The gap length between plasmonic nanoparticles determines the strength of the optical coupling that results in electromagnetic field enhancement for spectroscopic and other applications. Although gap plasmon resonances have been the focus of increasing research interest, experimental observations have primarily been limited to the coupling of spherical nanoparticles that may not provide clear spectral contrast of the optical response as the interaction evolves from capacitive to charge transfer with the gap size decreasing to sub-nanometer. Here, by taking advantage of the sharp plasmon resonances of colloidal gold nanorods coupled to gold film, we present the spectral evolution of gap plasmon resonance as the particle–film spacing varies from over 30 nm to the touching limit. We find that the capacitive gap plasmon resonance of the coupled system red-shifts and narrows continuously until it vanishes at the quantum tunneling limit, in contrast to the nonlocal and Landau damping effects that are expected to result in relative blue-shifting and spectral broadening. When the spacer thickness is further decreased, high order cavity modes appear, and eventually single peak broad resonances that are characteristic of tunneling and direct contact particle–film interaction emerge. The experimental observations show that nanorods are better suited for creating cavity plasmon resonances with high quality factor, and the spectral contrast at the transition provides clarity to develop improved theoretical modeling of optical coupling at sub-nanometer gap lengths.

No abstract

Localized surface plasmon resonances can increase the quantum efficiency of photon emitters through both absorption and spontaneous emission enhancement effects. Despite extensive studies, experimental results that clearly distinguish the two plasmonic enhancement effects are rarely available. Here, we present clear spectral signatures of the plasmonic enhancement effects on the absorption (excitation) and spontaneous emission (Purcell factor) by analyzing the temperature-dependent photoluminescence (PL) properties of an InGaAs/GaAs single quantum well (QW) coupled to colloidal gold nanorods (AuNRs) at different GaAs capping layer thicknesses (d). We find that when the emitting InGaAs layer is close to the AuNRs (d = 5 nm), the plasmonic enhancement effect on the QW PL is dominated by the Purcell factor, which significantly increases the external quantum efficiency of the QW that otherwise barely emits. When d is increased to 10 nm, the temperature dependence of the PL enhancement factor (F) reflects absorption enhancement in the capping layer followed by carrier diffusion and capture by the well. First, F increases with temperature and then decreases following the temperature dependence of the carrier diffusion coefficient in GaAs. By factoring out the contribution of the captured carriers to F, it is shown that carrier transfer to the well reaches saturation with increasing incident laser power. In addition to providing insight into the plasmonic enhancement mechanism, the results presented in this work suggest that colloidal plasmonic nanoparticles can be used as simple probes for understanding carrier transport phenomena in arbitrary semiconductor heterostructures.

The optomechanical interaction between nanocavity plasmons and molecular vibrations can result in interfacial phenomena that can be tailored for sensing and photocatalytic applications. Here, we report for the first time that plasmon-vibration interaction can induce laser-plasmon detuning dependent plasmon resonance linewidth broadening, indicating energy transfer from the plasmon field to collective vibrational modes. The linewidth broadening accompanied by the large enhancement of the Raman scattering signal is observed as the laser-plasmon blue-detuning approaches the CH vibrational frequency of the molecular systems integrated in gold nanorod-on-mirror nanocavities. The experimental observations can be explained based on the molecular optomechanics theory that predicts dynamical backaction amplification of the vibrational modes and high sensitivity of Raman scattering when the plasmon resonance overlaps with the Raman emission frequency. The results presented here suggest that molecular optomechanics coupling may be manipulated for creating hybrid properties based on interactions between molecular oscillators and nanocavity electromagnetic optical modes.

No abstract