Localized Plasmon Research Articles

A micro random laser of dye solution-filled tube system based on electrospun fibers

Random lasers (RLs) have good application prospects in speckle-free imaging, micro sensing and micro-nano photonic devices due to their properties such as cavityless, miniaturization and low-spatial coherence. The minimization, emission mechanism and lasing property control of RLs still need to be explored. In this paper, we present a novel micro RL system in a dye solution-filled tube, where the coherent random lasing action is facilitated by the integration of electrospun fibers and gold nanoparticles (Au NPs). The electrospun fibers serve as the scattering medium, while the Au NPs produce the local plasmon resonance effect. The interaction effect improves the photon scattering rate, makes the photons form a ring resonator in the system, and realizes the coherent RL in the tube system. The microtube RL has a very small size, a convenient preparation method and stable emission properties. It can withstand more than 2000 times pumping while maintaining a stable emission intensity. The electrospun fibers are stable and uniform in morphology, which makes it easy to achieve mass production of microtube RL. The speckle-free imaging experiment shows the RL has low spatial coherence, which indicates that it’s a good choice for micro speckle-free imaging. This work provides a convenient way to realize micro coherent RLs by electrospun fibers and could pave a way for applications in photonic devices.

Superhydrophobic silicone microcup array on periodic microswelling structure of silicone rubber formed by 193 nm ArF excimer laser-induced photodissociation

Many reports have been made on the study of imparting high functionality to materials surface by micro/nanofabrication of three-dimensional structures. In various three-dimensional structural geometries, the nanocups enable high-sensitivity analysis by combining with localized plasmon resonance. On the other hand, the formation of microcups and their applications have not been found much. In this paper, we found a new formation method of the silicone microcups and suggested its application. Single layer of silica glass microspheres was formed on silicone rubber, then a 193 nm ArF excimer laser irradiated the surface. Main chains of SiOSi bonds of the silicone rubber underneath the microspheres could be photodissociated to lower the molecular weight, resulting in the photochemical formation of periodic microswelling structure of silicone rubber. Concurrently, a hemispherical microcup was also formed on each the microswelling structure. The optimal laser irradiation conditions for their formation as well as the chemical etching time of microspheres were examined. It was also confirmed that the microcups are consisted of silicone. Moreover, the microcups exhibit superhydrophobicity. The results make it possible to confine the microcups in an air gap underwater, and it is expected to be applied as a micropower storage device that functions in seawater.

Numerical investigation of sequential phase-locked optical gating of free electrons

Recent progress in coherent quantum interactions between free-electron pulses and laser-induced near-field light have revolutionized electron wavepacket shaping. Building on these advancements, we numerically explore the potential of sequential interactions between slow electrons and localized dipolar plasmons in a sequential phase-locked interaction scheme. Taking advantage of the prolonged interaction time between slow electrons and optical near-fields, we aim to explore the effect of plasmon dynamics on the free-electron wavepacket modulation. Our results demonstrate that the initial optical phase of the localized dipolar plasmon at the starting point of the interaction, along with the phase offset between the interaction zones, can serve as control parameters in manipulating the transverse and longitudinal recoil of the electron wavefunction. Moreover, it is shown that the incident angle of the laser light is an additional control knop for tailoring the longitudinal and transverse recoils. We show that a sequential phase-locking method can be employed to precisely manipulate the longitudinal and transverse recoil of the electron wavepacket, leading to selective acceleration or deceleration of the electron energy along specific diffraction angles. These findings have important implications for developing novel techniques for ultrafast electron-light interferometry, shaping the electron wavepacket, and quantum information processing.

Enhancement and quenching of plasmon-enhanced spectroscopy of single molecule confined in metallic nanoparticle dimers

We present a theoretical analysis of plasmon-enhanced fluorescence (PEF) and Raman scattering (PERS) spectroscopy of a single molecule confined in the laser-irradiated metallic nanoparticles (NPs) dimer, focusing on the origin of the spectral enhancement and quenching effects. The theoretical method of D-parameters has been used to calculate the dimer distance-dependent nonlocal dielectric effect in Ag and Au NPs. Meanwhile, other damping rates and electric field enhancements are quantitatively computed by finite element method. Moreover, PEF and PERS spectra of rhodamine 6G are obtained within the density-functional theory. Our calculated results show that the PERS mainly depend on the excitation and emission field enhancements, and thus it occurs at the narrower dimer gap due to the stronger localized plasmon coupling. The PEF is related to fluorescence rate caused by the competition between excitation electric field and quantum efficiency, and the increase of former may enhance the fluorescence intensity while the lower latter lead to reduce the intensity as decreasing the dimer distance. The contribution of nonlocal dielectric effect can significantly reduce the quantum efficiency at smaller distance so that it overcomes the excitation field enhancement, leading to the fluorescence quenching for Au NPs dimer. Furthermore, by optimizing the dimer distance and NPs size, the maximum PERS and PEF cross sections reach 10−14 and 10−15 under 2.45 eV laser excitation for Ag NPs dimer, and 10−18 for Au NPs. Our study finely explains the experiment results showed either fluorescence enhancement or quenching with the change of molecule-NPs distance, and better guidance for optimizing the experiments.

Nonlinear Plasmonics in Nanostructured Phosphorene.

Phosphorene has emerged as an atomically thin platform for optoelectronics and nanophotonics due to its excellent optical properties and the possibility of actively tuning light-matter interactions through electrical doping. While phosphorene is a two-dimensional semiconductor, plasmon resonances characterized by pronounced anisotropy and strong optical confinement are anticipated to emerge in highly doped samples. Here we show that the localized plasmons supported by phosphorene nanoribbons (PNRs) exhibit high tunability in relation to both edge termination and doping charge polarity and can trigger an intense nonlinear optical response at moderate doping levels. Our explorations are based on a second-principles theoretical framework, employing maximally localized Wannier functions constructed from ab initio electronic structure calculations, which we introduce here to describe the linear and nonlinear optical response of PNRs on mesoscopic length scales. Atomistic simulations reveal the high tunability of plasmons in doped PNRs at near-infrared frequencies, which can facilitate the synergy between the electronic band structure and plasmonic field confinement to drive efficient high-harmonic generation. Our findings establish nanostructured phosphorene as a versatile atomically thin material candidate for nonlinear plasmonics.

Multiresonant plasmon excitation in slit antennas on metallic and hyperbolic metamaterials.

A comparative study of the optical properties of random and ordered arrays of metallic and hyperbolic slit antennas is presented. The metallic slits are fabricated on Au layers, whereas the hyperbolic ones are fabricated on Au/MgO multilayers. The random arrays show, for both types of antennas, similar slit plasmon resonances whose positions depend on the internal structure of the supporting layer. On the other hand, the spectra of the ordered arrays of the hyperbolic slits present additional resonances related to the excitation of Bloch plasmon polaritons in the hyperbolic layer. By varying the slit length and periodicity, an analysis of the interaction between slit localized resonance and Bloch plasmon polaritons is also presented.

(Invited) Plasmonic Enhancement of Electrochemical Reactions Using LSPR Phenomenon

Using Localized Surface Plasmon Resonance Effect for Enhancing Electrochemical reactions has been reported earlier both in terms of direct electron injection/transfer (DET) in outer-sphere reductive processes as well as charge injection into semiconductors via plasmon-induced resonant electron transfer processes (PIRE). While the former (DET) is mostly influenced by the lifetimes of the ejected hot electrons and their rapid cooling at the interface. For inner sphere reductive processes via the LSPR phenomenon, direct charge injection into the LUMO states of the adsorbed species is required. In this regard, it is imperative to distinguish between the inter-band charge transfer of the adsorbed species because of exposure to photons. In contrast to these charge injection into semiconductors via plasmon-induced resonant electron transfer processes (PIRE) is less understood and more complex. In this presentation, we will use the well-known endothermic anodic oxygen evolution reaction (OER) in alkaline pH to showcase fundamental aspects of charge injection and its effect on the hole-driven OER mechanism. For this well know OER catalyst, layered double hydroxides of Ni with Fe and Co dopants will be used. Electrochemical enhancement of OER will be explained based on detailed structural motifs of the semiconductors its band structure and the resonance effect of Au induced by the LSPR effect. The presence of direct and Indirect bandgaps will be discussed in the context of three possible mechanisms: (i) Charge carriers are directly injected via LSPR into the semiconductor. The conduction band of the semiconductor is usually (-0.1 to 0.0 eV vs. NHE) and the valence band is between (2.00 and 3.5 eV) which corresponds to electron energy between -2.00 to 3.5 eV vs NHE. For LSPR nanoparticles SPR energy is between 1.0 and 4.0 eV. Also, the Fermi energy of LSPR is usually 0.0 vs. NHE. Hence LSPR only enables energetic electrons to be transferred from metals to semiconductors. It is the interface between LSPR and the semiconductor which is important. Charge injection is more prevalent when metal LSPR is of lower energy than the semiconductor. Direct electron transfer (DET). (ii) Transfer not involving direct electron injection but via (a) near field electromagnetic and (b) resonant photon scattering mechanism. This has been shown to work by adding a thin dielectric material between the LSPR and semiconductor. This would be most likely in the case of OER where surface localized plasmons will be the most important determinant as opposed to recombination events in the bulk of the semiconductor. This is most important for OER as it depends on the surface hole concentration. It should be noted that larger nanoparticles (>50 nm) have increased resonant photon scattering. Such a mechanism is more prevalent when we have an overlap between metal LSPR and semiconductor bands leading to plasmon induced resonant electron transfer (PIRET). (iii) When metal LSPR is in direct contact with the semiconductor all three phenomenon could be active.

Enhanced circular dichroism in twisted double layer nanoparticle arrays with the excitation of hybridized surface lattice resonances

The realization of enhanced circular dichroism using chiral nanostructures is crucial for the development of functional nanophotonic devices. This study proposes to construct chiral structures by adjusting the relative orientation between two vertically shifted rectangular nanodisk arrays. In comparison to localized plasmon modes, the twisted array allows selective excitation of hybridized surface lattice resonances by left- or right-handed circularly polarized incidence, and the strong interactions among individual nanoparticles result in enhanced circular dichroism. The calculation results demonstrate a significant differential transmittance of up to 0.61, which is more than one order of magnitude stronger than that of localized modes. Moreover, the chiral responses can be effectively controlled by manipulating geometry parameters such as inter-layer separation, twisted angle, and lattice spacing, as these factors govern the coupling efficiency with the external field and the radiative damping of the hybridized modes. The proposed twisted array structure offers a versatile platform for manipulating chiral light fields.

Simulation of Fe2O3/Au@MoS2 plasmonic core/shell@shell nanocomposites: Optical properties and photothermal application

The plasmonic and magneto-plasmonic nanocomposites are multi-functional structures that are applicable to medical applications such as tumor therapy, diagnosis, and biosensors. Here, the simulation of the optical and photothermal properties of plasmonic nanocomposites has been done. The spherical core@shell and core/shell@shell nanocomposites have been modeled using the generalized Mie theory. Au and Fe2O3 have been used as plasmonic and magnetic structures because of their bio-compatibility and then the role of MoS2 shell has been examined. The results show that these structures are very effective in photothermal therapy since their localized surfaced plasmon resonance is situated in the near-infrared region of electromagnetic waves. Among the simulated structures, Fe2O3@Au shows the best plasmonic behavior and absorption efficiency enhanced about 7 when the core radius is 20 nm, and the shell thickness and wavelength of incident light are between 5 and 10 nm and 700–800 nm, respectively. Maxwell-Garnett's effective medium theory has been used to calculate the effective permittivity of nanocomposites as well as the simulation of the temperature increase under laser radiation. The temperature enhancement of single nanocomposites shows very promising results. The single Fe2O3/Au@MoS2core/shell@shell nanocomposite illustrates the highest performance in temperature increase with 10−3K.

Strong Acousto-Plasmonic Coupling in Film-Coupled Nanoparticles Mediated by Surface Acoustic Waves

The interaction between phonons and localized plasmons in film-coupled nanoparticles designs can be exploited both for modulating the scattered electromagnetic field and the understanding of the mechanical vibrations at nanoscale. In this paper, we show by finite element numerical analysis an enhanced optomechanical interaction in a film-coupled gold nanoridges or pillars mediated by surface acoustic waves. The metallic nanoparticles are placed atop a multilayer structure consisting of a thin dielectric spacer covering a gold film layer on a silicon dioxide/or silicon substrate. Optical simulations reveal the existence of surface localized plasmons in the infrared range confined under the nanoparticles in the dielectric spacer and/or in between such particles. Optomechanical coupling between the plasmonic modes and localized phonons is evaluated from the shift in the plasmon eigenfrequency. It is found that the compressional, the in-phase compressional and the out-of-phase flexural modes, yield the highest coupling rates. Such phonons are excited by means of SAW launched from the system inlet in front of the particles. The findings in this paper could help design new generation of acousto-optic modulators monitored by fast coherent surface acoustics.

Quantifying Efficiency of Remote Excitation for Surface-Enhanced Raman Spectroscopy in Molecular Junctions.

Surface-enhanced Raman spectroscopy (SERS) is enabled by local surface plasmon resonances (LSPRs) in metallic nanogaps. When SERS is excited by direct illumination of the nanogap, the background heating of the lattice and electrons can prevent further manipulation of the molecules. To overcome this issue, we report SERS in electromigrated gold molecular junctions excited remotely: surface plasmon polaritons (SPPs) are excited at nearby gratings, propagate to the junction, and couple to the local nanogap plasmon modes. Like direct excitation, remote excitation of the nanogap can generate both SERS emission and an open-circuit photovoltage (OCPV). We compare the SERS intensity and the OCPV in both direct and remote illumination configurations. SERS spectra obtained by remote excitation are much more stable than those obtained through direct excitation when the photon count rates are comparable. By statistical analysis of 33 devices, the coupling efficiency of remote excitation is calculated to be around 10%, consistent with the simulated energy flow.

Optical nonreciprocity in multilayer nanoisland systems of [Ag–Al2O3] N

We study the effect of optical nonreciprocity in [Ag–Al2O3] N multilayer structures. The percolation threshold for Ag films was found to be . An anomalously large optical nonreciprocity effect was found in the structures with Ag island layers. This effect appeared as a change in the reflected light polarization () when the sample was rotated around its axis from the initial position by 180∘. The effect magnitude reached . We suggest that a possible mechanism for the optical nonreciprocity effect in these structures can be related to the excitation of localized plasmons in Ag islands. We show that essentially depends on the interlayer and intralayer interaction between Ag layers in multilayer structures and is suppressed in the case of strong intralayer and interlayer interaction of plasma oscillations.

Ultrafast THz spectroscopy of carbon nanotube-graphene composites

Mixed nanomaterial composites can combine the excellent properties of well-known low-dimensional nanomaterials. Here we highlight the potential of one-dimensional single-walled carbon nanotubes interfaced with two-dimensional graphene by exploring the composite’s ac conductivity and photoconductivity, and the influence of HAuCl4 doping. In the composite, the equilibrium terahertz conductivity from free carrier motion was boosted, while the localised plasmon peak shifted towards higher frequencies, which we attribute to shorter conductivity pathways in the composite. A negative terahertz photoconductivity was observed for all samples under 410 nm optical excitation and was reproduced by a simple model, where the Drude spectral weight and the momentum scattering rate were both lowered under photoexcitation. The composite had an enhanced modulation depth in comparison to reference carbon nanotube films, while retaining their characteristically fast (picosecond) response time. The results show that carbon nanotube-graphene composites offer new opportunities in devices by controlling charge carrier transport and tuning their optoelectronic properties.

Scattering Amplitude of Surface Plasmon Polariton Excited by a Finite Grating.

Unusual optical properties of laser-ablated metal surfaces arise from the excitation of local plasmon resonances in nano- and microstructures produced by laser-processing and from the mutual interaction of those structures through surface plasmon polariton (SPP) waves. This interaction provides a synergistic effect, which can make the optical properties of the composite nanostructure drastically different from the properties of its elements. At the same time, the prediction and analysis of these properties are hampered by the complexity of the analytical solution to the problem of SPP excitation by surface objects of arbitrary configuration. Such a problem can be reduced to a simpler one if one considers the geometry of a structured surface as a superposition of harmonic Fourier components. Therefore, the analytical solution to the problem of surface plasmon polariton excitation through the scattering of light by a sinusoidally perturbed plasmonic metal/vacuum boundary becomes very important. In this work, we show that this problem can be solved using a well-known method for calculating guided-mode amplitudes in the presence of current sources, which is used widely in the waveguide theory. The calculations are carried out for the simplest 2D cases of (1) a sinusoidal current of finite length and (2) a finite-length sinusoidal corrugation on a plasmonic metal surface illuminated by a normally incident plane wave. The analytical solution is compared with the results of numerical simulations. It is shown that, in the first case, the analytical and numerical solutions agree almost perfectly. In the second case, the analytical solution correctly predicts the optimum height of the corrugation xopt, providing the maximum SPP excitation efficiency. At the same time, the analytical and numerical values of the SPP amplitude agree very well when the corrugation height x turns out to be x≪xopt or x≫xopt (at least up to 3xopt); at x=xopt, the mismatch of those does not exceed 25%. The limitations of the analytical model leading to such a mismatch are discussed. We believe that the presented approach is useful for modeling various phenomena associated with SPP excitation.

Dynamically Adjusting Borophene-Based Plasmon-Induced Transparency in a Polymer-Separated Hybrid System for Broadband-Tunable Sensing.

Borophene, an emerging two-dimensional (2D) material platform, is capable of supporting highly confined plasmonic modes in the visible and near-infrared wavebands. This provides a novel building block for light manipulation at the deep subwavelength scale, thus making it well-suited for designing ultracompact optical devices. Here, we theoretically explore a borophene-based plasmonic hybrid system comprising a continuous borophene monolayer (CBM) and sodium nanostrip gratings (SNGs), separated by a polymer spacer layer. In such a structure, a dynamically tunable plasmon-induced transparency (PIT) effect can be achieved by strongly coupling dark and bright plasmonic modes, while actively controlling borophene. Here, the bright mode is generated through the localized plasmon resonance of SNGs when directly excited by TM-polarized incident light. Meanwhile, the dark mode corresponds to a propagating borophene surface plasmon (BSP) mode in the CBM waveguide, which cannot be directly excited, but requires phase matching with the assistance of SNGs. The thickness of the polymer layer has a significant impact on the coupling strength of the two modes. Owing to the BSP mode, highly sensitive to variations in the ambient refractive index (RI), this borophene-based hybrid system exhibits a good RI-sensing performance (643.8 nm/RIU) associated with a wide range of dynamically adjustable wavebands (1420-2150 nm) by tuning the electron density of borophene. This work offers a novel concept for designing active plasmonic sensors dependent on electrically gating borophene, which has promising applications in next-generation point-of-care (PoC) biomedical diagnostic techniques.

Nanoplasmonic biosensors for precision medicine.

Nanoplasmonic biosensors have a huge boost for precision medicine, which allows doctors to better understand diseases at the molecular level and to improve the earlier diagnosis and develop treatment programs. Unlike traditional biosensors, nanoplasmonic biosensors meet the global health industry's need for low-cost, rapid and portable aspects, while offering multiplexing, high sensitivity and real-time detection. In this review, we describe the common detection schemes used based on localized plasmon resonance (LSPR) and highlight three sensing classes based on LSPR. Then, we present the recent applications of nanoplasmonic in other sensing methods such as isothermal amplification, CRISPR/Cas systems, lab on a chip and enzyme-linked immunosorbent assay. The advantages of nanoplasmonic-based integrated sensing for multiple methods are discussed. Finally, we review the current applications of nanoplasmonic biosensors in precision medicine, such as DNA mutation, vaccine evaluation and drug delivery. The obstacles faced by nanoplasmonic biosensors and the current countermeasures are discussed.

Optical coupling of bio-inspired mustard protein-based bimetallic nanohybrids with propagating surface plasmon polaritons for femtomolar nitrite ion sensing: Cellphone-based portable detection device

Different classes of biologically and environmentally relevant molecules and ions are quantitatively and qualitatively analyzed using the synergistic approach wherein the properties of both the plasmonic nanomaterials and the fluorescent moieties are explored. In this study, such hybrid systems, called plasmophores (or plasmon coupled fluorophores), are investigated using the surface plasmon-coupled emission (SPCE) platform with silver, gold and silver-gold hybrid nano-structures synthesized via sustainable bio-inspired routes. A simple, rapid, user-friendly and green chemistry approach has been adopted using biocompatible mustard protein as both the reducing and capping agent during nanosynthesis. The morphologically and functionally tunable plasmonic nanomaterials were synthesized by simply exposing a mixture of the respective metal ions and protein to UV-light irradiation. Comprehensive analysis of the out-coupled spontaneous emission in the SPCE framework using spacer, cavity and extended cavity nanointerfaces yielded intriguing results, presenting optimum prerequisites for realizing high SPCE enhancements. More than a 950-fold improvement in the fluorescence signal intensity of rhodamine B was demonstrated utilizing the plasmonic cavity hotspots rendered by the hybrid coupling of the propagating surface plasmon polaritons of Ag with localized plasmon resonances of the bimetallic AgAu nanohybrids. The sharply directional and highly polarized SPCE enhancements, realized without increasing the illumination intensity, were utilized for quantitative detection of biologically relevant nitrite ions in drinking water samples at trace concentrations (limit of detection: 0.1 femtomolar). The applicability and relevance of the demonstrated method for sustainable use of plasmonic nanomaterials in photo-plasmonic research is presented by accomplishing the sensing using a cost-effective smartphone camera with a good correlation with the data obtained from a conventional detector system. Hence, the bio-nano-inspired strategy described here reveals several potential opportunities for the development of environmentally benign portable chemosensing devices for utility in academia and industry, especially for low-and-middle income countries.

Greatly Enhanced Raman Scattering of Graphene on Metals by a Boron Nitride Film Covering.

Raman spectroscopy, a nondestructive fingerprinting technique, is mainly utilized to identify molecular species and phonon modes of materials. However, direct Raman characterization of two-dimensional materials typically synthesized on catalytic metal substrates is extremely challenging because of the significant electric screening and interfacial electronic couplings. Here, we demonstrate that by covering as-grown graphene with boron nitride (BN) films, the Raman intensity of graphene can be enhanced by two orders of magnitude and is also several times stronger than that of suspended graphene. This great Raman enhancement originates from the optical field amplification by Fabry-Pérot cavity in BN films and the local field plasmon near copper steps. We further demonstrate the direct characterization of the local strain and doping level of as-grown graphene and in situ monitoring of the molecule reaction process by enhanced Raman spectroscopy. Our results will broaden the optical investigations of interfacial sciences on metals, including photoinduced charge transfer dynamics and photocatalysis at metal surfaces.

A Simple Method to Fabricate the Highly Sensitive SERS Substrate by Femtosecond Laser-Based 3D Printer

Surface-enhanced Raman spectroscopy (SERS) is a potent technique for analyzing and detecting various targets, including toxic ions, pesticides, and biomarkers, at the single-molecule level. The efficiency of SERS techniques relies heavily on the underlying SERS substrate, which is primarily responsible for the strong induction of localized plasmon resonance on nanostructures. Noble metals such as gold and silver were commonly used to fabricate SERS substrates, leveraging the electromagnetic mechanism (EM) to enhance the Raman signal. However, chemically synthesized nanoparticle-based SERS substrates suffer from low uniformity and reproducibility. Furthermore, the high cost associated with noble metals makes most SERS substrates expensive to produce. In this study, we present a straightforward method for fabricating a highly uniform and reproducible SERS substrate using a femtosecond laser-based 3D printer. Notably, our method offers good cost competitiveness since it requires only a minimal amount of gold coating for the SERS signal. Moreover, the proposed method exhibits exceptional versatility in SERS analysis and detection, catering to numerous targets in the field.

Plasmonic Nanopyramid Array Enhancing Luminescence of MoS2 Investigated by Cathodoluminescence

AbstractTransition metal dichalcogenides (TMDs) like molybdenum disulfide (MoS2) have unique optical properties such as strong luminescence and a tunable bandgap. However, the small interaction distance due to the atomically thin nature of these materials is a limitation for applications. In this study, a significant enhancement of the A‐ and B‐exciton emission in MoS2 flakes through coupling with plasmonic Au nano‐pyramid arrays fabricated by a colloidal lithography technique is reported. This study experimentally maps local emission enhancement from the structure with a nanometer spatial resolution by cathodoluminescence (CL) technique. Strongly enhanced emission intensity within the MoS2‐Au pyramids is achieved due to the localized surface plasmon resonance confined in nano‐pyramids and its interaction with the periodicity‐based resonance of the array structure. The results provide an approach to significantly improve the luminescence intensity of MoS2 through optical interaction with the local plasmonic field, which is promising for applications in optoelectronic devices and nanophotonics.