Plasmonic Diamond Membranes for Ultrafast Silicon Vacancy Emission.

Silicon vacancy centers (SiVs) in diamond have emerged as a promising platform for quantum sciences due to their excellent photostability, minimal spectral diffusion, and substantial zero-phonon line emission. However, enhancing their slow nanosecond excited-state lifetime by coupling to optical cavities remains an outstanding challenge, as current demonstrations are limited to ∼10-fold. Here, we couple negatively charged SiVs to sub-diffraction-limited plasmonic cavities and achieve an instrument-limited ≤8 ps lifetime, corresponding to a 135-fold spontaneous emission rate enhancement and a 19-fold photoluminescence enhancement. Nanoparticles are printed on ultrathin diamond membranes on gold films which create arrays of plasmonic nanogap cavities with ultrasmall volumes. SiVs implanted at 5 and 10 nm depths are examined to elucidate surface effects on their lifetime and brightness. The interplay between cavity, implantation depth, and ultrathin diamond membranes provides insights into generating ultrafast, bright SiV emission for next-generation diamond devices.

Uncovering the Mechanisms of Triplet-Triplet Annihilation Upconversion Enhancement via Plasmonic Nanocavity Tuning.

The nonlinear conversion of photons from lower to higher energy is important for a wide range of applications, from quantum communications and optoelectronics to solar energy conversion and medicine. Triplet-triplet annihilation upconversion (TTA UC), which utilizes an absorber/emitter molecular pair, is a promising tool for upconversion applications requiring low intensity light such as photovoltaics, photocatalysis, and bioimaging. Despite demonstrations of efficient TTA UC in solution, practical applications have proven difficult, as thin films retard the necessary energy transfer steps and result in low emission yields. In this work, TTA UC emission from a thin film is greatly enhanced through integration into plasmonic nanogap cavities consisting of a silver mirror, a nanometer-scale polymer spacer containing a TTA molecular pair, and colloidally synthesized silver nanocubes. Mechanistic studies performed by varying the nanocube side length (45-150 nm) to tune the nanogap cavity resonance paired with simulations reveal absorption rate enhancement to be the primary operative mechanism in overall TTA UC emission enhancement. This absorption enhancement decreases the TTA UC threshold intensity by an order of magnitude and allows TTA UC emission to be excited with light up to 120 nm redder than the usable wavelength range for the control samples. Further, combined nanogap cavities composed of two distinct nanocube sizes result in surfaces which simultaneously enhance the absorption rate and emission rate. These dual-size nanogap cavities result in 45-fold TTA UC emission enhancement. In total, these studies present TTA UC emission enhancement, illustrate how the usable portion of the spectrum can be expanded for a given sensitizer-emitter pair, and develop both mechanistic understanding and design rules for TTA UC emission enhancement by plasmonic nanostructures.

Tracking light-induced charge transport.

Precise charge dynamics could help to improve the operation of solar cells and sensors.

Ultrathin Pyroelectric Photodetector with Integrated Polarization-Sensing Metasurface.

An abundance of metallic metasurfaces have been realized with miniscule, intricate features capable of tailored scattering, reflection, and absorption; however, high losses through heat limit their use in optoelectronics. Here, codesign of a detector and a polarization-sensing metasurface overcomes this challenge by utilizing the heat generation for integrated pyroelectric detection of the incoming light polarization. Using a nanogap metasurface with asymmetric metallic elements, polarization-sensitive photodetection exhibits high extinction ratios up to 19 for orthogonally polarized light and allows extraction of Stokes parameters with <12% deviation from theoretical values. This polarization-sensitive photodetector is ultrathin, consisting of active layers of only 290 nm, and exhibits fast response times of ∼2 ns. The structure is fully integrated, requiring no external cameras, detectors, or power sources, and points toward the creation of layered, multifunctional devices that utilize exotic metasurface properties for novel and compact sensing and imaging.

Plasmonic Fluorescence Enhancement in Diagnostics for Clinical Tests at Point-of-Care: A Review of Recent Technologies.

Fluorescence-based biosensors have widely been used in the life-sciences and biomedical applications due to their low limit of detection and a diverse selection of fluorophores that enable simultaneous measurements of multiple biomarkers. Recent research effort has been made to implement fluorescent biosensors into the exploding field of point-of-care testing (POCT), which uses cost-effective strategies for rapid and affordable diagnostic testing. However, fluorescence-based assays often suffer from their feeble signal at low analyte concentrations, which often requires sophisticated, costly, and bulky instrumentation to maintain high detection sensitivity. Metal- and metal oxide-based nanostructures offer a simple solution to increase the output signal from fluorescent biosensors due to the generation of high field enhancements close to a metal or metal oxide surface, which has been shown to improve the excitation rate, quantum yield, photostability, and radiation pattern of fluorophores. This article provides an overview of existing biosensors that employ various strategies for fluorescence enhancement via nanostructures and have demonstrated the potential for use as POCT. Biosensors using nanostructures such as planar substrates, freestanding nanoparticles, and metal-dielectric-metal nanocavities are discussed with an emphasis placed on technologies that have shown promise towards POCT applications without the need for centralized laboratories.

Control of Nanoscale Heat Generation with Lithography-Free Metasurface Absorbers.

Metasurfaces, artificially engineered surfaces comprised of subwavelength resonators, show promise for realizing a new generation of optical materials and devices. However, current metasurface architectures suffer from environmental degradation, a limited spectral range, and a lack of scalability. Here, we demonstrate a novel large-area embedded metasurface architecture that is environmentally robust and capable of a spectrally selective absorption of greater than 80% spanning from 330 to 2740 nm. These fully encapsulated metasurfaces leverage the capabilities of colloidal plasmonic nanoparticles with various crystallinities, materials, shapes, and sizes to access a larger spectral range and allow for control of nanoscale spatial losses and subsequent heat generation within the constituent elements of the metasurface. Through the selection of material, particle size, and shape, these metasurfaces can be designed across the ultraviolet (UV) to short-wave infrared (SWIR) region for various hot-electron, photodetection, photocatalysis, and photothermal processes.

Actively Tunable Metasurfaces via Plasmonic Nanogap Cavities with Sub-10-nm VO2 Films.

Actively tunable optical materials integrated with engineered subwavelength structures could enable novel optoelectronic devices, including reconfigurable light sources and tunable on-chip spectral filters. The phase-change material vanadium dioxide (VO2) provides a promising solid-state solution for dynamic tuning; however, previous demonstrations have been limited to thicker and often rough VO2 films or require a lattice-matched substrate for growth. Here, sub-10-nm-thick VO2 films are realized by atomic layer deposition (ALD) and integrated with plasmonic nanogap cavities to demonstrate tunable, spectrally selective absorption across 1200 nm in the near-infrared (NIR). Upon inducing the phase transition via heating, the absorption resonance is blue-shifted by as much as 60 nm. This process is reversible upon cooling and repeatable over more than ten temperature cycles. Dynamic, ultrathin VO2 films deposited by ALD, as demonstrated here, open up new potential architectures and applications where VO2 can be utilized to provide reconfigurability including three-dimensional, flexible and large-area structures.

Ultrafast Lifetime and Bright Emission from Graphene Quantum Dots Using Plasmonic Nanogap Cavities.

Graphene quantum dots (GQDs) are quasi-zero-dimensional, carbon-based luminescent nanomaterials that possess desirable physical properties, such as high photostability, low cytotoxicity, good biocompatibility, and excellent water solubility; however, their long radiative lifetimes significantly limit their use in, e.g., light emitting devices where a fast spontaneous emission rate is essential. Despite a few reports on GQD fluorescence enhancements using metal nanostructures, studies of enhanced spontaneous emission rate remain outstanding. Here, we report fast and bright luminescence by coupling gap plasmon modes to nanoparticle emitters. Through precise control over the nanoparticle's local density of states (LDOS), we achieved a 220-fold increase in the PL intensity. The shortest radiative lifetime obtained was below 8.0 ps and limited by the instrument response, which is over 288-fold shorter than the lifetime of uncoupled GQDs. These findings may benefit the future development of rapid displays and open the possibility of constructing high-frequency classical or quantum telecommunication systems.

Ultrasensitive point-of-care immunoassay for secreted glycoprotein detects Ebola infection earlier than PCR.

Ebola virus (EBOV) hemorrhagic fever outbreaks have been challenging to deter due to the lack of health care infrastructure in disease-endemic countries and a corresponding inability to diagnose and contain the disease at an early stage. EBOV vaccines and therapies have improved disease outcomes, but the advent of an affordable, easily accessed, mass-produced rapid diagnostic test (RDT) that matches the performance of more resource-intensive polymerase chain reaction (PCR) assays would be invaluable in containing future outbreaks. Here, we developed and demonstrated the performance of a new ultrasensitive point-of-care immunoassay, the EBOV D4 assay, which targets the secreted glycoprotein of EBOV. The EBOV D4 assay is 1000-fold more sensitive than the U.S. Food and Drug Administration-approved RDTs and detected EBOV infection earlier than PCR in a standard nonhuman primate model. The EBOV D4 assay is suitable for low-resource settings and may facilitate earlier detection, containment, and treatment during outbreaks of the disease.

Ultrabright Fluorescence Readout of an Inkjet-Printed Immunoassay Using Plasmonic Nanogap Cavities.

Fluorescence-based microarrays are promising diagnostic tools due to their high throughput, small sample volume requirements, and multiplexing capabilities. However, their low fluorescence output has limited their implementation for in vitro diagnostics applications in point-of-care (POC) settings. Here, by integration of a sandwich immunoassay microarray within a plasmonic nanogap cavity, we demonstrate strongly enhanced fluorescence which is critical for readout by inexpensive POC detectors. The immunoassay consists of inkjet-printed antibodies on a polymer brush which is grown on a gold film. Colloidally synthesized silver nanocubes are placed on top and interact with the underlying gold film creating high local electromagnetic field enhancements. By varying the thickness of the brush from 5 to 20 nm, up to a 151-fold increase in fluorescence and 14-fold improvement in the limit-of-detection is observed for the cardiac biomarker B-type natriuretic peptide (BNP) compared to the unenhanced assay, paving the way for a new generation of POC clinical diagnostics.

Ultrafast pyroelectric photodetection with on-chip spectral filters.

Thermal detectors, such as bolometric, pyroelectric and thermoelectric devices, are uniquely capable of sensing incident radiation for any electromagnetic frequency; however, the response times of practical devices are typically on the millisecond scale1-7. By integrating a plasmonic metasurface with an aluminium nitride pyroelectric thin film, we demonstrate spectrally selective, room-temperature pyroelectric detectors from 660-2,000 nm with an instrument-limited 1.7 ns full width at half maximum and 700 ps rise time. Heat generated from light absorption diffuses through the subwavelength absorber into the pyroelectric film producing responsivities up to 0.18 V W-1 due to the temperature-dependent spontaneous polarization of the pyroelectric films. Moreover, finite-element simulations reveal the possibility of reaching a 25 ps full width at half maximum and 6 ps rise time rivalling that of semiconductor photodiodes8. This design approach has the potential to realize large-area, inexpensive gigahertz pyroelectric detectors for wavelength-specific detection from the ultraviolet to short-wave infrared or beyond for, for example, high-speed hyperspectral imaging.

Extreme nanophotonics from ultrathin metallic gaps.

Ultrathin dielectric gaps between metals can trap plasmonic optical modes with surprisingly low loss and with volumes below 1 nm3. We review the origin and subtle properties of these modes, and show how they can be well accounted for by simple models. Particularly important is the mixing between radiating antennas and confined nanogap modes, which is extremely sensitive to precise nanogeometry, right down to the single-atom level. Coupling nanogap plasmons to electronic and vibronic transitions yields a host of phenomena including single-molecule strong coupling and molecular optomechanics, opening access to atomic-scale chemistry and materials science, as well as quantum metamaterials. Ultimate low-energy devices such as robust bottom-up assembled single-atom switches are thus in prospect.

Probing the origin of highly-efficient third-harmonic generation in plasmonic nanogaps.

Plasmonic structures can precisely localize electromagnetic energy to deep subwavelength regions resulting in significant field enhancement useful for efficient on-chip nonlinear generation. However, the origin of large nonlinear enhancements observed in plasmonic nanogap structures consisting of both dielectrics and metals is not fully understood. For the first time, here we probe the third harmonic generation (THG) from a variety of dielectric materials embedded in a nanogap plasmonic cavity. From comprehensive spectral analysis of the THG signal, we conclude that the nonlinear response results primarily from the dielectric spacer layer itself as opposed to the surrounding metal. We achieved a maximum enhancement factor of more than six orders of magnitude compared to a bare gold film, which represents a nonlinear conversion efficiency of 8.78 × 10-4%. We expect this new insight into the nonlinear response in ultrathin gaps between metals to be promising for on-chip nonlinear devices such as ultrafast optical switching and entangled photon sources.

Surpassing Single Line Width Active Tuning with Photochromic Molecules Coupled to Plasmonic Nanoantennas.

Active plasmonic nanostructures with tunable resonances promise to enable smart materials with multiple functionalities, on-chip spectral-based imaging and low-power optoelectronic devices. A variety of tunable materials have been integrated with plasmonic structures, however, the tuning range in the visible regime has been limited to less than the line width of the resonance resulting in small on/off ratios. Here we demonstrate dynamic tuning of plasmon resonances up to 71 nm through multiple cycles by incorporating photochromic molecules into plasmonic nanopatch antennas. Exposure to ultraviolet (UV) light switches the molecules into a photoactive state enabling dynamic control with on/off ratios up to 9.2 dB and a tuning figure of merit up to 1.43, defined as the ratio between the spectral shift and the initial line width of the plasmonic resonance. Moreover, the physical mechanisms underlying the large spectral shifts are elucidated by studying over 40 individual nanoantennas with fundamental resonances from 550 to 720 nm revealing good agreement with finite-element simulations.

Publisher Correction: Enhanced generation and anisotropic Coulomb scattering of hot electrons in an ultra-broadband plasmonic nanopatch metasurface.

The originally published version of this Article contained an error in Equation 1. The two ℏ terms were missing from this equation. This has now been corrected in the PDF and HTML versions of the Article.

Enhanced generation and anisotropic Coulomb scattering of hot electrons in an ultra-broadband plasmonic nanopatch metasurface.

The creation of energetic electrons through plasmon excitation of nanostructures before thermalization has been proposed for a wide number of applications in optical energy conversion and ultrafast nanophotonics. However, the use of "nonthermal" electrons is primarily limited by both a low generation efficiency and their ultrafast decay. We report experimental and theoretical results on the use of broadband plasmonic nanopatch metasurfaces comprising a gold substrate coupled to silver nanocubes that produce large concentrations of hot electrons, which we measure using transient absorption spectroscopy. We find evidence for three subpopulations of nonthermal carriers, which we propose arise from anisotropic electron-electron scattering within sp-bands near the Fermi surface. The bimetallic character of the metasurface strongly impacts the physics, with dissipation occurring primarily in the gold, whereas the quantum process of hot electron generation takes place in both components. Our calculations show that the choice of geometry and materials is crucial for producing strong ultrafast nonthermal electron components.The creation of energetic electrons through plasmon excitation has implications in optical energy conversion and ultrafast nanophotonics. Here, the authors find evidence for three subpopulations of nonthermal carriers which arise from anisotropic electron-electron scattering near the Fermi surface.

Millimeter-Scale Spatial Coherence from a Plasmon Laser.

Coherent light sources have been demonstrated based on a wide range of nanostructures, however, little effort has been devoted to probing their underlying coherence properties. Here, we report long-range spatial coherence of lattice plasmon lasers constructed from a periodic array of gold nanoparticles and a liquid gain medium at room temperature. By combining spatial and temporal interferometry, we demonstrate millimeter-scale (∼1 mm) spatial coherence and picosecond (∼2 ps) temporal coherence. The long-range spatial coherence occurs even without the presence of strong coupling with the lattice plasmon mode extending over macroscopic distances in the lasing regime. This plasmonic lasing system thus provides a platform for understanding the emergence of long-range coherence from collections of nanoscale resonators and points toward novel types of distributed lasing sources.

Toward Multispectral Imaging with Colloidal Metasurface Pixels.

Multispectral colloidal metasurfaces are fabricated that exhibit greater than 85% absorption and ≈100 nm linewidths by patterning film-coupled nanocubes in pixels using a fusion of bottom-up and top-down fabrication techniques over wafer-scale areas. With this technique, the authors realize a multispectral pixel array consisting of six resonances between 580 and 1125 nm and reconstruct an RGB image with 9261 color combinations.

Colloidal Synthesis of Nanopatch Antennas for Applications in Plasmonics and Nanophotonics.

We present a method for colloidal synthesis of silver nanocubes and the use of these in combination with a smooth gold film, to fabricate plasmonic nanoscale patch antennas. This includes a detailed procedure for the fabrication of thin films with a well-controlled thickness over macroscopic areas using layer-by-layer deposition of polyelectrolyte polymers, namely poly(allylamine) hydrochloride (PAH) and polystyrene sulfonate (PSS). These polyelectrolyte spacer layers serve as a dielectric gap in between silver nanocubes and a gold film. By controlling the size of the nanocubes or the gap thickness, the plasmon resonance can be tuned from about 500 nm to 700 nm. Next, we demonstrate how to incorporate organic sulfo-cyanine5 carboxylic acid (Cy5) dye molecules into the dielectric polymer gap region of the nanopatch antennas. Finally, we show greatly enhanced fluorescence of the Cy5 dyes by spectrally matching the plasmon resonance with the excitation energy and the Cy5 absorption peak. The method presented here enables the fabrication of plasmonic nanopatch antennas with well-controlled dimensions utilizing colloidal synthesis and a layer-by-layer dip-coating process with the potential for low cost and large-scale production. These nanopatch antennas hold great promise for practical applications, for example in sensing, ultrafast optoelectronic devices and for high-efficiency photodetectors.

Probing the origin of excitonic states in monolayer WSe2.

Two-dimensional transition metal dichalcogenides (TMDCs) have spurred excitement for potential applications in optoelectronic and valleytronic devices; however, the origin of the dynamics of excitons, trions, and other localized states in these low dimensional materials is not well-understood. Here, we experimentally probed the dynamics of excitonic states in monolayer WSe2 by investigating the temperature and polarization dependent photoluminescence (PL) spectra. Four pronounced PL peaks were identified below a temperature of 60 K at near-resonant excitation and assigned to exciton, trion and localized states from excitation power dependence measurements. We find that the localized states vanish above 65 K, while exciton and trion emission peaks remain up to room temperature. This can be explained by a multi-level model developed for conventional semiconductors and applied to monolayer TMDCs for the first time here. From this model, we estimated a lower bound of the exciton binding energy of 198 meV for monolayer WSe2 and explained the vanishing of the localized states. Additionally, we observed a rapid decrease in the degree of circular polarization of the PL at increasing temperatures indicating a relatively strong electron-phonon coupling and impurity-related scattering. Our results reveal further insight into the excitonic states in monolayer WSe2 which is critical for future practical applications.