Longitudinal Plasmon Modes Research Articles

Effects of swift heavy ions on metal nanoparticles embedded in silica: Using linearly polarized light to monitor the elongation kinetics.

The elongation of metallic nanoparticles (NPs) embedded in a dielectric matrix after irradiation with swift heavy ions is a phenomenon that has been known for several years. However, the precise mechanism behind this deformation process is still not fully understood, primarily due to the dearth of information during intermediate stages of deformation. In this study, we report the continuation of our previous work [Peña-Rodríguez et al., Sci. Rep. 7(1), 922 (2017)], exploiting the strong dependence of the localized surface plasmon resonance on the aspect ratio of elongated metal NPs to study the elongation kinetics in situ. In situ optical absorption spectra were measured using a polarizing beam splitter to separate the longitudinal and transverse plasmon modes of the anisotropic NPs. Then, the detailed geometrical and compositional parameters were determined from a fit of these spectra. The use of linearly polarized light allowed for a more accurate analysis of the elongation kinetics, particularly useful in the first stages, where longitudinal and transverse modes overlap.

Multi-wavelength and broadband plasmonic switching with V-shaped plasmonic nanostructures on a VO2 coated plasmonic substrate

In this paper, periodic arrays of identical V-shaped gold nanostructures and variable V-shaped gold nanostructures are designed on top of a gold-coated silicon dioxide (SiO2) substrate with a thin spacer layer of vanadium dioxide (VO2) to realize multi-wavelength and broadband plasmonic switches, respectively. The periodic array of identical V-shaped nanostructures (IVNSs) with small inter-particle separation leads to coupled interactions of the elementary plasmons of a V-shaped nanostructure (VNS), resulting in a hybridized plasmon response with two longitudinal plasmonic modes in the reflectance spectra of the proposed switches when the incident light is polarized in the x-direction. The x-direction is oriented along the axis that joins the V-junctions of all VNSs in one unit cell of the periodic array. On exposure to temperature, electric field, or optical stimulus, the VO2 layer transforms from its monoclinic semiconducting state to its rutile metallic state, leading to an overall change in the reflectance spectra obtained from the proposed nanostructures and resulting in an efficient multi-wavelength switching action. Finite difference time domain modelling is employed to demonstrate that an extinction ratio (ER) >12 dB at two wavelengths can be achieved by employing the proposed switches based on periodic arrays of IVNSs. Further, plasmonic switches based on variable V-shaped nanostructures—i.e. multiple VNSs with variable arm lengths in one unit cell of a periodic array—are proposed for broadband switching. In the broadband operation mode, we report an ER >5 dB over an operational wavelength range >1400 nm in the near-IR spectral range spanning over all optical communication bands, i.e. the O, E, S, C, L and U bands. Further, it is also demonstrated that the wavelength of operation for these switches can be tuned by varying the geometrical parameters of the proposed switches. These switches have the potential to be employed in communication networks where ultrasmall and ultrafast switches with multi-wavelength operation or switching over a wide operational bandwidth are inevitably required.

Plasmon resonances of GZO core-Ag shell nanospheres, nanorods, and nanodisks for biosensing and biomedical applications in near-infrared biological windows I and II.

There is currently a great deal of interest in realizing localized surface plasmon resonances (LSPRs) in two distinct windows in the near-infrared (NIR) spectrum for in vivo biosensing and medical applications, the biological window (BW) I and II (BW I, 700-900 nm; BW II, 1000-1700 nm). This study aims to demonstrate that LSPRs of Ga-doped ZnO (GZO) core-silver (Ag) shell structures exhibit promising features for biological applications in the NIR BW I and II. Here, we study three different shapes for nanoshells: the core-shell nanosphere, nanorod, and nanodisk. In the calculation of the optical response of these nanoshells, an effective medium approach is first used to reduce the dielectric function of a nanoshell to that of an equivalent homogenous NP with an effective dielectric function. Then, the LSPR spectra of nanoshells are calculated using the modified long-wavelength approximation (MLWA), which corrects the polarizability of the equivalent NP as obtained by Gans theory. Through numerical investigations, we examine the impacts of the core and shell sizes of the proposed nanoshells as well as the medium refractive index on the position and line width of the plasmon resonance peaks. It is shown that the plasmon resonances of the three proposed nanoshells exhibit astonishing resonance tunability in the NIR region by varying their geometrical parameters. Specifically, the improved spectrum characteristics and tunability of its plasmon resonances make the GZO-Ag nanosphere a more viable platform for NIR applications than the spherical metal colloid. Furthermore, we demonstrate that the sensitivity and figure of merit (FOM) of the plasmon resonances may be significantly increased by using GZO-Ag nanorods and nanodisks in place of GZO-Ag nanospheres. It is found that the optical properties of the transverse plasmon resonance of the GZO-Ag nanodisk are superior to all plasmon resonances produced by the GZO-Ag nanorods and GZO-Ag nanospheres in terms of sensitivity and FOM. The FOM of the transverse plasmon mode of the GZO-Ag nanodisk is almost two orders of magnitude higher than that of the longitudinal and transverse plasmon modes of the GZO-Ag nanorod in BW I and BW II. And it is 1.5 and 2 times higher than the plasmon resonance FOM of GZO-Ag nanospheres in BW I and BW II, respectively.

Coupling Nd3+:Y2O3 fluorescent submicron particles to linear plasmonic chains

We report on the fabrication and optical characterization of a new hybrid material consisting of Nd3+ doped Y2O3 submicron particles associated with linear chains of plasmonic nanostructures. By drop-casting deposition, single Nd3+ doped Y2O3 polycrystalline particles are dispersed and located in the vicinities of plasmonic chains of silver nanoparticles formed on the surface a LiNbO3 substrate. The interaction between the plasmonic modes of the chain with the fluorescent yttria submicron particles is analyzed by micro-luminescence experiments. Orthogonal polarization configurations of the excitation radiation, namely, perpendicular and parallel to plasmonic chain axis, are employed to study the effect of the longitudinal and transverse chain plasmonic modes on the luminescence of the particles. A remarkable dependence of the emission intensity of the Nd3+:Y2O3 submicron particles on the excitation polarization is observed, showing the capability of plasmonic chains to modulate the emission of fluorescent submicron particles in contact with the chain. Numerical simulations evidence a different distribution of the excitation radiation field within the Nd3+:Y2O3 particle depending on the type of excited plasmonic mode, longitudinal or transversal, of the chain, and hence, the ability of plasmonic chains for controlling the emission of Rare Earth doped submicron particles.

Asymmetric L-shaped resonant optical antennas with plasmon length tuning and high-electric field enhancement

L-shaped resonant optical antennas (ROAs) are low-symmetry plasmonic nanostructures with the unique ability to show two tunable resonances in the optical and near-infrared wavelength regions. The plasmon length of the so-called longitudinal dipolar fundamental plasmon mode of these asymmetric L-shaped ROAs can be used as plasmon resonance building blocks to design polarization-sensitive devices. This paper introduces and numerically analyzes a novel design of asymmetric L-shape ROAs. The reported design offers two resonance modes, i.e., bimodal longitudinal antenna resonance behavior with a high enhancement factor. These two resonances can be selectively excited by changing the linear polarization angle. It is found that the coupled L-shaped ROA with a very small 2 nm gap width exhibits field enhancements 40 and 147.3 on scale left|{E}_{TOT}right|/left|{E}_{IN}right| for the high energy and low energy resonance, respectively. The obtained results and the analysis open a new route for multiple plasmon resonance devices with ultra-high field enhancement that can be easily integrated with future nano-optical circuits with multiple operational frequencies.

Surfactant Layers on Gold Nanorods.

ConspectusGold nanorods (Au NRs) are an exceptionally promising tool in nanotechnology due to three key factors: (i) their strong interaction with electromagnetic radiation, stemming from their plasmonic nature, (ii) the ease with which the resonance frequency of their longitudinal plasmon mode can be tuned from the visible to the near-infrared region of the electromagnetic spectrum based on their aspect ratio, and (iii) their simple and cost-effective preparation through seed-mediated chemical growth. In this synthetic method, surfactants play a critical role in controlling the size, shape, and colloidal stability of Au NRs. For example, surfactants can stabilize specific crystallographic facets during the formation of Au NRs, leading to the formation of NRs with specific morphologies.The process of surfactant adsorption onto the NR surface may result in various assemblies of surfactant molecules, such as spherical micelles, elongated micelles, or bilayers. Again, the assembly mode is critical toward determining the further availability of the Au NR surface to the surrounding medium. Despite its importance and a great deal of research effort, the interaction between Au NPs and surfactants remains insufficiently understood, because the assembly process is influenced by numerous factors, including the chemical nature of the surfactant, the surface morphology of Au NPs, and solution parameters. Therefore, gaining a more comprehensive understanding of these interactions is essential to unlock the full potential of the seed-mediated growth method and the applications of plasmonic NPs. A plethora of characterization techniques have been applied to reach such an understanding, but many open questions remain.In this Account, we review the current knowledge on the interactions between surfactants and Au NRs. We briefly introduce the state-of-the-art methods for synthesizing Au NRs and highlight the crucial role of cationic surfactants during this process. The self-assembly and organization of surfactants on the Au NR surface is then discussed to better understand their role in seed-mediated growth. Subsequently, we provide examples and elucidate how chemical additives can be used to modulate micellar assemblies, in turn allowing for a finer control over the growth of Au NRs, including chiral NRs. Next, we review the main experimental characterization and computational modeling techniques that have been applied to shed light on the arrangement of surfactants on Au NRs and summarize the advantages and disadvantages for each technique. The Account ends with a "Conclusions and Outlook" section, outlining promising future research directions and developments that we consider are still required, mostly related to the application of electron microscopy in liquid and in 3D. Finally, we remark on the potential of exploiting machine learning techniques to predict synthetic routes for NPs with predefined structures and properties.

Strong coupling between longitudinal and U-shaped localized surface plasmon modes in rectangular grating-shaped gold nanostructures

Strong couplings between localized surface plasmon resonance (LSPR) modes and single quantum emitters have been intensively investigated recently, and meanwhile the coupling between different LSPR modes inside individual metallic nanoparticle is still rarely researched. Herein, the strong coupling is investigated for different LSPR modes inside individual rectangular-grating-shaped gold nanostructure composed of one main-cuboid and two side-attached subcuboids. Original uncoupled LSPR modes are revealed to be longitudinal and U-shaped LSPRs. For the nanostructure with increased main-cuboid length, the dispersion curves of simulated dual-original LSPR scattering wavelengths and dual-coupled LSPR scattering wavelengths show typical strong coupling patterns featuring anti-crossing and large Rabi splitting of 598.1 meV. The strong coupling is considered to be caused by the overlap of longitudinal and U-shaped LSPR oscillation modes in the gold nanostructure. The extracted coupling strength is found in order of 1013 Hz and it increases with the LSPR overlap length. The spatial mode and time evolution of the coupled LSPR modes are also numerically investigated. The simulated results are well comprehended with the classical strong coupling model of oscillators, further confirming the coupling between the longitudinal and the U-shaped LSPRs. The experimental dark-field scattering spectrum shows the existence of U-shaped LSPR mode in the gold nanostructure.

Controlled synthesis and computational analysis of gold nanostars for the treatment of Fusarium oxysporum.

Fusarium oxysporum (F. oxysporum) is linked to the widespread fusarium wilt in plants affecting the quality and yield of food crops. Management of fusarium wilt by synthetic fertilizers poses safety concerns. Safer-by-design nanomaterials synthesized with a greener approach can meet the needs of commercial antifungal drug resistance. Herein, a simple aqueous reduction method has been adopted for the synthesis of anisotropic gold nanostars (AuNSs) using quercetin-para aminobenzoic acid (QPABA) as both a reducing and stabilizing agent at room temperature for the treatment of F. oxysporum. QPABA was used to control the growth of Au3+ star-shaped nanoparticles at increasing concentrations in the ratio of 2 : 1 (QPABA : Au3+ ions) respectively. Transmission electron microscopy (TEM) analysis of the as-prepared gold nanoparticles confirmed the formation of nanostars with sizes of 40 ± 2 nm. The formation of anisotropic gold nanoparticles was evaluated by UV-vis characterizations which showed longitudinal surface plasmon modes at 540 and 800 nm. The gold nanoparticles exhibit excellent antifungal activity against F. oxysporum with the minimum inhibitory concentration (MIC) of 100 μg mL-1 using an agar well-diffusion assay. AuNSs proved to be efficacious in controlling F. oxysporum, as shown in the SEM analysis with a disintegrated cell membrane upon treatment. Computational analysis was performed to determine the specific binding sites on the QPABA ligand for gold ion interactions using the DFT B3LYP method, with a 6-31+G(d) basis set. Results showed that the interaction between Au3+ and QPABA at the 4 and 3 positions yielded the highest stability and formation of gold nanostars. The results suggest that the synthesized AuNSs act as a promising antifungal agent with great potential in treating frequent fungal infections that affect agricultural production.

Colloidal titanium nitride nanobars for broadband inexpensive plasmonics and photochemistry from visible to mid-IR wavelengths

Developing colloidal plasmonic nanomaterials with high carrier density that show optical resonances and photochemical activity extending from the visible to the mid-infrared (MIR) ranges remains a challenging pursuit. Here, we report the fabrication of titanium nitride (TiN) nanobars obtained using a two–step procedure based on a wet chemical route synthesis of TiO2 nanowires and their subsequent high temperature annealing in ammonia flow. Electromagnetic simulations of the resulting TiN nanobars reveal a rich set of optical resonances featuring transverse, longitudinal and mixed transverse–longitudinal plasmonic modes that cover energies from the visible to MIR region. TiN nanobars decorated with Pt co-catalyst nanocrystals show enhanced photocatalytic hydrogen evolution activity in comparison to both isotropic TiN nanospheres of similar size and TiN nanocubes under near infrared excitation at 940 nm due to the enhanced hot electron generation. We also demonstrate that plasmonic TiN nanobars can be used for the detection of furfural molecular vibrations by providing a strong surface enhanced infrared absorption (SEIRA) effect in the MIR region.

An effective one-step aqueous-phase synthesis of finely controllable Ag nanorods with tunable short aspect ratios and electronic dynamics properties

Ag nanorods with finely controllable aspect ratios (especially 1–5) were synthesized in high yield via an effective one-step aqueous-phase method, in which the longitudinal plasmon modes in visible and infrared regions of short Ag nanorods were well adjustable. Meanwhile, excitation wavelength- and excitation fluence-dependent electronic dynamics of short Ag nanorods were acquired and were found to be regular. This suggested that short Ag nanorods would have great potential in plasmonic and photoelectronic fields.

Theoretical simulation of nonlinear regulation of wall thickness dependent longitudinal surface plasmon in pentagonal gold nanotubes

In this paper, the longitudinal plasmon mode optical properties and localized electric field distribution of a single pentagonal gold nanotube are investigated for the first time by the discrete dipole approximation. It is found that pentagonal gold nanotube has stronger electric field distribution compared with circular gold nanotubes when the incident wavelength is located at the plasmon resonance peak. Additionally, we observed that the longitudinal plasmon resonance peak can blue shift nonlinearly with increasing wall thickness, but red shifts linearly with the increase of the length of the pentagonal gold nanotube. The localized electric field analysis reveals that the longitudinal plasmon peak of the pentagonal gold nanotube originates from the dipole resonance mode. The local electric field intensity is controlled by the wall thickness and length. Notably, the effect of wall thickness on the longitudinal plasmon resonance and electric field enhancement can be attributed to the change of the plasmon coupling position and intensity. This work has enriched the theoretical research of pentagonal gold nanotubes and provided ideas for the preparation of high sensitivity nanoprobes biosensors.

Atomic-scale control of plasmon modes in graphene nanoribbons

We address the possibility of atomic-scale control of the plasmon modes of graphene nanostructures. Using the time-dependent many-body approach we show that for the zigzag and armchair nanoribbons, the single carbon atom vacancy results in ``on'' and ``off'' switching of the longitudinal plasmon modes or in a change of their frequency. The effect stems from the robust underlying physical mechanism based on the strong scattering of the two-dimensional (2D) electrons on the vacancy defects in graphene lattice. Thus our findings establish a platform for optical response engineering or sensing in 2D materials.

Ultrafast Dynamics of Colloidal Copper Nanorods: Intraband versus Interband Excitation

Colloidal copper nanorods (NRs) display transverse and longitudinal localized surface plasmon resonances. The longitudinal localized surface plasmon modes are tunable through the near‐infrared electromagnetic radiation energies with NR aspect ratios. Visible and near‐infrared transient optical response of the copper NRs is investigated under excitation conditions spanning intraband and interband excitation (0.79−3.50 eV). In both the visible and near‐infrared regions, the spectral response of the samples under intraband excitation (<2 eV) differs substantially from their response under interband excitation (>2 eV). However, the timescale of the electron−phonon coupling estimated from pump fluence‐dependent measurements (τep) is less sensitive to excitation conditions than reports for gold. τep shortens slightly from ≈616 fs with intraband excitation (at visible probe energies) to ≈565 fs with interband excitation. The observed dynamics correspond to an average sample electron−phonon coupling parameter varying across all conditions from 4.4 × 1016 to 6.4 × 1016 J m−3 K−1, which is similar to bulk copper. Furthermore, coherent acoustic phonons are observed for the longitudinal localized surface plasmon resonance with a range of oscillatory periods reflecting sample size dispersion.

Interplays of Dipole and Charge‐Transfer‐Plasmon Modes in Capacitively and Conductively Coupled Dimer with High Aspect Ratio Nanogaps

AbstractCharge transfer plasmons (CTPs) in coupled plasmonic cavities have gained attention for their interesting resonance mechanisms and potential applications in sensing. The authors present the first investigation of the CTP mode in top‐down fabricated tall plasmonic nanostructures with deep nanogaps, whose excitation becomes possible by the interaction of transversal and longitudinal plasmonic modes. Hybridization of dipole and CTP modes at different parts of the plasmonic nanostructures, for both capacitively coupled dimer of sub‐5 nm gap and conductively coupled dimer with junction bridge is extensively studied. Importantly, the authors demonstrate the conditional emergence of a hybrid dimer‐CTP mode based on the cladding refractive index and analyte thickness, which can present an opportunity for highly specific surface sensing applications. The sensing performances of these modes are evaluated, showing a figure‐of‐merit of ≈18.4 and Q ≈ 44 for the hybrid dimer‐CTP mode in the visible spectrum. Surface sensing based on alkanethiol adsorption shows surface sensitivity as high as ≈3.2 nm/carbon‐chain for this mode, which is higher than the typical values obtained by LSP structures.

Enhancement of the Photocurrent of a Single Photosystem I Complex by the Localized Plasmon of a Gold Nanorod.

A combination of conductive atomic force microscopy (AFM) and confocal fluorescence microscopy was used to measure photocurrents passing through single trimeric photosytem I (PSI) complexes located in the vicinity of single gold nanorods (AuNRs). Simultaneous excitation of PSI and of the AuNR longitudinal plasmon mode and detection of photocurrents from individual PSI in relation to the position of single AuNRs enable insight into plasmon-induced phenomena that are otherwise inaccessible in ensemble experiments. We have observed photocurrent enhancement by the localized plasmons by a factor of 2.9 on average, with maximum enhancement values of up to 8. Selective excitation of the longitudinal plasmon modes by the polarization of the excitation laser enables controllable switch-on of the photocurrent enhancement. The dependence of the extent of enhancement on the distance between PSI and AuNRs indicates that, apart from the enhancement of absorption, there is an additional enhancement mechanism affecting directly the electron transport process. The present study provides deeper insight into the molecular mechanisms of plasmon-enhanced photocurrents, not only in PSI but also potentially in other systems as well.

Hybrid nanowire-hyperbolic metamaterial based broadband absorber for the visible and near-infrared regions

In this work, spectral absorbance of hybrid nanowire-hyperbolic metamaterial was investigated numerically by using transfer-matrix method. The hybrid nanowire-hyperbolic metamaterial is consisted of two-dimensional periodically arranged arrays of subwavelength-sized hybrid nanowires (with circular cross-section) embedded in silicon dioxide host matrix. Each hybrid nanowire is made by core-shell structure used silicon as a core and gold as a shell. The hybrid nanowire-hyperbolic metamaterial is used as a top layer of a broadband absorber. The top layer is over on a planar silicon dioxide layer, which is backed by a nano-sized layer of gold as a perfect reflector for guaranteeing high absorbance. When electromagnetic waves in the range of 400–1600 nm wavelength are obliquely incident on the top hybrid nanowire-hyperbolic metamaterial surface, the absorption spectra of the designed absorber structure are analyzed for different incident angles, and radii of hybrid nanowire components or fill-factor of the hyperbolic metamaterial layer. The multiple absorption peaks, which are continuously generated from multiple longitudinal and transverse surface plasmon modes and are supported by the hybrid nanowires, are observed directly. The absorption feature can be also tuned by various operational conditions. The proposed structure is made by in-complex nano-fabricating techniques comparing with the another and it provides acceptable broadband absorptivity.

Interband, Surface Plasmon and Fano Resonances in Titanium Carbide (MXene) Nanoparticles in the Visible to Infrared Range

Since the discovery of the optical properties of two-dimensional (2D) titanium carbide (MXene) conductive material, an ever increasing interest has been devoted towards understanding it as a plasmonic substrate or nanoparticle. This noble metal-free alternative holds promise not only due to its lower cost but also its 2D nature, hydrophilicity and apparent bio-compatibility. Herein, the optical properties of the most widely studied Ti3C2Tx MXene nanosheets are theoretically analyzed and absorption cross-sections are calculated exploiting available experimental data on its dielectric function. The occurrence of quadrupole surface plasmon mode in the optical absorption spectra of large MXene nanoparticles is demonstrated for the first time. The resonance wavelengths corresponding to interband transitions, longitudinal and transversal dipole oscillations and quadrupole longitudinal surface plasmon mode are identified for single and coupled nanoparticles by modeling their shapes as ellipsoids, disks and cylinders. A new mechanism of excitation of longwave transversal surface plasmon oscillations by an external electric field perpendicular to the direction of charge oscillations is presented. Excitingly enough, a new effect in coupled MXene nanoparticles—Fano resonance—is unveiled. The results of calculations are compared to known experimental data on electron absorption spectroscopy, and good agreement is demonstrated.

Semiconductor Quantum Plasmonics.

We investigate the frontier between classical and quantum plasmonics in highly doped semiconductor layers. The choice of a semiconductor platform instead of metals for our study permits an accurate description of the quantum nature of the electrons constituting the plasmonic response, which is a crucial requirement for quantum plasmonics. Our quantum model allows us to calculate the collective plasmonic resonances from the electronic states determined by an arbitrary one-dimensional potential. Our approach is corroborated with experimental spectra, realized on a single quantum well, in which higher order longitudinal plasmonic modes are present. We demonstrate that their energy depends on the plasma energy, as is also the case for metals, but also on the size confinement of the constituent electrons. This work opens the way toward the applicability of quantum engineering techniques for semiconductor plasmonics.

Photoluminescence of single gold nanorods following nonlinear excitation.

The photoluminescence (PL) mechanisms of gold nanorods following nonlinear excitation are described. Using single-particle nonlinear optical measurements, we compare PL signals resulting from both the plasmon-resonant and non-resonant excitations. In both cases, spectrally broad interband PL emission was observed. However, we also show that resonant excitation of the longitudinal plasmon mode leads to an increased photonic density of states at energies corresponding to the transverse plasmon resonance. This increased density of states is achieved by a multi-step mechanism, which is initiated by three-photon excitation and followed by an Auger relaxation process. Importantly, the results show that nonlinear excitation can lead to energy and polarization modulation of nanoparticle optical signals that are not observed using linear excitation. This work also demonstrates the effectiveness of single-nanoparticle PL studies for understanding how plasmon-resonant excitations can be used to modify hot carrier distributions.

Nonlocality Induced Cherenkov Threshold

AbstractCherenkov radiation is generally believed to be threshold‐free in hyperbolic metamaterials owing to the extremely large photonic density of states in classical local framework. Although recent advances in nonlocal and quantum plasmonics extend our understanding of light‐matter interactions in metamaterials, how such effects influence Cherenkov radiation in hyperbolic metamaterials still remains unknown. Here, it is demonstrated that effects of nonlocality add a new degree of freedom to engineer Cherenkov thresholds in hyperbolic metamaterials. The interplay between finite structural dimensions and nonlocal nature of metallic electrons results in a nonzero Cherenkov threshold. Counterintuitively, such nonlocality‐induced Cherenkov threshold can be significantly smaller than the classically predicted one if the metamaterial is designed to work around the epsilon‐near‐zero frequency. This phenomenon is attributed to the excitation of longitudinal plasmon modes which are absent in classical electromagnetic framework. These findings apply to a general class of hyperbolic materials, including metallodielectric layered structures, nanorod/nanoribbon arrays, hyperbolic van der Waals crystals, etc.