Tunable Properties of Surface Plasmon Resonances: The Influence of Core–Shell Thickness and Dielectric Environment

In the present study, we have investigated the extinction spectra of coated sphere (using dipole model) with different core–shell radius, in which the core is TiO₂ and the shell is made up of silver or gold nanoparticles. Nanoparticles exhibit surface plasmon resonance peak; these plasmonic peaks are highly tunable in wavelength range of 300 to 1,100 nm; in fact, the blue and red shifting of resonance peak highly depends on the core–shell thickness. The broadness of resonance peaks are analysed in terms of full width at half maxima (FWHM), and the width of these resonance peaks is also the function of core–shell radius.     

Plasmonic Core–Shell Nanowires for Enhanced Second-Harmonic Generation

We demonstrate the synthesis and characterization of core–shell nanowires consisting of a non-centrosymmetric KNbO₃ core and a gold shell. This type of nanostructure combines the nonlinear optical properties of the core and the plasmonic resonance of the shell in the near infrared spectral range. We report successful spectroscopic measurements on coated single wires to characterize the resonant behavior of the gold shell. We present a theoretical model based on the electrostatic approximation to estimate the enhancement of second-harmonic generation in a nanowire due to the shell. It suggests a possible enhancement factor of up to 4,000 for a system with a nanoshell of 16 nm thickness at a wavelength of 900 nm.     

Dual-Band Plasmonic Enhancement of Ag-NS@SiO2 on Gain Medium??s Spontaneous Emission

We present a theoretical study on plasmonic enhancement of molecular fluorescence near a nanocomposite, Ag nanoshell (Ag-NS) coated by a gain medium of molecule-doped SiO₂ layer. We use an average enhancement factor (AEF), which considers contributions from all possible orientations and locations of molecules in the silica layer to estimate the overall performance of Ag-NS@SiO₂ at specific excitation and emission wavelengths. Our results on the AEF reveal that Ag-NS@SiO₂ is a dual-band enhancer on the spontaneous emission of the gain medium; one is a narrowband in a shorter wavelength regime (quadrupole mode) and the other is a broadband in a longer wavelength regime (dipole mode). These two bands are tunable by adjusting the core size and the thickness of the Ag shell. Due to this merit, Ag-NS@SiO₂ has great potentials to enhance Forster resonance energy transfer between a donor and a corresponding acceptor with large Stokes shifts.     

Surface‐Plasmon Assisted Energy Conversion in Dye‐Sensitized Solar Cells

In this study, the effect of plasmonic core‐shell structures, consisting of dielectric cores and metallic nanoshells, on energy conversion in dye‐sensitized solar cells (DSSCs) is investigated. The structure of the core‐shell particles is controlled to couple with visible light so that the visible component of the solar spectrum is amplified near the core‐shell particles. In core‐shell particle – TiO₂ nanoparticle films, the local field intensity and light pathways are increased due to the surface plasmons and light scattering. This, in turn, enlarges the optical cross‐section of dye sensitizers coated onto the mixed films. When 22 vol% of core‐shell particles are added to a 5 μm thick TiO₂ film, the energy conversion efficiency of DSSCs increases from 2.7% to 4.0%, in spite of a more than 20% decrease in the amount of dyes adsorbed on the composite films. The correlation between core‐shell particle content and energy conversion efficiency in DSSCs is explained by the balance among near‐field effects, light scattering efficiency, and surface area in the composite films.     

Enhanced Optical Absorption and Spectral Photocurrent in a-Si:H by Single- and Double-Layer Silver Plasmonic Interfaces

Single and double plasmonic interfaces consisting of silver nanoparticles embedded in media with different dielectric constants including SiO₂, SiN_x, and Al:ZnO have been fabricated by a self-assembled dewetting technique and integrated to amorphous silicon films. Single plasmonic interfaces exhibit plasmonic resonances whose frequency is red-shifted with increasing particle size and with the thickness of a dielectric spacer layer. Double plasmonic interfaces consisting of two different particle sizes exhibit resonances consisting of double minima in the transmittance spectra. The optical extinction of a-Si:H deposited on these interfaces is broadened into the red indicating higher absorption and/or scattering at wavelengths higher than those typically absorbed by a-Si:H without plasmonic interfaces. While the photocurrent shows an overall decrease for the samples with the interfaces, significant enhancement of photocurrent is observed near the low-energy edge of the bandgap (600–700 nm). These results correlate well with the broadened extinction spectra of the interfaces and are interpreted in terms of enhanced absorption in that region.     

The Effect of Negative Curvature on the Plasmonic Coupling of Concentric Core–Shell Metallic Nanostructures

Negative curvature-dependent localized surface plasmon resonance (LSPR) properties of concentric core–shell metallic nanostructure have been studied using quasistatic approach and plasmon hybridization theory. Whether in single-layered gold nanoshell or double gold nanoshells, the oscillating surface charges always concentrate close to the poles of the metal surface with negative curvature, which results in the anisotropic local electric field distribution and affects both the inter-surface plasmonic coupling and inter-shell plasmonic coupling. Therefore, the change of the radius of the gold surface with negative curvature could modulate the plasmon hybridization and lead to the LSPR shifting. The physical mechanism of the negative curvature-dependent LSPR presents a potential for design and fabrication of nanoscale optical device based on core–shell type metallic nanostructures.     

A Study of the Surface Plasmon Resonance of Silver Nanoparticles by the Discrete Dipole Approximation Method: Effect of Shape,Size, Structure,and Assembly

The surface plasmon resonance (SPR) of silver nanoparticles (AgNPs) was studied with the discrete dipole approximation considering different shapes, sizes, dielectric environments, and supraparticles assemblies. In particular, we focused our simulations on AgNPs with sizes below 10 nm, where the correction of silver dielectric constant for intrinsic size effects is necessary. We found that AgNPs shape and assembly can induce distinctive features in the extinction spectra and that SPR is more intense when AgNPs have discoid or flat shapes and are embedded in a dielectric shell with high refractive index. However, the SPR loses much of its distinctive features when size effects and stabilizing molecules induce significant broadening of the extinction bands that is often observed in the case of thiolated AgNPs smaller than about 5 nm. These results are useful indications for in situ characterization and monitoring of AgNPs synthesis and for the engineering of AgNPs with new plasmonic properties.     

Broadband Enhancement of PbS Quantum Dot Solar Cells by the Synergistic Effect of Plasmonic Gold Nanobipyramids and Nanospheres

For the first time, the plasmonic gold bipyramids (Au BPs) are introduced to the PbS colloidal quantum dot (CQD) solar cells for improved infrared light harvesting. The localized surface plasmon resonance peaks of Au BPs matches perfectly with the absorption peaks of conventional PbS CQDs. Owing to the geometrical novelty of Au BPs, they exhibit significantly stronger far‐field scattering effect and near‐field enhancement than conventional plasmonic Au nanospheres (NSs). Consequently, device open‐circuit voltage (V_oc) and short‐circuit current (J_sc) are simultaneously enhanced, while plasmonic photovoltaic devices based on Au NSs only achieve improved J_sc. The different effects and working mechanisms of these two Au nanoparticles are systematically investigated. Moreover, to realize effective broadband light harvesting, Au BPs and Au NSs are used together to simultaneously enhance the device optical and electrical properties. As a result, a significantly increased power conversion efficiency (PCE) of 9.58% is obtained compared to the PCE of 8.09% for the control devices due to the synergistic effect of the two plasmonic Au nanoparticles. Thus, this work reveals the intriguing plasmonic effect of Au BPs in CQD solar cells and may provide insight into the future plasmonic enhancement for solution‐processed new‐generation solar cells.     

Optical Absorption Modeling of Plasmonic Organic Solar Cells Embedding Silica-Coated Silver Nanospheres

We numerically study plasmonic solar cells in which a square periodic array of core–shell Ag@SiO₂ nanospheres (NSs) are placed on top of the indium tin oxide (ITO) layer using a 3D finite-difference time-domain (FDTD) method. We investigate the influence of various parameters such as the periodicity of the array, the Ag core diameter, the active layer thickness, the shell thickness, and the refractive index of the shell materials on the optical performance of the organic solar cells (OSC). Our results show that the optimal periodicity of the array of NSs is dependent on the size of Ag core NSs in order to maximize optical absorption in the active layer. A very thin active layer (<70 nm) and an ultrathin (<5 nm) SiO₂ shell are needed in order to obtain the highest optical absorption enhancement. Strong electric field localization is observed around the plasmonic core–shell nanoparticles as a result of localized surface plasmon resonance (LSPR) excited by Ag NSs with and without silica shell. Embedding 50 nm Ag NSs with 1-nm-thick SiO₂ shell thickness on top of ITO leads to an enhanced intrinsic optical absorption in a 40-nm-thick poly(3-hexylthiophene):phenyl-C₆₁-butyric acid methyl ester (P3HT:PCBM) active layer by 24.7% relative to that without the NSs. The use of 1-nm-thick ZnO shell instead of SiO₂ leads to an enhanced intrinsic absorption in a 40-nm-thick P3HT:PCBM active layer by 27%.

     

Substrate-Independent Lattice Plasmon Modes for High-Performance On-Chip Plasmonic Sensors

We systematically study the lattice plasmon resonance structures, which are known as core/shell SiO₂/Au nanocylinder arrays (NCAs), for high-performance, on-chip plasmonic sensors using the substrate-independent lattice plasmon modes (LPMs). Our finite-difference time-domain simulations reveal that new modes of localized surface plasmon resonances (LSPRs) show up when the height-diameter aspect ratio of the NCAs is increased. The height-induced LSPRs couple with the superstrate diffraction orders to generate the substrate-independent LPMs. Moreover, we show that the high wavelength sensitivity and the narrow linewidth of the substrate-independent LPMs lead to the plasmonic sensors with high figure of merit (FOM) and high signal-to-noise ratio (SNR). In addition, the plasmonic sensors are robust in asymmetric environments for a wide range of working wavelengths. Our further study of both far- and near-field electromagnetic distribution in the NCAs confirms the height-enabled tunability of the plasmonic “hot spots” at the sub-nanoparticle resolution and the large field enhancement in the substrate-independent LPMs, which are responsible for the high FOM and SNR of the plasmonic sensors.     

Numerical Simulation of Broadband Scattering by Coated and Noncoated Metal Nanostructures Using Discrete Dipole Approximation Method

We suggest numerical method to study the optical response of metal nanostructures. The analysis of optical properties such as scattering and absorption by coated and noncoated nanogeometry has been done using discrete dipole approximation (DDA) method. The core-shell nanogeometry supports surface plasmon resonances, which are highly tunable from 400 to 1100 nm. The tunability of surface plasmon resonance (SPR) highly depends on the structural anisotropy and chosen core-shell material. Further, we have observed that aspect ratio is one of the key parameter to decide the nature and position of the plasmonic peaks and magnitude of optical cross section. We have also shown that coated nanospheroid is a more appropriate geometry as compared to coated nanosphere and noncoated nanospheroid in terms of wide tunability of surface plasmon resonance. The wide tunability in SPR is observed for the effective radii 90 nm core-shell (Au@SiO₂) nanospheroid with aspect ratio 0.1.     

Decorated Core-Shell Architectures: Influence of the Dimensional Properties on Hybrid Resonances

Emerging nanoplasmonics utilizing asymmetric core-shell architectures present opportunities to precisely control the plasmon position and signal amplification within a single particle. In particular, asymmetric gold nanorods, assembled into a “matryoshka” structure (gold nanorod core, silica spacer shell, and outer gold shell) have the unique ability to enhance and precisely manipulate the plasmonic signature when compared to single gold nanorods via the generation of hybridized plasmonic modes. Currently, the fundamental understanding of the impact of the gold nanorod matryoshka dimensional parameters on the subsequent resonance behavior is incomplete. In this work, we elucidate the structural-hybridized resonance relationship of gold nanorod nanomatryoshka designs by experimentally varying the key geometrical properties; including silica spacer thickness, gold nanorod core size, and gold shell thickness/continuity.     

Optical and Thermal Enhancement of Plasmonic Nanofluid Based on Core/Shell Nanoparticles

The plasmonic effect is introduced in solar thermal areas to enhance light harvest and absorption. The optical properties of plasmonic nanofluid are simulated by finite difference time domain (FDTD) method. Due to the excitation of localized surface plasmon resonance (LSPR) effect, an intensive absorption peak is observed at 0.5 μm. The absorption characteristics are sensitive to particle size and concentration. As the particle size increases, the absorption peak is broadened and shifted to longer wavelength. The absorption of SiO₂/Ag plasmonic nanofluid is improved gradually as the volume concentration increases, especially in the UV region. The absorption edge is shifted from 0.6 to 1.0 μm as the volume concentration increases from 0.001 to 0.01. The thermal simulation of suspended SiO₂/Ag nanoparticle shows a uniform temperature rise of 17.91 K under solar irradiation (AM 1.5), while under the same condition, the temperature rises in Ag nanoparticle and Al nanoparticle are 11.12 and 5.39 K, respectively. The core/shell plasmonic nanofluid exhibits a higher photothermal performance, which has a potential application in photothermal areas. A higher temperature rise can be obtained by improving the incident light intensity or optical absorption properties of nanoparticles.     

Plasmonic Modes of Ag Nanoshell Excited by Bi-Dipole

We studied plasmonic dipole, quadrupole, and sextupole modes of Ag nanoshell (NS) excited by a pair of aligned radial electric dipoles (bi-dipole) in symmetric and antisymmetric configurations by using dyadic Green’s functions. The mutual excitation rate and the radiative and nonradiative powers of bi-dipole in the presence of Ag NS were analyzed. Our results show that these modes are in accordance with the surface plasmon resonances of Ag NS irradiated by a polarized plane wave. In addition, the mutual excitation rate retains local maxima at these modes. Moreover, the quadrupole and octupole modes are only excited in the cases of the symmetric radial bi-dipole, while the dipole and sextupole modes are only excited in the cases of the antisymmetric ones. The dipole mode is broadband, while the other higher-order modes are narrowband. Moreover, all of these plasmonic modes are red-shifted as the ratio of the core radius to the shell thickness increases.     

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.     

Higher Order Tunable Fano Resonances in Multilayer Nanocones

We present a computational study of the plasmonic response of a gold–silica–gold multilayered nanostructure based on truncated nanocones. Symmetry breaking is introduced by rotating the nanostructure and by offsetting the layers. Nanocones with coaxial multilayers show dipole–dipole Fano resonances with resonance frequencies depending on the polarization of the incident light, which can be changed by rotating the nanostructure. By breaking the axial symmetry, plasmonic modes of distinct angular momenta are strongly mixed, which provide a set of unique and higher order tunable Fano resonances. The plasmonic response of the multilayered nanocones is compared to that of multishell nanostructures with the same volume and the former are discovered to render visible high-order dark modes and to provide sharp tunable Fano resonances. In particular, higher order tunable Fano resonances arising in non-coaxial multilayer nanocones can vary the plasmon lines at various spectral regions simultaneously, which makes these nanostructures greatly suitable for plasmon line shaping both in the extinction and near field spectra.     

Plasmonic Perovskite Solar Cells Utilizing Au@SiO<Subscript>2</Subscript> Core-Shell Nanoparticles

The role of Au@SiO₂ core-shell nanoparticles on optical properties of perovskite solar cells has been explored using both the theoretical computations and the experiments. A quasi-static model is used to study the surface plasmon resonances (SPRs) of Au@SiO₂ core-shell nanospheres. Au@SiO₂ core-shell nanoparticles, with varying shell thickness and core radius, were assumed to be embedded in methylammonium lead triiodide (CH₃NH₃PbI₃) perovskite active layer. Enhanced absorption in the active layer is obtained due to the near-field plasmonic effect of the embedded core-shell nanoparticles. Theoretical modelling shows that a shell thickness of 1 nm and core diameter of 20 nm provide absorption enhancement in the orange-red region of the electromagnetic spectrum. Experiments performed using ～20-nm-sized Au@SiO₂ core-shell nanoparticles (with a shell thickness of ～1 nm) clearly demonstrate the enhanced absorption and the resulting enhancement in photocurrent due to the plasmonic effects. An efficiency enhancement of over 18 % is obtained for the best plasmonic perovskite solar cell containing Au@SiO₂ nanoparticles in Au@SiO₂-TiO₂ weight ratio of ～1 %. Incident photon-to-current conversion efficiency (IPCE) data also showed enhancement in photocurrent for the plasmonic device. The quasi-static modelling approach provides a good correlation between theory and experiment.     

Synthesis,Characterization, and Functionalization of Hybrid Au/CdS and Au/ZnS Core/Shell Nanoparticles

Plasmonic nanoparticles are an attractive material for light harvesting applications due to their easily modified surface, high surface area and large extinction coefficients which can be tuned across the visible spectrum. Research into the plasmonic enhancement of optical transitions has become popular, due to the possibility of altering and in some cases improving photo-absorption or emission properties of nearby chromophores such as molecular dyes or quantum dots. The electric field of the plasmon can couple with the excitation dipole of a chromophore, perturbing the electronic states involved in the transition and leading to increased absorption and emission rates. These enhancements can also be negated at close distances by energy transfer mechanism, making the spatial arrangement of the two species critical. Ultimately, enhancement of light harvesting efficiency in plasmonic solar cells could lead to thinner and, therefore, lower cost devices. The development of hybrid core/shell particles could offer a solution to this issue. The addition of a dielectric spacer between a gold nanoparticles and a chromophore is the proposed method to control the exciton plasmon coupling strength and thereby balance losses with the plasmonic gains. A detailed procedure for the coating of gold nanoparticles with CdS and ZnS semiconductor shells is presented. The nanoparticles show high uniformity with size control in both the core gold particles and shell species allowing for a more accurate investigation into the plasmonic enhancement of external chromophores.     

Elucidating the Sole Contribution from Electromagnetic Near‐Fields in Plasmon‐Enhanced Cu2O Photocathodes

Despite many promising reports of plasmon‐enhanced photocatalysis, the inability to identify the individual contributions from multiple enhancement mechanisms has delayed the development of general design rules for engineering efficient plasmonic photocatalysts. Herein, a plasmonic photocathode comprised of Au@SiO₂ (core@shell) nanoparticles embedded within a Cu₂O nanowire network is constructed to exclusively examine the contribution from one such mechanism: electromagnetic near‐field enhancement. The influence of the local electromagnetic field intensity is correlated with the overall light‐harvesting efficiency of the device through variation of the SiO₂ shell thickness (5–22 nm) to systematically tailor the distance between the plasmonic Au nanoparticles and the Cu₂O nanowires. A threefold increase in device photocurrent is achieved upon integrating the Au@SiO₂ nanoparticles into the Cu₂O nanowire network, further enabling a 40% reduction in semiconductor film thickness while maintaining photocathode performance. Photoelectrochemical results are further correlated with photoluminescence studies and optical simulations to confirm that the near‐field enhancement is the sole mechanism responsible for increased light absorption in the plasmonic photocathode.     

Tunable Fano Resonance Based Mode Interference in Waveguide-Cavity-Graphene Hybrid Structure

In this paper, a graphene strip is introduced into a metal-insulator-metal (MIM)-integrated square cavity hybrid structure; the transmission spectra are theoretically investigated by the finite different time domain (FDTD) methods. An asymmetric Fano resonance dip that has high figure of merit (FOM) value appears in the transmission band. According to the multimode interference coupled mode theory (MICMT) analytical method, the Fano resonance originates from the coherent coupling between TM₁₀ cavity magnetic mode and graphene plasmonic resonance electric mode. The center wavelength, full width at half maximum (FWHM), and FOM value of the Fano resonance can be tuned dynamically by altering the Fermi level of the graphene. Through breaking the symmetry of the hybrid structure or introducing double graphene strips with different Fermi level into hybrid structure, double Fano resonance are realized. This study can provide some theoretical basis and design reference for designing ultrahigh sensitivity plasmonic sensor.