Novel and Sensitive Core-Shell Nanoparticles Based on Surface Plasmon Resonance

In this paper, a rough silver core-shell nanoparticle with strong electric field enhancement in the vicinity of a bumpy structure on the silver core-shell surface is reported. A dipolar plasmonic mode of the silver nanoshell is investigated by using the quasi-static approach and plasmon hybridization theory, which analytical results identify the electric field enhancement spectra in which the enhancement is optimized. As the silver shell thickness is small, the hot spots play an important role in the plasmonic field enhancement. In addition, the deposition of a rough silver shell can generate a stronger near-field enhancement near the silver surface which is more desirable than that of a smooth silver shell for sensitive detection based on SPR and surface enhanced Raman scattering (SERS). The plasmonic field enhancement of a bumpy silver core-shell nanoparticle permits the detection and characterization of bovine serum albumin (BSA) protein molecule and hemoglobin solution with a high sensitivity.     

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.     

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.     

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.     

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.     

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.     

Enhanced Intermolecular Energy Transfer in the Vicinity of a Plasmonic Nanorice

The problem of radiationless Förster energy transfer between a donor and an acceptor molecule is studied in the vicinity of a metallic nanorice. Using a recently formulated effective medium theory, the modified dipole–dipole interaction between the molecules in the vicinity of a spheroidal metallic nanoshell can be easily formulated, from which huge enhancement of the energy transfer rate is obtained due to the resonant excitation of the bonding and the antibonding plasmonic modes of the nanoshell. Effects due to the different locations and orientations of the molecules are also studied. The results show that the plasmonic resonances depend mainly on the nanorice geometry and much less on the configuration of the molecules, whereas the enhancement is more sensitive to the relative orientations and locations of the molecules.     

The Effect of Bumpy Structure on Optical Properties of Bimetallic Nanoshells

In this paper, a sensitive bumpy bimetallic nanoshell for detection of thyroid cancer market (Thyroglobulin, Tg) and bovine serum albumin (BSA) proteins is reported. The physical origin of plasmonic properties of bimetal nanoshells is described by plasmon hybridization theory which indicates three intense and clearly separated plasmon modes. The electric field intensity enhancement of the bumpy bimetal nanoshell increases by ~559 %, at the surface of the bump in comparison with a smooth shell. The presence of bumpy structure on the nanoshell surface provides a high enhancement of the resulting Raman signal through an electromagnetic field of the order of 10⁷ which leads to an increase in sensitivity detection of Tg and BSA proteins. In addition, a refractive index (RI) sensitivity of 332.54 nm/RIU is achieved for this bumpy bimetallic nanoshell.     

Design of Plasmonic Nanoparticles for Efficient Subwavelength Light Trapping in Thin-Film Solar Cells

This paper explores geometry-sensitive scattering from plasmonic nanoparticles deposited on top of a thin-film amorphous silicon solar cell to enhance light trapping in the photo-active layer. Considering the nanoparticles as ideal spheroids, the broadband optical absorption by the silicon layer is analyzed and optimized with respect to the nanoparticle aspect ratio in both the cases of resonant (silver) and nonresonant (aluminum) plasmonic nanostructures. It is demonstrated how the coupling of sunlight with the semiconductor can be improved through tuning the nanoparticle shape in both the dipolar and multi-polar scattering regimes, as well as discussed how the native oxide shell formed on the nanospheroid surface after the prolonged action of air and moisture affects the light trapping in the active layer and changes the photocurrent generation by the solar cell.     

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%.

     

Strong Suppression of Surface Plasmon Radiation Damping Rate in Noble Metal Nanoshells

Radiation damping of surface plasmon oscillations in metallic nanoparticles is proportional to their volume. For relatively large particles, this canal dominates the other mechanisms of relaxation and becomes the main limiting factor for spectral sensitivity of nanoparticles. In this communication, we consider metallic nanoshell with the dielectric core and calculate the radiation damping rate of surface plasmon oscillations, depending on the geometry and dielectric constants of the surrounding environment and the core. It is shown that surface plasmon radiation damping in nanoshell is suppressed by several orders of magnitude as compared to the solid particle of the same outer radius. This effect is conditioned by strong redshift of surface plasmon frequencies with the decrease of shell thickness. It is also demonstrated that the radiation damping rate of core–shell particle is highly sensitive with respect to the refractive index of surrounding media.     

Numerical Study of Plasmonic Effects of Ag Nanoparticles Embedded in the Active Layer on Performance Polymer Organic Solar Cells

In this paper, the light absorption in the active layer of polymer solar cells (OPV) by using plasmonic nanocrystals with a hexagonal lattice structure is investigated. To study the relationship between the performance of the OPV solar cell and its active layer, a three-dimensional model of its morphology is utilized. Therefore, the three-dimensional (3D) finite-difference time-domain method and Lumerical software were used to measure the field distribution and light absorption in the active layer in terms of wavelength. OPV solar cells with bilayer and bulk heterojunction structured cells were designed using hexagonal lattice crystals with plasmonic nanoparticles, as well as core–shell geometry to govern a design to optimize light trapping in the active layer. The parameters of shape, material, periodicity, size, and the thickness of the active layer as a function of wavelength in OPV solar cells have been investigated. A very thin active layer and an ultra-thin shell were used to achieve the highest increase in optical absorption. The strong alternating electromagnetic field around the core–shell plasmonic nanoparticles resulting from the localized surface plasmon resonance (LSPR) suggested by the Ag plasmonic nanocrystals increased the intrinsic optical absorption in the active layer poly(3-hexylthiophene):phenyl-C61-butyric acid methyl ester (P3HT:PCBM). Based on the photovoltaic results, the short circuit current ranged from 19.7 to 26.7 mA/cm².

     

Strong Fluorescence Enhancement with Silica-Coated Au Nanoshell Dimers

Fluorescence intensity is vital for fluorescence sensing and imaging because it determines the sensing sensitivity and imaging brightness. This study reports plasmon-enhanced fluorescence by engineering plasmonic nanostructures, that are SiO₂-coated Au nanoshell dimers with a high yield exceeding 60 %. With this elaborately designed nanostructure, we show that the thin SiO₂ shell can conveniently distance the fluorophore from the underneath metal, thereby effectively avoiding fluorescence quenching. Meanwhile, the inner Au nanoshell dimers create abundant hot spots at particle-particle junctions and enable near-infrared fluorescence enhancement. The largest fluorescence enhancement achieved is 69 times for the design with a 9 nm external SiO₂ shell, as is also confirmed by three-dimensional finite-difference time-domain simulations. This dramatically increased fluorescence has great significance in fluorescence-based sensing and imaging.     

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.     

Influence of Anisotropy on Optical Bistability in Plasmonic Nanoparticles with Cylindrical Symmetry

In this paper, the effect of radial anisotropy on optical bistability in the cylindrical nanoshells is theoretically investigated within the quasi-static approximation. We consider two cases: when the shell is anisotropic and the core is nonlinear metal and when the core is anisotropic and the shell is a nonlinear metal. The dependence of optical bistability on the size of the nonlinear/anisotropic shell or core, the embedding medium, the anisotropy parameter, and the type of noble metals as candidates for plasmonics is studied and demonstrated. We show that by changing the type of the plasmonic metal, the switching threshold field changes can be used to design nanoparticle-based all-optical sensors. It is also shown that significant optical bistability and all-optical switching behavior can be obtained in the cylindrical nanoshells due to nonlinearity enhancement via the plasmonic structure.     

Tailoring LSPR-Based Absorption and Scattering Efficiencies of Semiconductor-Coated Au nanoshells

Absorption and scattering efficiencies of semiconductor-coated Au nanoshell have been studied by the extended Mie theory for their possible solar cell, optical imaging, and photothermal applications, etc. The effect of Au shell layer thickness, core size, and surrounding medium on the absorption and scattering efficiencies at the localized surface plasmon resonance (LSPR) wavelengths has been reported. It has been found that both the absorption and scattering efficiencies get blue-shifted with an increase in Au shell layer thickness from 2 to 10 nm and with an increase in surrounding refractive index whereas the corresponding LSPR peaks shift towards red. It has also been found that the spectra are red-shifted with an increase in the core radius from 20 to 40 nm while keeping the shell thickness same. The effect of shell thickness on the absorption peak position and absorption linewidth has also been studied. Hence, the optical response of both CdSe- and CdTe-coated Au nanoshells can be tuned and controlled from the visible to the near-infrared (NIR) region of the electromagnetic (EM) spectrum. Finally, the CdSe-coated Au nanoshell exhibits high scattering and absorption efficiencies in comparison to the CdTe-coated nanoshell.     

High Activity Hydrogen Evolution Catalysis by Uniquely Designed Amorphous/Metal Interface of Core–shell Phosphosulfide/N‐Doped CNTs

A cost effective hydrogen evolution reaction (HER) catalyst that does not use precious metallic elements is a crucial demand for environment‐benign energy production. The family of earth‐abundant transition metal compounds of nitrides, carbides, chalcogenides, and phosphides is one of the promising candidates for such a purpose, particularly in acidic conditions. However, its catalytic performance is still needed to be enhanced through novel material designs and crystalline engineering. Herein, a chemically and electronically coupled transition metal phosphosulfide/N‐doped carbon nanotubes (NCNT) hybrid electrocatalyst is fabricated via a two‐step synthesis. The uniquely designed synthesis leads to the material morphology featuring a core–shell structure, in which the crystalline metal phosphide core is surrounded by an amorphous phosphosulfide nanoshell. Notably, due to the favorable modification of chemical composition and surface properties, core–shell CoP@PS/NCNT exhibits the noticeable HER activity of approximately ?80 mV @ ?10 mA cm^?2 with excellent durability, which is one of the highest active nonnoble metal electrocatalysts ever reported thus far.     

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.     

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.     

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.