Simulations of the Surface Plasmon Resonances of Au@Ag Core-Shell Nanocubes: Effect of Core-Shell Size Ratio

Plasmonics - This paper reports a systematic investigation on the optical properties of Au@Ag core-shell nanocubes as a function of the core-shell size ratio with the boundary element method...     

Localized Surface Plasmon Resonances of Simple Tunable Plasmonic Nanostructures

Plasmonics - We derive and present systematic relationships between the analytical formulas for calculation of the localized surface plasmon resonances (LSPR) of some plasmonic nanostructures which...     

Shell Thickness-Dependent Plasmon Coupling and Creation of SERS Hot Spots in Au@Ag Core-Shell Nanostructures

The main objective of the present study is to investigate the shell thickness-dependent Raman enhancement activity of silver-coated gold nanoparticles (Au@Ag NPs) when bound to a model analyte 2-mercaptobenzoic acid (2-MBA). With an optimized Ag:Au ratio, dimeric and trimeric Au@Ag nanostructures were prepared in the presence of 2-MBA and are characterized by spectroscopic and microscopic techniques. These dimeric junctions act as hot spots and the molecules trapped at these junctions showed higher Raman signal enhancements due to the presence of amplified electric field.     

Eigenmode Decomposition of the Near-Field Enhancement in Localized Surface Plasmon Resonances of Metallic Nanoparticles

I present a direct and intuitive eigenmode method that evaluates the near-field enhancement around the surface of metallic nanoparticles of arbitrary shape. The method is based on the boundary integral equation (BIE) in the electrostatic limit. Besides the nanoparticle polarizability and the far-field response, the near-field enhancement around nanoparticles can be also conveniently expressed as an eigenmode sum of resonant terms. Moreover, the spatial configuration of the near-field enhancement depends explicitly on the eigenfunctions of both the BIE integral operator and of its adjoint. It has also established a direct physical meaning of the two types of eigenfunctions. While it is well known that the eigenfunctions of the BIE operator are electric charge modes, it is less known and used that the eigenfunctions of the adjoint represent the electric potential generated by the charge modes. For the enhanced spectroscopies, the present method allows an easy identification of hot spots which are located in the regions with maximum charge densities and/or regions with fast variations of the electric potential generated by the charge modes on the surface. This study also clarifies the similarities and the differences between the far-field and the near-field behavior of plasmonic systems. Finally, the analysis of concrete examples like the nearly touching dimer, the prolate spheroid, and the nanorod illustrate some modalities to improve the near-field enhancement.     

Theoretical Study of Sensitivity and Localized Surface Plasmon Resonance of Ag-Dielectric Core-Shell Multi-layered Nanosphere

Localized surface plasmon resonances (LSPRs) of Ag-dielectric-Ag multi-layered nanoshell are studied by quasi-static approximation and plasmon hybridization theory. Absorption properties of multi-layered nanoshell with the silver core and nanoshell separated by a dielectric layer exhibit strong coupling between the core and nanoshell. The result shows absorption spectrum of LSPRS is influenced by the refractive index of surrounding medium, the dielectric constant of middle dielectric layer, the thickness of inner core radius and outer shell layer. LSPR shift of the longest wavelength \(\left |\omega _{-}^{-}\right >\) is red-shifted with increasing the inner core radius. It is interesting to find that longer wavelength \(\left |\omega _{-}^{+}\right >\) mode is mainly effected by the ratio constant of the surrounding medium refractive index ε ₄ to the middle layer dielectric constant ε ₂. \(\left |\omega _{-}^{+}\right >\) mode takes place a blue-shift with increasing inner core radius when ε ₂ > ε ₄, a red-shift when ε ₂ < ε ₄, and no-shifting when ε ₂ = ε ₄. However, the influence of dielectric layer radius to \(\left |\omega _{-}^{+}\right >\) mode shows the different property as that of increasing the inner core radius. The underlying mechanisms are analyzed with the plasmon hybridization theory and the distribution of induced charge interaction between the inner core and outer shell. In addition, the influence of core radius, middle dielectric layer radius and outer shell radius to sensitivity of Ag-dielectric-Ag multi-layered nanoshell are also reported, a higher sensitivity could be gotten by adjusting geometrical parameters. Our theoretical study could give an easy way to analyze properties of the core-shell nanosphere based on plasmon hybridization theory and the induced charge interaction, and usefully broaden the applications in nano-optics.     

Surface Plasmon Resonances of Clustered Nanoparticles

Linear clusters made by tightly connecting two or more metallic nanoparticles have new types of surface plasmon resonances as compared with isolated nanoparticles. These new resonances are sensitive to the size of the junction and to the number of interconnected particles and are described by eigenmodes of a boundary integral equation. This formulation allows effective separation of geometric and shape contribution from electric properties of the constituents. Results for particles covered by a thin shell are also provided highlighting ultrasensitive sensing applications. The present analysis sheds a new light on the interpretation of recent experiments.     

Study of Surface Plasmon Resonances of Core-Shell Nanosphere: A Comparison between Numerical and Analytical Approach

An investigation of the wavelength dependent extinction spectra of coated sphere with different core@shell compositions based on discrete dipole approximation technique has been presented in this paper. We have used combinations of A g, A u, and S i O ₂ for this analysis. Specifically, we study the impact of spherical core-shell thickness on its surface plasmon resonance (SPR) peak positions and corresponding spectral widening in distinct regimes of the spectrum. We observe that SPR peak of core-shell nanoparticle(CSNP) can be tuned over the visible to near-infrared spectrum region by manipulating the core/shell ratio and composition of core and shell. Specifically, for dielectric@metal (core@shell) nanoparticle, SPR peak position shifted towards lower wavelength as we increase the shell thickness, which is opposite to the SPR behavior of metal@dielectric. The extinction spectrum shows linear relation between SPR position and thickness of the shell. Further, we observed two resonant peaks for the case of metal@metal CSNP. The SPR peak of Au@Ag (a _eff 100 nm with shell thickness 8 nm) reveals two resonant peak corresponding to Au (594 nm) in red domain, while the peak in blue domain corresponds to Ag (402 nm). We also observe that optical resonance of CSNP can be tuned across the near-infrared region by changing the surrounding medium of higher refractive index. Further, near field pattern of core@shell geometry at resonance wavelength is also shown in the present study. We have also compared the numerical and analyticalmethod for smaller size CSNP with varying thickness and the results show good agreement.     

Slab Thickness Dependence of Localized Surface Plasmon Resonance Behavior in Gold Nanorings

We present detailed experimental and numerical studies of plasmonic properties of gold nanoring (NR) arrays with different slab thicknesses from 15 to 125 nm. The hybrid plasmon resonances for the bonding and antibonding modes in gold NRs exhibit a high slab thickness dependence behavior in optical properties. For the thinner slab thickness below 50 nm, both hybrid modes show large spectral tunabilities by varying the slab thickness. Furthermore, for such hollow NR structure, the enhancements of electric field intensities at the inner and outer ring surfaces when reducing the slab thickness are investigated. We observe a significant transition of field distributions for the antibonding mode. All these features can be understood by surface charge distributions from our simulations. The results of this study offer a potential strategy to design a composite plasmonic nanostructure with large field enhancement for numerous applications.     

Tuning the Fano Resonance Between Localized and Propagating Surface Plasmon Resonances for Refractive Index Sensing Applications

Localized and propagating surface plasmon resonances are known to show very pronounced interactions if they are simultaneously excited in the same nanostructure. Here, we study the Fano interference that occurs between localized surface plasmon resonance (LSPR) and propagating surface plasmon polariton (SPP) modes by means of phase-sensitive spectroscopic ellipsometry. The sample structures consist of periodic gratings of gold nanodisks on top of a continuous gold layer and a thin dielectric spacer, in which the structural dimensions were tuned in such a way that the dipolar LSPR mode and the propagating SPP modes are excited in the same spectral region. We observe pronounced anti-crossing and strongly asymmetric line shapes when both modes move to each other’s vicinity, accompanied of largely increased phase differences between the respective plasmon resonances. Moreover, we show that the anti-crossing can be exploited to increase the refractive index sensitivity of the localized modes dramatically, which result in largely increased values for the figure-of-merit which reaches values between 24 and 58 for the respective plasmon modes.     

InGaN/GaN MQW Photoluminescence Enhancement by Localized Surface Plasmon Resonance on Isolated Ag Nanoparticles

Spectroscopic study of photoluminescence (PL) enhancement due to the coupling of the light emitters in InGaN/GaN multiple quantum wells (MQWs) with the localized surface plasmon (LSP) resonance on silver (Ag) nanoparticles (NPs) is performed using the confocal microscopy and scanning near-field optical microscopy (SNOM) techniques. The paper is focused on revealing the emission enhancement due to coupling with a single metal nanoparticle. The enhancement is confirmed by time-resolved study of differential transmission (DT). The enhancement suppression caused by potential fluctuations due to the variations of indium content and quantum well (QW) width is also studied. A strong photoexcitation intensity dependence of the emission enhancement due to spectral runaway of the MQW emission from the resonance as carrier density increases is observed both in spatially integrated spectra and in the vicinity of a single nanoparticle.     

Surface Plasmon Dynamics of High-Aspect-Ratio Gold Nanorods

Ultrafast transient absorption studies are reported for high-aspect-ratio gold nanorods that were fabricated by electrochemical deposition in polycarbonate templates. The nanorods are 60 nm in diameter with distribution of lengths of up to 6 μm. The average aspect ratio was ∼50, resulting in a longitudinal surface plasmon resonance (SPR_L) band in the mid-IR, as well as a transverse (SPR_T) band in the visible. The rods were excited at 400 nm and probed at a range of wavelengths from the visible to the mid-IR to interrogate both SPR bands. The dynamics observed, including the electron–phonon coupling time and coherent acoustic breathing mode oscillations, closely resemble those previously reported for gold spherical nanoparticles and smaller-aspect-ratio nanorods. The electron–phonon coupling time was similarly determined to be 3.3 ± 0.2 ps for both of the SPR bands. Also, oscillations with a 32-ps period were observed for probing near the SPR_T band in the visible region due to impulsive coherent excitation of the acoustic breathing mode, which are consistent with the 60-nm diameter of the nanorods determined by scanning electron microscopy. The results demonstrate that the dynamics for long gold nanorods are similar to those for smaller nanoparticles. Gerald M. Sando is a NRL-ASEE Research Associate     

Tunable Absorption of Light via Localized Plasmon Resonances on a Metal Surface with Interspaced Ultra-thin Metal Gratings

We studied optical reflection properties of complex metal (Ag) surfaces with close-interspaced ultra-thin metal gratings. Prominent reflection minima were observed corresponding to enhanced absorption of light. Our analysis convinced us that the period-dependent mode is ascribed to Bloch-wave-like resonances of surface plasmon waves at the overall effective metal surfaces, and the ridge-width-dependent mode to Fabry-Pérot-like resonances of localized surface plasmon waves in micro-/nanocavities defined by regions of the grating ridges. The latter resonance mode is shown highly tunable with variation of the grating ridge width. Such structures may be applied in spectrum resolvable photovoltaic devices, bio-sensing, and studying optical properties of cavity-coupled molecules or functional nanomaterials.     

Broadband Tunable and Double Dipole Surface Plasmon Resonance by TiO2 Core/Ag Shell Nanoparticles

A design of a TiO₂ core and Ag shell spherical nanoparticle is theoretically presented. The nanoparticles display double dipole plasmonic resonance peaks: one located at the ultraviolet range, the other is widely tunable from the visible to the near infrared region. The tunability can be easily controlled by varying the sizes of the core and the shell. The near field patterns of the double plasmonic resonance peaks are analyzed, and the dipole resonance modes for those two peaks are confirmed for the suitable core–shell sizes.     

The Study of Surface Plasmon in Au/Ag Core/Shell Compound Nanoparticles

Au/Ag core/shell nanoparticles are fabricated by laser-ablating Ag plates in Au colloid solution. The absorption band is found to blue shift with increasing ablation time. Mie theory calculations show that the shift is caused by the increase of the Ag shell thickness. The average Ag shell thickness can be determined from the measured absorption peak. Using the plasmon hybridization approach, we show that the absorption band around 510 nm originates from an anti-bonding mode ω _?+ caused by the interaction between a bonding Ag shell mode ω _?? and Au sphere mode ω _S-Au. The blue shift of the ω _?+ mode with the increase of Ag shell thickness is also well predicted by the hybridization theory.     

Emission Enhancement of Light-Emitting Diode by Localized Surface Plasmon Induced by Ag Inserts in p-GaN and TiO2-Ag Grating

Plasmonics - The structure composed of a TiO2-Ag grating on the surface of p-GaN layer is proposed and investigated. The performance of light-emitting diodes is enhanced by coupling of localized...     

Development of Localized Surface Plasmon Resonance-Based Point-of-Care System

Plasmonics - This paper describes our point-of-care system development based on localized surface plasmon resonance (LSPR). Although LSPR has been a hot research area for a few decades, there are...     

A Localized Surface Plasmon Resonance Biosensor Based on Integrated Controllable Au2S/AuAgS-Coated Gold Nanorods Composite

In this work, we have demonstrated that the exquisite optical properties based on localized surface plasmon resonance (LSPR) of Au₂S/AuAgS-coated gold nanorods (Au₂S/AuAgS-coated GNRs) can be utilized to develop a simple and sensitive biosensor, and goat anti-human IgG can be detected by the human IgG probe as low as 0.2 nM. Moreover, we introduce an integrated LSPR biosensor constructed by integrating Au₂S/AuAgS-coated GNRs immobilized on glass slide and isolated Au₂S/AuAgS-coated GNRs in the form of liquid. The detection of target binding was performed via direct spectral changes induced by changes of refractive index in the vicinity of individual particles. The integrated LSPR optical biosensor is label-free, cost-effective, and easy to fabricate and requires only a visible/near-infrared spectrometer for detection purposes. Additionally, the investigation on the mutual influence of the two types of nanorods in the integrated LSPR biosensor was performed. The results of separate experiments indicate that the nanorods in the form of isolate or in integrated exhibit a similar behavior.     

Coupling Behaviors of Surface Plasmon Polariton and Localized Surface Plasmon with an InGaN/GaN Quantum Well

Plasmonics - Surface plasmon (SP) coupling behaviors of an InGaN/GaN quantum well (QW) with surface plasmon polariton (SPP) induced on a smooth Ag-film/GaN interface and localized surface plasmon...     

The Tunable and Well-Controlled Surface Plasmon Resonances of Au Hollow Nanostructures by a Chemical Route

Au plasmonic hollow spherical nanostructures were synthesized by electrochemical reduction (GRR, the Galvanic Replacement Reaction) using Ag nanoparticles as templates. From UV-visible absorption spectroscopy, it was found that the surface plasmon resonance (SPR) of gold hollow spherical nanostructures first showed red shift and then blue shift. However, further addition of gold precursor (HAuCl₄) resulted into a red shift of SPR peak. The morphological changes from Ag nanoparticles to Au hollow nanostructures were assessed by transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDX)analysis. The Mie Scattering theory based simulations of SPR of Au hollow nanostructures were performed which are in good agreement with the experimental observations. Based on the experimental observations and theoretical calculations, a complete growth mechanism for Au hollow nanostructures is proposed.     

Surface Plasmon Resonances of Metallic Nanostars/Nanoflowers for Surface-Enhanced Raman Scattering

We investigate theoretically the optical properties associated to plasmon resonances of metal nanowires with cross section given by low-order Chebyshev nanoparticles (like rounded-tip nanostars or nanoflowers). The impact of the nanoflower shape is analyzed for varying symmetry and deformation parameter through the spectral dependence of resonances and their corresponding near field distributions. Large field intensity enhancements are obtained at the gaps between petals, apart from the tips themselves, which make these nanostars/nanoflowers specially suitable to host molecules for surface-enhanced Raman scattering sensing applications.