Localized Plasmon Research Articles

Smartphone-Based Attomolar Cyanide Ion Sensing Using Au-Graphene Oxide Cryosoret Nanoassembly and Benzoxazolium-Based Fluorophore in a Surface Plasmon-Coupled Enhanced Fluorescence Interface

Photoplasmonic platforms are being demonstrated as excellent means for bridging nanochemistry and biosensing approaches at advanced interfaces, thereby augmenting the sensitivity and quantification of the desired analytes. Although resonantly coupled electromagnetic waves at the surface plasmon-coupled emission (SPCE) interface are investigated with myriad nanomaterials in order to boost the detection limits, rhodamine moieties are ubiquitously used as SPCE reporter molecules in spite of their well-known limitations. In order to overcome this constraint, in this work, a benzoxazolium-based fluorescent molecule, (E)-2-(4-(dimethylamino)styryl)-3-methylbenzo[d]oxazol-3-ium iodide (DSBO), was synthesized to selectively detect the cyanide (CN-) ions in water samples. To this end, the sensitivity of the fabricated SPCE substrates is tested in spacer, cavity, and extended cavity nanointerfaces to rationalize the configurational robustness. The performance of the sensor is further improved with the careful engineering of gold (Au)-graphene oxide (GO) cryosoret nanoassemblies fabricated via an adiabatic cooling technology. The unique dequenching (turn-on) of the quenched (turn-off) fluorescent signal is demonstrated with the hybridized metal-π plasmon synergistic coupling in the nanovoids and nanocavities assisting delocalized Bragg and localized Mie plasmons. The spectro-plasmonic analysis yielded highly directional, polarized (>95%), and enhanced emission attributes with an attomolar limit of detection of 10 aM of CN- ions with high linearity (R2 = 0.996) and excellent reliability, in addition to an exceptional correlation with the theoretically obtained TFclac simulations. The CN- ion sensing is experimentally validated with the smartphone-based cost-effective SPCE detection technology to render the device amenable to resource-limited settings. We believe that the unique fluorophore-cryosoret nanoassemblage presented here encourages development of frugal, unconventional, and highly desirable strategies for the selective quantitation of environmentally and physiologically relevant analytes at trace concentrations for use in point-of-care diagnostics.

All-optical control of ultrafast plasmon resonances in the pulse-driven extraordinary optical transmission

Understanding ultrafast processes in their natural timescale is crucial for controlling and manipulating nanoscale optoelectronic devices under light–matter interaction. Here, we demonstrate that ultrafast plasmon resonances, attributed to the phenomenon of extraordinary optical transmission (EOT), can be significantly modified by tuning the spectral and temporal properties of the ultrashort light pulse. In this scheme, all-optical active tuning governs the spatial and temporal enhancement of plasmon oscillations in the EOT system without device customization. We analyze the spectral and temporal evolution of the system using two approaches. First, we develop a theoretical framework based on the coupled harmonic oscillator model, which analytically describes the dynamics of plasmon modes in the coupled and uncoupled states. Later, we compare the evolution of the system under continuous-wave and pulsed illumination. Further, we discuss the time-resolved spectral and spatial dynamics of plasmon modes using a 3D finite difference time-domain simulation method and wavelet transform. Our results show that optical tuning of the oscillation time, intensity, and spectral properties of propagating and localized plasmon modes yields a three-fold enhancement in the EOT signal. The active tuning of the EOT sensor through ultrashort light pulses paves the way for the development of on-chip photonic devices employing high-resolution imaging and sensing of abundant atomic and molecular systems.

Plasmon-Controlled Selective Emission Enhancement of Eu3+ with (Au Core)@(Y(V,P)O4:Eu) Nanostructures.

Plasmonic nanostructures have a capability to control the photoluminescence (PL) emission properties of optical species and thus can dramatically enhance the performances of diverse optical systems and devices. Lanthanide ions typically exhibit multiple PL emission lines. Systematic studies on the plasmon-enabled selective enhancement for the different emission lines of lanthanide ions are still highly desired in order to achieve the fine manipulation on the spectral profile and luminescence intensity ratio (LIR). Herein we report on the synthesis and PL emission properties of monodisperse spherical (Au core)@(Y(V,P)O4:Eu) nanostructures, which integrate the plasmonic and luminescent units into an individual core@shell structure. The localized surface plasmon resonance adjusted through control of the size of the Au nanosphere core enables the systematic modulation of the selective emission enhancement of Eu3+. As revealed by single-particle scattering and PL measurements, the five luminescence emission lines of Eu3+ originating from the 5D0,1 excitation states are affected by the localized plasmon resonance to different extents, which are dependent on both the dipole transition nature and the intrinsic quantum yield of the emission line. Based on the plasmon-enabled tunable LIR, high-level anticounterfeiting and optical temperature measurements for photothermal conversion are further demonstrated. Our architecture design and PL emission tuning results offer many possibilities for constructing multifunctional optical materials by integrating plasmonic and luminescent building blocks into hybrid nanostructures with different configurations.

Gold nanosponges: fascinating optical properties of a unique disorder-dominated system

Nanoporous gold is a three-dimensional bulk material that is percolated with a random network of nanometer-sized ligaments and made by selective corrosion of bimetallic alloys. It has intriguing geometric, catalytic, and optical properties that have fascinated scientists for many decades. When such a material is made into the form of small, 100-nm-sized particles, so-called nanosponges emerge that offer much flexibility in controlling their geometric, electronic, and optical properties. Importantly, these particles act as an antenna for light that can efficiently localize optical fields on a deep subwavelength scale in certain hotspots at the particle surface. This makes such nanosponges an interesting platform for plasmonic sensing, photocatalysis, and surface-enhanced Raman spectroscopy. Since the optical properties of these nanosponges can be controlled to a large degree by tuning their geometry and/or composition, they have attracted increasing attention in recent years. Here, we provide a concise overview of the current state of the art in this field, covering their fabrication, computational modeling, and specifically the linear and nonlinear optical properties of individual and hybrid nanosponges, for example, plasmon localization in randomly disordered hotspots with a size <10nm and a long lifetime with an exceptionally high Purcell factor. The resulting nonlinear optical and photoemission properties are discussed for individual and hybrid nanosponges. The results presented have strong implications for further applications of such nanosponges in photonics and photocatalysis.

Single-mode lasing by tailoring the excitation of localized surface plasmon resonances to whispering gallery modes in a microring laser.

Cavity mode manipulation in lasers is urgent for the stable single-mode operation of a microring laser. Here, we propose and experimentally demonstrate the plasmonic whispering gallery mode microring laser for strong coupling between local plasmonic resonances and whispering gallery modes (WGM) on the microring cavity to achieve pure single-mode lasing. The proposed structure is fabricated based on integrated photonics circuits consisting of gold nanoparticles deposited on a single microring. Additionally, our numerical simulation provides deep insight into the interaction between the gold nanoparticles and WGM modes. The manufacture of microlasers for the advancement of lab-on-a-chip devices and all-optical detection of ultra-low analysts may benefit from our findings.

Near-field spectroscopy of Dirac plasmons in Bi2Se3 ribbon arrays

Plasmons supported in the massless electron surface states of topological insulators (TIs), known as Dirac plasmons, have great potential in next generation optoelectronics. However, their inherent confinement to the surface makes the investigation of Dirac plasmons challenging. Near-field techniques provide the ideal platform to directly probe Dirac plasmons due to the sensitivity to evanescent fields at the surface. Here, we demonstrate the use of aperture near-field spectroscopy for the investigation of localized terahertz (THz) Dirac plasmon resonances in Bi2Se3 ribbon arrays with widths ranging from 10 to 40 µm. Unlike scattering THz near-field techniques, the aperture method is most sensitive to plasmons with the relevant lower-momenta corresponding to plasmon wavelengths on the scale of ∼20 µm. The combination of THz time-domain spectroscopy and aperture near-field microscopy enables sampling of localized Dirac plasmons in the near-field zone in the 0.5–2.5 THz range. We map the plasmon dispersion, which reveals a coupled plasmon–phonon polariton interaction. The near-field spectra show a higher contrast of the upper polariton branch in comparison with far-field observations. The information revealed by aperture near-field spectroscopy could deepen our understanding of the behavior of Dirac plasmons, leading to the potential development of real-world TI devices.

Exploring the resonance absorption of subwavelength-patterned epitaxial-grown group-IV semiconductor composite structures.

We experimentally and theoretically demonstrate a mid-infrared perfect absorber with all group-IV epitaxial layered composite structures. The multispectral narrowband strong absorption (>98%) is attributed to the combined effects of the asymmetric Fabry-Perot (FP) interference and the plasmonic resonance in the subwavelength-patterned metal-dielectric-metal (MDM) stack. The spectral position and intensity of the absorption resonance were analyzed by reflection and transmission. While a localized plasmon resonance in the dual-metal region was found to be modulated by both the horizontal (ribbon width) and vertical (spacer layer thickness) profile, the asymmetric FP modes were modulated merely by the vertical geometric parameters. Semi-empirical calculations show strong coupling between modes with a large Rabi-splitting energy reaching 46% of the mean energy of the plasmonic mode under proper horizontal profile. A wavelength-adjustable all-group-IV-semiconductor plasmonic perfect absorber has potential for photonic-electronic integration.

Bandwidth-tunable absorption enhancement of visible and near-infrared light in monolayer graphene by localized plasmon resonances and their diffraction coupling

Bandwidth-tunable light absorption enhancement in monolayer graphene is practically important for graphene-based photoelectric devices. Especially, it is still a huge challenge to achieve high-efficiency graphene absorption with extremely narrow sub-nanometer bandwidth much smaller than one nanometer. In this work, both broadband and narrowband absorption peaks of monolayer graphene are numerically achieved in visible and near-infrared wavelength ranges. The broadband absorption peak is ascribed to localized dipolar plasmon resonances in individual silver nanodisks, and the narrowband absorption peak arises from collective first-order diffraction coupling effect in periodic array of silver nanodisks. By changing the array period, the full width at half maximum (FWHM) of the broadband absorption peak can vary from 100 nm to 50 nm. Correspondingly, the FWHM of the narrowband absorption peak is tuned from about 6.4 nm to only 0.25 nm, thus realizing an ultra-narrow sub-nanometer bandwidth.

Interaction of plasmonic bound states in the continuum

Bound states in continuum (BICs) are believed to have the ability to achieve high quality factor (Q factor) resonances, which is very important for plasmonics. However, the study of plasmonic BICs is not sufficient. Herein, we design and fabricate a metal−insulator−metal (MIM) metasurface and demonstrate a one-dimensional plasmonic BIC experimentally. The even-order localized surface plasmon resonance (LSPR) modes have even parity at normal incidence. The symmetry-protected BIC can be achieved at Γ point. The band structure can be tuned by strong coupling between the localized plasmonic resonance and plasmonic lattice mode. Interestingly, two of the hybrid modes are also BICs. Although BICs cannot interact with the far field, we successfully demonstrate BIC splitting through far-field excitation. By further tuning the pitch of the MIM grating, the Friedrich–Wintgen BIC is also observed. Finally, we propose and preliminarily demonstrate an ultrathin bandpass spatial filter. These findings provide a new platform to study optical multipole BICs and can have applications in fields such as nano lasers, ultrasensitive sensors, filters, nonlinearity enhancement, and quantum optics.

Enantioselective optical trapping of single chiral molecules in the superchiral field vicinity of metal nanostructures.

In this study, we theoretically analyzed the optical force acting on single chiral molecules in the plasmon field induced by metallic nanostructures. Using the extended discrete dipole approximation, we quantitatively examined the optical response of single chiral molecules in the localized plasmon by numerically analyzing the internal polarization structure of the molecules obtained from quantum chemical calculations, without phenomenological treatment. We evaluated the chiral gradient force due to the optical chirality gradient of the superchiral field near the metallic nanostructures for chiral molecules. Our calculation method can be used to evaluate the molecular-orientation dependence and rotational torque by considering the chiral spatial structure inside the molecules. We theoretically showed that the superchiral field induced by chiral plasmonic nanostructures can be used to selectively optically capture the enantiomers of a single chiral molecule.

Highly Efficient Single-Exciton Strong Coupling with Plasmons by Lowering Critical Interaction Strength at an Exceptional Point.

The single-exciton strong coupling with the localized plasmon mode (LPM) at room temperature is highly desirable for exploiting quantum technology. However, its realization has been a very low probability event due to the harsh critical conditions, severely compromising its application. Here, we present a highly efficient approach for achieving such a strong coupling by reducing the critical interaction strength at the exceptional point based upon the damping inhibition and matching of the coupled system, instead of enhancing the coupling strength to overcome the system's large damping. Experimentally, we compress the LPM's damping linewidth from about 45nm to about 14nm using a leaky Fabry-Perot cavity, a good match to the excitonic linewidth of about 10nm. This method dramatically relaxes the harsh requirement in mode volume by more than an order of magnitude and allows a maximum direction angle of the exciton dipole relative to the mode field of up to around 71.9°, significantly improving the success rate of achieving the single-exciton strong coupling with LPMs from about 1% to about 80%.

Surface-enhanced Raman scattering of As2S3 and Se thin films formed on Au nano-structures

The effect of plasmonic nanostructures (NSs) on the Raman spectra and underlying structural changes in thin chalcogenide films is investigated. Several tens of nanometers thick As 2 S 3 and Se films were deposited by thermal sputtering on glass and surface-enhanced Raman spectroscopy (SERS) substrates based on gold nanostructures for comparison. The films on glass were practically not detectable by the Raman spectroscopy. Using gold NSs as the substrates enabled reliable registration of the Raman spectra of both the As 2 S 3 and Se films. The registered Raman spectra contained all the features usually present in the films with the thicknesses ~1 μm or more. Based on our analysis of the spectra obtained at different excitation wavelengths, we may conclude that the SERS chemical mechanism makes the main contribution to the enhancement of the Raman signal from chalcogenide films. Adjustment of the parameters of SERS substrates to tune their plasmon band position in resonance with the excitation laser radiation enables increasing the plasmonic enhancement contribution. Besides the effect of enhancement, localized plasmon resonance in the gold NSs causes local heating of the chalcogenide film around them leading to local structural transformations, which can be controlled using the Raman spectra.

Magnetoplasmonics in confined geometries: Current challenges and future opportunities

Plasmonics represents a unique approach to confine and enhance electromagnetic radiation well below the diffraction limit, bringing a huge potential for novel applications, for instance, in energy harvesting, optoelectronics, and nanoscale biochemistry. To achieve novel functionalities, the combination of plasmonic properties with other material functions has become increasingly attractive. In this Perspective, we review the current state of the art, challenges, and future opportunities within the field of magnetoplasmonics in confined geometries, an emerging area aiming to merge magnetism and plasmonics to either control localized plasmons, confined electromagnetic-induced collective electronic excitations, using magnetic properties, or vice versa. We begin by highlighting the cornerstones of the history and principles of this research field. We then provide our vision of its future development by showcasing raising research directions in hybrid magnetoplasmonic systems to overcome radiation losses and novel materials for magnetoplasmonics, such as transparent conductive oxides and hyperbolic metamaterials. Finally, we provide an overview of recent developments in plasmon-driven magnetization dynamics, nanoscale opto-magnetism, and acousto-magnetoplasmonics. We conclude by giving our personal vision of the future of this thriving research field.

Finite element analysis on the near field properties of metallic cavities with atomic sharpness

Using finite element calculations, we investigated the near field properties of two types of commonly used metal nanostructures (a tip-substrate model representing a scanning tunneling microscope type setup (TS) and a nanoparticle-on-mirror (NPoM) configuration) with atomic sharpness and extreme focusing capabilities. The spatial confinement and electric field enhancement of the local field as well as the fluorescence quantum efficiency of a model molecule (as represented by an oscillating dipole) in the cavity region of the two models were systematically studied. It was found that the TS model tends to support higher local electric field enhancement while the NPoM model can provide a more localized plasmon electric field near the nanoparticle. Calculations with the radiating model molecule indicate that both TS and NPoM can cause significant enhancements to the non-radiative decay rates at the order of 106 in the wavelength range of 500–1000 nm. The TS model shows better performance for the radiative enhancements and the resulting emission quantum yield. These results are not only helpful to improve the understanding of such important nanocavities but also supply a reference for their further applications in different areas.

High-rectification near-field radiative thermal diode using Weyl semimetals

Thermal diodes, which allow heat transfer in a preferential direction while being blocked in a reverse direction, have numerous applications in thermal management, information processing, energy harvesting, etc. Typical materials of thermal diodes in previous works include phase-change and magneto-optical materials. However, such thermal diodes depend highly on specific working temperatures or external magnetic fields. In this work, we propose a near-field radiative thermal diode (NFRTD) based on two Weyl semimetal (WSM) nanoparticles (NPs) mediated by a WSM planar substrate, which works without an external magnetic field and with flexible temperatures. Numerical results show that the maximum rectification ratio of NFRTD can be up to 2673 when the emitter is 200 K and receiver is 180 K, which exceeds the maximum value reported in some previous works by more than 10 times. The underlying physical mechanism is the strong coupling of the localized plasmon modes in the NPs and nonreciprocal surface plasmon polaritons in the substrate. In addition, we calculate the distribution of the Green's function and reflection coefficient to investigate nonreciprocal energy transfer in NFRTDs. Finally, we discuss the effects of momentum separation on the rectification performance of the NFRTD. This work demonstrates the great potential of WSMs in thermal rectification and paves a path for designing high-performance NFRTDs.

Tailoring nanowire lasing modes via coupling to metal gratings

Tailoring the emission of plasmonic nanowire-based lasers represents one of the major challenges in the field of nanoplasmonics, given the envisaged integration of such devices into on-chip all-optical circuits. In this study, we proposed a mode selection scheme based on distributed feedback, achieved via the external coupling of single zinc oxide nanowires to an aluminum grating, which enabled a quasi-single mode lasing action. The nano-manipulation of a single nanowire allowed for a reliable comparison of lasing emission characteristics in both planar (i.e., a nanowire on the metallic substrate) and on-grating configurations. We found that, by varying the orientation of the nanowire on the grating, only when the nano-cavity was perpendicular to the ridge direction, an additional peak emerged in the emission spectrum on the low-energy side of the gain envelope. As a consequence of the fulfillment of the Bragg condition, such a peak was attributed to a hybrid mode dominating the mode competition. Simulation results showed that the hybrid mode could be efficiently waveguided along the nanowire cavity and supported by localized plasmon polaritons building up at the raised features (“fences”) on top of metal grating ridges. Moreover, the hybrid mode was found to experience an extra reflectance of nearly 50% across the grating periods in addition to that provided by nanowire end facets.

DRIFTS-SSITKA-MS investigations on the mechanism of plasmon preferentially enhanced CO2 hydrogenation over Au/γ-Al2O3

The localized plasmon resonance (LSPR) is recognized as an effective way to convert incident light energy and significantly boost the catalytic reaction. However, a comprehensive understanding of the plasmon-thermo coupling mechanism is still lacking. To address this knowledge gap, we investigate reaction pathway and plasmonic enhancement mechanism of the photo-thermo coupled catalytic reverse water gas shift (RWGS) reactions over Au/γ-Al2O3. The results indicate that both formate and carboxyl pathways contribute to the overall reaction. The m-formate pathway is suggested as the main reaction mechanism at low reaction temperature over small Au NPs. Spectro-kinetics and theoretical calculation analyses indicate that the plasmonic energy preferentially transfers to HCOO* via a combination of hot electron and resonance energy transfer mechanisms. The plasmonic energy facilitates the dehydration of HCOO* to CO, which is the rate-determining step (RDS) of the overall RWGS reaction.

Sensing Performance Analysis of Spiral Metasurface Utilizing Phase Spectra Measurement Technique

We have demonstrated both numerically and experimentally a 2D plasmonic metamaterial the unit cell of which comprised an Archimedean spiral with a C-shaped resonator. Such metasurface enables the excitation of spoof localized plasmon resonances (LPRs) in the terahertz frequency range, similar in properties to the familiar LPRs in the visible range. We have compared the thin-film sensing potentials of the fundamental and dark resonant modes supported by the metasurface in the range of 0.2–0.5 THz. Both the amplitude and phase transmission spectra have been studied. A sensitivity of 21.1%/RIU (78.7 GHz/RIU) and a figure of merit (FOM) of 14.4 RIU−1 have been achieved. The FOM and Q factor obtained from the phase transmission spectra were shown to be about twice higher than those obtained from the amplitude spectra.

Metal–Adsorbate Interactions Modulate Plasmonic Reactivity of Chemisorbed Nitrophenyl Derivatives

Energetic hot electrons generated upon nonradiative decay of localized plasmons in metallic nanostructures can be effectively harnessed to catalyze photochemical transformations of molecular adsorbates through unique reaction pathways. When designing metal–adsorbate hybrid systems for hot electron-driven photocatalysis, both the intrinsic plasmonic properties of metallic photocatalysts and the chemical nature of metal–adsorbate interactions should be taken into careful considerations. In this work, we show that the reactivity of nitrophenyl derivative adsorbates on Ag nanoparticle surfaces toward plasmon-driven reductive coupling reactions is intimately tied to the bonding nature of molecular chemisorption. We focus on the comparative studies of three representative nitrophenyl derivatives, specifically para-nitrothiophenol, para-nitrophenylacetylene, and para-nitrophenylisocyanide, which covalently interact with the Ag photocatalysts using chemically distinct surface-anchoring groups. Taking full advantage of the unique time-resolving and molecular fingerprinting capabilities offered by surface-enhanced Raman spectroscopy, we have been able to precisely correlate the chemical nature of metal–adsorbate interactions to the kinetic characteristics of molecular transformations under a broad range of reaction conditions. Although the kinetic features of the coupling reactions change substantially upon variation of the excitation wavelength, the light illumination power, and the pH of the reaction medium, we have consistently observed that the plasmonic reactivity of the nitrophenyl derivative adsorbates drops drastically, as reflected by significant decrease in both reaction rates and yields, when the bonding modes dominating the metal–adsorbate interactions are switched from σ-donation to π-back-donation.

Strongly Coupled Plasmon and Phonon Polaritons as Seen by Photon and Electron Probes

The ability to control and modify infrared excitations in condensed matter is of both fundamental and applied interest. Here we explore a system supporting low-energy excitations, in particular, mid-infrared localized plasmon modes and phonon polaritons that are tuned to be strongly coupled. We study the coupled modes by using far-field infrared spectroscopy, state-of-the-art monochromated electron energy-loss spectroscopy, numerical simulations, and analytical modeling. We demonstrate that the electron probe facilitates a precise characterization of polaritons constituting the coupled system, and enables an active control over the coupling and the resulting sample response both in frequency and space. Although far-field optical spectra can be substantially different from near-field electron energy-loss spectra, we show that a direct comparison is possible via postprocessing and right positioning of the electron beam. The resulting spectra allow us to evaluate the key parameters of the coupled system, such as the coupling strength, which we demonstrate to be probe independent. Our work establishes a rigorous description of the spectral features observed in light- and localized electron-based spectroscopies, which can be extended to the analysis of analogous optical systems with applications in heat management and electromagnetic field concentration or nanofocusing.