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Molecular vibrations couple to visible light only weakly, have small mutual interactions, and hence are often ignored for non-linear optics. Here we show the extreme confinement provided by plasmonic nano- and pico-cavities can sufficiently enhance optomechanical coupling so that intense laser illumination drastically softens the molecular bonds. This optomechanical pumping regime produces strong distortions of the Raman vibrational spectrum related to giant vibrational frequency shifts from an optical spring effect which is hundred-fold larger than in traditional cavities. The theoretical simulations accounting for the multimodal nanocavity response and near-field-induced collective phonon interactions are consistent with the experimentally-observed non-linear behavior exhibited in the Raman spectra of nanoparticle-on-mirror constructs illuminated by ultrafast laser pulses. Further, we show indications that plasmonic picocavities allow us to access the optical spring effect in single molecules with continuous illumination. Driving the collective phonon in the nanocavity paves the way to control reversible bond softening, as well as irreversible chemistry. Extreme confinement of light in plasmonic nanocavities strongly enhances the optomechanical coupling of light with molecular vibrations. Here, the authors use a giant optical spring effect to reversibly weaken molecular bonds.

Anti-Stokes photoluminescence (PL) is light emission at a higher photon energy than the excitation, with applications in optical cooling, bioimaging, lasing, and quantum optics. Here, we show how plasmonic nano-cavities activate anti-Stokes PL in WSe 2 monolayers through resonant excitation of a dark exciton at room temperature. The optical near-fields of the plasmonic cavities excite the out-of-plane transition dipole of the dark exciton, leading to light emission from the bright exciton at higher energy. Through statistical measurements on hundreds of plasmonic cavities, we show that coupling to the dark exciton leads to a near hundred-fold enhancement of the upconverted PL intensity. This is further corroborated by experiments in which the laser excitation wavelength is tuned across the dark exciton. We show that a precise nanoparticle geometry is key for a consistent enhancement, with decahedral nanoparticle shapes providing an efficient PL upconversion. Finally, we demonstrate a selective and reversible switching of the upconverted PL via electrochemical gating. Our work introduces the dark exciton as an excitation channel for anti-Stokes PL in WSe 2 and paves the way for large-area substrates providing nanoscale optical cooling, anti-Stokes lasing, and radiative engineering of excitons. Here, the authors perform statistical measurements on hundreds of plasmonic nano-cavities embedding WSe 2 monolayers, and show the activation of anti-Stokes photoluminescence in WSe 2 through resonant excitation of a dark exciton at room temperature.

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.Mid-infrared light absorbed in the phonon-bands of a plasmonic nanocavity substrate perturb the Raman scattering signals on sub-µs timescales, allowing development of single-photon mid-infrared detectors.

Effective control of terahertz radiation requires fast and efficient modulators with a large modulation depth—a challenge that is often tackled by using metamaterials. Metamaterial-based active modulators can be created by placing graphene as a tuneable element shunting regions of high electric field confinement in metamaterials. However, in this common approach, the graphene is used as a variable resistor, and the modulation is achieved by resistive damping of the resonance. In combination with the finite conductivity of graphene due to its gapless nature, achieving 100% modulation depth using this approach remains challenging. Here, we embed nanoscale graphene capacitors within the gaps of the metamaterial resonators, and thus switch from a resistive damping to a capacitive tuning of the resonance. We further expand the optical modulation range by device excitation from its substrate side. As a result, we demonstrate terahertz modulators with over four orders of magnitude modulation depth (45.7 dB at 1.68 THz and 40.1 dB at 2.15 THz), and a reconfiguration speed of 30 MHz. These tuneable capacitance modulators are electrically controlled solid-state devices enabling unity modulation with graphene conductivities below 0.7 mS. The demonstrated approach can be applied to enhance modulation performance of any metamaterial-based modulator with a 2D electron gas. Our results open up new frontiers in the area of terahertz communications, real-time imaging, and wave-optical analogue computing. By switching from a variable resistance to a tunable capacitance modulation principle using nanoscale lateral capacitors and leveraging substrate-side reflection, we achieve 100% amplitude modulation in graphene-based metamaterial terahertz modulators.

Room-temperature detection of molecular vibrations in the mid-infrared (MIR, λ = 3–30 µm) has numerous applications, including real-time gas sensing, medical imaging and quantum communication. However, existing technologies rely on cooled semiconductor detectors because of thermal noise limitations. One way to overcome this challenge is to upconvert the low-energy MIR photons into high-energy visible wavelengths (λ = 500–800 nm) where detection of single photons is easily achieved using silicon technologies. This process suffers from weak cross-sections and the MIR-to-visible wavelength mismatch, limiting its efficiency. Here we exploit molecular emitters possessing both MIR and visible transitions from molecular vibrations and electronic states, coupled through Franck–Condon factors. By assembling molecules into a plasmonic nanocavity resonant at both MIR and visible wavelengths, and optically pumping them below the electronic absorption band, we show transduction of MIR light. The upconverted signal is observed as enhanced visible luminescence. Combining Purcell-enhanced visible luminescence with enhanced rates of vibrational pumping gives transduction efficiencies of >10%. MIR frequency-dependent upconversion gives the vibrational signatures of molecules assembled in the nanocavity. Transient picocavity formation further confines MIR light down to the single-molecule level. This allows us to demonstrate single-molecule MIR detection and spectroscopy that is inaccessible to any previous detector.Detecting the vibrations of individual molecules directly in the mid-infrared regime is hindered by thermal noise. Here researchers bypass conventional detectors and upconvert the mid-infrared photons into visible light using molecular bonds, yielding an optical readout for single-molecule vibrational spectroscopy.

Using the localized surface plasmon resonance (LSPR) of gold nanoparticles for sensing applications has attracted considerable interest, since it can be very sensitive, even down to a single molecule, and selective for a specific analyte molecule with a suitable surface modification. LSPR sensing is usually based on the wavelength shift of the LSPR or a Fano resonance. Here, we present a new experimental approach based on the phase of the light scattered by a single gold nanoparticle by equipping a confocal microscope with an additional interferometer arm similar to a Michelson interferometer. The detected phase depends on the shape of the nanoparticle and the refractive index of the surrounding medium and can even be detected for off-resonant excitation. This can be used as a new and sensitive detection method in LSPR sensing, allowing the detection of changes to the local refractive index or the binding of molecules to the nanoparticle surface.

Molecular vibrations couple to visible light only weakly, have small mutual interactions, and hence are often ignored for non-linear optics. Here we show the extreme confinement provided by plasmonic nano- and pico-cavities can sufficiently enhance optomechanical coupling so that intense laser illumination drastically softens the molecular bonds. This optomechanical pumping regime produces strong distortions of the Raman vibrational spectrum related to giant vibrational frequency shifts from an optical spring effect which is hundred-fold larger than in traditional cavities. The theoretical simulations accounting for the multimodal nanocavity response and near-field-induced collective phonon interactions are consistent with the experimentally-observed non-linear behavior exhibited in the Raman spectra of nanoparticle-on-mirror constructs illuminated by ultrafast laser pulses. Further, we show indications that plasmonic picocavities allow us to access the optical spring effect in single molecules with continuous illumination. Driving the collective phonon in the nanocavity paves the way to control reversible bond softening, as well as irreversible chemistry.

Room temperature detection of molecular vibrations in the mid-infrared (MIR, \\(\\) =3-30\\(\\)m) has numerous applications including real-time gas sensing, chemical reactivity, medical imaging, astronomical surveys, and quantum communication [1,2]. However, MIR detection is severely hindered by thermal noise, hence current technologies rely on energy-intensive cooled semiconductor detectors (mercury cadmium telluride, MCT) [3,4,5]. One way to overcome this challenge is to upconvert the low-energy MIR light into high-energy visible wavelengths (\\(\\) =500-800nm) where detection of single photons is easily achieved using silicon technologies [6,7]. This process suffers from weak cross sections and the mismatch between MIR and visible wavelengths, limiting its efficiency. Here, we exploit molecular emitters possessing both MIR and visible transitions from molecular vibrations and electronic states, coupled through Frank-Condon factors. By assembling molecules into a nanoscale cavity and continuously optically pumping them below the electronic absorption band, we show the transduction of MIR light absorbed by the molecular vibrations. The upconverted signal is observed as enhanced high-energy luminescence. Combining Purcell-enhanced visible luminescence with enhanced rates of vibrational pumping gives transduction efficiencies exceeding 10%. By down-scaling the cavity volume below \\(1nm^3\\), we show MIR detection of single-molecular bonds, inaccessible to any previous detector.

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 nano-gap 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\\(\\)m absorption bands of SiO\\(_2\\) 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 100ns. Our observations reveal that the phonon resonances of SiO\\(_2\\) can trap intense MIR surface plasmons within the Reststrahlen band, tuning the visible-wavelength localized plasmons by reversibly perturbing the nanostructure crevices. This suggests new ways to couple nano-scale bond vibrations for optomechanics, with potential to push detection limits down to single-photon and single-molecule regimes.