Optoelectronic modulators that operate by the electrical tuning of plasmonic resonator structures have demonstrated fast (>MHz) manipulation of terahertz (THz) radiation for communications, imaging, and spectroscopy applications. Among this class of THz device, chiral metamaterial-based polarization modulators have attracted increasing attention due to the importance of THz polarization control for chemistry, biology, and spectroscopy applications, as well as for THz communication protocols. In this paper, active polarization modulation of a THz quantum cascade laser is demonstrated by the electrical tuning of a 2D chiral metamaterial array. The operating principle of this device is based on an electromagnetically induced transparency analogue, produced by the coupling between a bright resonator and two dark resonators. The orientation of these resonators is such that a radiating electric dipole orthogonal to the incident electric field polarization is induced, causing a rotation of the polarization angle of the transmitted radiation. By variably dampening the dark resonators using graphene, the coupling condition is electrically modulated such that continuous tuning of the transmitted polarization angle is achieved. This device, operating at room temperature, can be readily implemented as a fast, optoelectronic, polarization modulator with a maximum tuning range of 20 degrees at 1.75 THz, with demonstrated reconfiguration speeds of >5 MHz.

Recent developments in surface-enhanced Raman scattering (SERS) enable observation of single-bond vibrations in real time at room temperature. By contrast, mid-infrared (MIR) vibrational spectroscopy is limited to inefficient slow detection. Here we develop a new method for MIR sensing using SERS. This method utilizes nanoparticle-on-foil (NPoF) nanocavities supporting both visible and MIR plasmonic hotspots in the same nanogap formed by a monolayer of molecules. Molecular SERS signals from individual NPoF nanocavities are modulated in the presence of MIR photons. The strength of this modulation depends on the MIR wavelength, and is maximized at the 6–12 μm absorption bands of SiO2 or polystyrene placed under the foil. Using a single-photon lock-in detection scheme we time-resolve the rise and decay of the signal in a few 100 ns. Our observations reveal that the phonon resonances of SiO2 can trap intense MIR surface plasmons within the Reststrahlen band, tuning the visible-wavelength localized plasmons by reversibly perturbing the localized few-nm-thick water shell trapped in the nanostructure crevices. This suggests new ways to couple nanoscale bond vibrations for optomechanics, with potential to push detection limits down to single-photon and single-molecule regimes.

KEYWORDS (Word Style "BG_Keywords"). If you are submitting your paper to a journal that requires keywords, provide significant keywords to aid the reader in literature retrieval.In this work, we present a novel technique to directly measure the phase shift of the optical signal scattered by single plasmonic nanoparticles in a diffraction-limited laser focus. We accomplish this by equipping an inverted confocal microscope with a Michelson interferometer and scanning single nanoparticles through the focal volume while recording interferograms of the scattered and a reference wave for each pixel. For the experiments, lithographically prepared gold nanorods where used, since their plasmon resonances can be controlled via their aspect ratio. We have developed a theoretical model for image formation in confocal scattering microscopy for nanoparticles considerably smaller than the diffraction limited focus We show that the phase shift observed for particles with different longitudinal particle plasmon resonances can be well explained by the harmonic oscillator model. The direct measurement of the phase shift can further improve the understanding of the elastic scattering of individual gold nanoparticles with respect to their plasmonic properties.

The plasmon ruler has drawn substantial attention for measuring small separations between two plasmonic nanoparticles (NPs), which can be as sensitive as to observe the bending of DNA. Usually, the plasmon ruler is based on the spectral shift of the localized surface plasmon resonance (LSPR) caused by the distance-dependent dipole−dipole coupling between two plasmonic NPs. Here, we present an approach to the plasmon ruler by detecting the phase of the scattered light. We have developed a combination of a confocal microscope and a Michelson interferometer, which allows us to measure the phase change caused by a single nanoparticle in a diffraction-limited focal volume. The plasmon ruler is realized by a gold nanoparticle dimer (GND) deposited on a flexible polydimethylsiloxane substrate, where the same GND can be investigated with variable gaps by applying strain by stretching of the substrate. In this experimental configuration, the GND is located at a low reflecting interface leading to a large phase difference of more than 100°relative to the substrate, which allows us to easily detect a single GND. Interestingly, an increase of the gap by 11 nm leads to a large phase shift of 94°, even though there is only a 11 nm spectral shift of the LSPR. We find that both the spectral and phase shifts have the same r −3 dependence on the particle gap, which is expected for pure dipole−dipole coupling.

Surface-enhanced Raman scattering (SERS) is typically assumed to occur at individual molecules neglecting intermolecular vibrational coupling. Here, we show instead how collective vibrations from infrared (IR) coupled dipoles are seen in SERS from molecular monolayers. Mixing IR-active molecules with IR-inactive spacer molecules controls the intermolecular separation. Intermolecular coupling leads to vibrational frequency upshifts up to 8 cm −1 , tuning with the mixing fraction and IR dipole strength, in excellent agreement with microscopic models and density functional theory. These cooperative frequency shifts can be used as a ruler to measure intermolecular distance and disorder with angstrom resolution. We demonstrate this for photochemical reactions of 4-nitrothiophenol, which depletes the number of neighboring IR-active molecules and breaks the collective vibration, enabling direct tracking of the reaction. Collective molecular vibrations reshape SERS spectra and need to be considered in the analysis of vibrational spectra throughout analytical chemistry and sensing.