is a more important mechanism affecting the plasmonic properties of ultra-low electron density nanoparticles than the spill-out effect.Comment: 19 pages, 5 figures. Accepted for publication in The Journal of Physical Chemistry Letter

Realizing strong light-matter interactions between single nanoparticle plasmons and molecular excitons at ambient conditions

Realizing strong light-matter interactions between individual 2-level systems and resonating cavities in atomic and solid state systems opens up possibilities to study optical nonlinearities on a single photon level, which can be useful for future quantum information processing networks. However, these efforts have been hampered by the unfavorable experimental conditions, such as cryogenic temperatures and ultrahigh vacuum, required to study such systems and phenomena. Although several attempts to realize strong light-matter interactions at room-temperature using so-called plasmon resonances have been made, successful realizations on the single nanoparticle level are still lacking. Here, we demonstrate strong coupling between plasmons confined within a single silver nanoprism and excitons in molecular J-aggregates at ambient conditions. Our findings show that the deep subwavelength mode volumes, $V$, together with high quality factors, $Q$, associated with plasmons in the nanoprisms result in strong coupling figure-of-merit -- $Q/\sqrt{V}$ as high as $\sim6\times10^{3}$~$\mu$m$^{-3/2}$ -- a value comparable to state-of-art photonic crystal and microring resonator cavities, thereby suggesting that plasmonic nanocavities and specifically silver nanoprisms can be used for room-temperature quantum optics

Strong coupling out of the blue: an interplay of quantum emitter hybridization with plasmonic dark and bright modes

Strong coupling between a single quantum emitter and an electromagnetic mode is one of the key effects in quantum optics. In the cavity QED approach to plasmonics, strongly coupled systems are usually understood as single-transition emitters resonantly coupled to a single radiative plasmonic mode. However, plasmonic cavities also support non-radiative (or "dark") modes, which offer much higher coupling strengths. On the other hand, realistic quantum emitters often support multiple electronic transitions of various symmetry, which could overlap with higher order plasmonic transitions -- in the blue or ultraviolet part of the spectrum. Here, we show that vacuum Rabi splitting with a single emitter can be achieved by leveraging dark modes of a plasmonic nanocavity. Specifically, we show that a significantly detuned electronic transition can be hybridized with a dark plasmon pseudomode, resulting in the vacuum Rabi splitting of the bright dipolar plasmon mode. We develop a simple model illustrating the modification of the system response in the "dark" strong coupling regime and demonstrate single photon non-linearity. These results may find important implications in the emerging field of room temperature quantum plasmonics

Suppression of photo-oxidation of organic chromophores by strong coupling to plasmonic nanoantennas

Intermixed light-matter quasiparticles - polaritons - possess unique optical properties owned to their compositional nature. These intriguing hybrid states have been extensively studied over the past decades in a wide range of realizations aiming at both basic science and emerging applications. However, recently it has been demonstrated that not only optical, but also material-related properties, such as chemical reactivity and charge transport, may be significantly altered in the strong coupling regime of light-matter interactions. Here, we show that a nanoscale system, comprised of a plasmonic nanoprism strongly coupled to excitons in J-aggregated form of organic chromophores, experiences modified excited state dynamics and therefore modified photo-chemical reactivity. Our experimental results reveal that photobleaching, one of the most fundamental photochemical reactions, can be effectively controlled and suppressed by the degree of plasmon-exciton coupling and detuning. In particular, we observe a 100-fold stabilization of organic dyes for the red-detuned nanoparticles. Our findings contribute to understanding of photochemical properties in the strong coupling regime and may find important implications for the performance and improved stability of optical devices incorporating organic dyes.Comment: 5 figures; includes Supplementary Material