Designing Commensurate and Incommensurate Resonances for Enhanced Dipole Emission in Coupled Plasmonic Nanorods

Plasmonic nanorods and their clusters are the fundamental units in plasmonic nanoantenna engineering. A theory that can predict the resonance of single nanorod already exists but is in lack for a heterodimer. Here, we propose a model combining the effective circuit theory for the response of spherical nanoparticles together with standard transmission line theory for hemispherically capped nanorod antennas. The resonances of multiple orders are predictable by defining the reflection phase at the terminals of such antennas, in both symmetric and asymmetric coupled nanorods. The theoretical results compare favorably with full-wave finite element numerical calculations. By the analytical formula, it is easy to control the length of the antennas for regulating the cooperative resonant properties and consequently the radiation characteristics of a nearby electric dipole. Consequently, we obtain both commensurate and incommensurate resonance features in such nanorod-based heterodimer antennas, showing respectively cumulative and selective responses from the individual nanorods.     

Intriguing Standing Wave Numbers and Plasmonic Effects on the Solid-Metal/Metal-Shell Nanorod Surface

In this paper, the intriguing standing wave numbers (SWNs) and surface plasmon resonance (SPR) effects on the solid-Ag/Ag-shell nanorod surface are numerically investigated by using finite element method. Various SPR effects due to the variation in rod aspect ratio (AR) and shell thickness on the scattering cross section (SCS), electromagnetic (EM) wave patterns, and the SWNs on the solid-Ag/Ag-shell nanorod surface are discussed in detail. Results reveal characteristic features of plasmon modes with respect to SWNs in photoluminescence images, which can enable us to obtain the mechanism of EM wave distributions near the solid-Ag/Ag-shell nanorods. The large EM wave with respect to their SWNs on the metal nanorod surface is very important for the applications of metal nanorod to be used to design devices like wavelength-selective photodetector, modulators, waveguides, metal nanorod-based solar cells, and plasmonic nanoantenna.     

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.     

Near-Infrared Dye Immobilized in Porous Silica Layer on Gold Nanorod and Its Fluorescence Enhancement by Strengthened Electromagnetic Field Based on Surface Plasmon Resonance

We report immobilizing Nile Blue A, which is a cationic fluorescent dye emitting in the near-infrared region, in the porous silica layer on gold nanorod and its fluorescence enhancement by strengthened electromagnetic field based on surface plasmon resonance. The effect of the spacer corresponding to the silica layer on the metal-enhanced fluorescence effect is also discussed in detail. Hollow silica nanorod was in advance prepared, and then the silica layer was partly etched to increase the porosity for the improvement of the mass transfer. Subsequently, gold nanorod was fabricated in the restricted space of hollow silica nanorod. Finally, Nile Blue A was physically immobilized in the porous silica layer on gold nanorod through electrostatic interactions. The fluorescence enhancement of Nile Blue A based on surface plasmon resonance was semi-quantified by comparative experiments using hollow silica nanorod, which is exactly the same structure except for gold as silica-coated gold nanorod. Since our results demonstrated that the porosity degree of the silica layer significantly affected the fluorescence enhancement of Nile Blue A, it is hopeful that our design concept, distinct from the conventional one, can lay a foundation for further development of near-infrared fluorescence nanomaterials.

     

Comparative Theoretical Study of the Optical Properties of Silicon/Gold,Silica/Gold Core/Shell and Gold Spherical Nanoparticles

The scattering and absorption efficiencies of light by individual silicon/gold core/shell spherical nanoparticles in air are analysed theoretically in the framework of Lorenz-Mie formalism. We have addressed the influence of particle-diameter and gold-shell thickness on the scattering and absorption efficiencies of such nano-heterostructures. For comparison, we also considered the famous silica/gold core/shell nanoparticle and pure gold nanoparticle. Our simulation clearly shows that the optical response of the illuminated Si/Au core/shell nanoparticle differs markedly from that of the famous SiO₂/Au heterostructure which in turn does not show a significant difference with that of the pure gold nanoparticle. This difference is clearly evident for shell thickness to outer particle radius ratio of less than 0.5. It manifests itself essentially by the occurrence of a strong and sharp absorption resonance beyond the wavelength of 600 nm where the silica/gold and the pure gold nanoparticles never absorb. The characteristics of this resonance are found to be sensitive to the particle diameter and the shell thickness. In particular, its spectral position can be adjusted over a wide spectral range from the visible to the mid-IR by varying the particle diameter and/or the shell thickness.     

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.     

Sensitive and Robust Colorimetric Sensing of Sulfide Anion by Plasmonic Nanosensors Based on Quick Crystal Growth

A highly sensitive and selective method for colorimetric sensing of sulfide anions in aqueous solutions is illustrated. The sensing mechanism is based on quick crystallization from Ag to Ag₂S in the presence of sulfide anions which alter the dielectric properties of the Au/Ag core/shell nanorods. The longitudinal surface plasmon resonance peak of the Au/Ag nanorods at about 686 nm undergoes a redshift and the color of the nanorod solution also changes from light green to purple. Sulfide ions at a concentration of 4.0 μM (1.3 ppb) can be detected visually and a sensitivity of 0.5 μM (167 ppt) is achieved by Vis–near-infrared spectrophotometry. Compared to other plasmonic sensors, our Au/Ag nanorod probe does not require surface modification while exhibiting high stability and robustness under different pH conditions. This simple and cost-effective sensing platform provides a rapid and convenient detection for sulfide anions at concentrations far below the hazardous limit in aqueous media.     

Enhanced photoinactivation of Staphylococcus aureus with nanocomposites containing plasmonic particles and hematoporphyrin

We fabricated composite nanoparticles consisting of a plasmonic core (gold nanorods or gold–silver nanocages) and a hematoporphyrin‐doped silica shell. The dual photodynamic and photothermal activities of such nanoparticles against Staphylococcus aureus 209 P were studied and compared with the activities of reference solutions (hematoporphyrin or silica‐coated plasmonic nanoparticles). Bacteria were incubated with nanocomposites or with the reference solutions for 15 min, which was followed by CW light irradiation with a few exposures of 5 to 30 min. To stimulate the photodynamic and photothermal activities of the nanocomposites, we used LEDs (405 and 625 nm) and a NIR laser (808 nm), respectively. We observed enhanced inactivation of S. aureus 209 P by nanocomposites in comparison with the reference solutions. By using fluorescence microscopy and spectroscopy, we explain the enhanced antimicrobial effect of hematoporphyrin‐doped nanocomposites by their selective accumulation in the vicinity of the bacteria. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Grating-based surface plasmon resonance detection of core-shell nanoparticle mediated DNA hybridization

In this report, we have investigated enhanced surface plasmon resonance (SPR) detection of DNA hybridization using gold core - silica shell nanoparticles in localized plasmonic fields. The plasmonic fields were localized by periodic linear gratings. Experimental results measured for hybridization of 24-mer single-stranded DNA oligomers suggest that core-shell nanoparticles (CSNPs) on gratings of 400 nm period provide enhanced optical signatures by 36 times over conventional thin film-based SPR detection. CSNP-mediated DNA hybridization produced 3 times larger angular shift compared to gold nanoparticles of the same core size. We have also analyzed the effect of structural variation. The enhancement using CSNPs was associated with increased surface area and index contrast that is combined by improved plasmon coupling with localized fields on gratings. The combined approach for conjugated measurement of a biomolecular interaction on grating structures is expected to lower the limit of detection to the order of a few tens of fg/mm(2).     

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.     

Modulation of Optical Properties of Gold Nanorods on Addition of KOH

Gold nanorods are known to exhibit two distinct surface plasmon oscillations namely, transverse and longitudinal bands corresponding to oscillations of conduction electrons along width and length of gold nanorods. Considerable changes in these surface plasmon resonance peak positions occurred when KOH was added to the nanorod solution. Nanorods with initial longitudinal plasmon band at 739, 796, and 895 nm are studied with variation in KOH concentration. While the longitudinal plasmon resonance peak showed blue shift, transverse plasmon resonance peak exhibited only intensity variations. Changes could be attributed to the shape transition of gold nanorods on variation of pH in the solution. Shape transition of gold nanorods is confirmed by transmission electron microscopy images.     

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.     

Fano Resonances Induced by Strong Interactions Between Dipole and Multipole Plasmons in T-Shaped Nanorod Dimer

A simple T-shaped plasmonic nanostructure composed of two perpendicular coupled nanorods is proposed to produce strong Fano resonances. By the near-field coupling between the “bright” dipole and “dark” quadrupole plasmons of the nanorods, a deep Fano dip is formed in the extinction spectrum, which can be well fitted by the Fano interference model. The effects of the geometry parameters including nanorod length, coupling gap size, and coupling location to the Fano resonances are analyzed in detail, and a very high refractive index sensitivity is achieved by the Fano resonance. Also by adjusting the incident polarization direction, double Fano resonances can be formed by the interferences of the dipole, quadrupole, and hexapole plasmons. The proposed nanorod dimer structure is agile, and a trimer which supports double Fano resonances can be easily formed by introducing a third perpendicular coupled nanorod. The proposed T-shaped nanorod dimer structure may have applications in the fields of biological sensing and plasmon-induced transparency.     

Optimization of Nanoparticle Size for Plasmonic Enhancement of Fluorescence

This paper reports on the enhancement of fluorescence that can result from the proximity of fluorophores to metallic nanoparticles (NPs). This plasmonic enhancement, which is a result of the localized surface plasmon resonance at the metal surface, can be exploited to improve the signal obtained from optical biochips and thereby lower the limits of detection. There are two distinct enhancement effects: an increase in the excitation of the fluorophore and an increase in its quantum efficiency. This study focuses on the first of these effects where the maximum enhancement occurs when the NP plasmon resonance wavelength coincides with the fluorophore absorption band. In this case, the excitation enhancement is proportional to the square of the amplitude of the electric field. The scale of the enhancement depends on many parameters, such as NP size and shape, metal type, and NP–fluorophore separation. A model system consisting of spherical gold/silver alloy NPs, surrounded by a silica spacer shell, to which is attached a fluorescent ruthenium dye, was chosen and the dependence of the fluorescence enhancement on NP diameter was investigated. Theoretical calculations, based on Mie theory, were carried out to predict the maximum possible enhancement factor for spherical NPs with a fixed composition and a range of diameters. Spherical NPs of the same composition were fabricated by chemical preparation techniques. The NPs were coated with a thin silica shell to overcome quenching effects and the dye was attached to the shell.     

金纳米棒的光学性质及其在生物医学领域的应用

简要介绍金纳米棒的光学性质和合成方法,重点阐述其在生物医学领域研究的最新进展,并对其今后的研究方向进行展望．金纳米棒是一种胶囊状的金纳米颗粒,具有一个横向等离子共振吸收峰和一个纵向等离子共振吸收峰,分别对应其横轴和纵轴两个特征尺寸．通过调节金纳米棒的长径比,纵向等离子共振吸收峰可由可见光区跨越至近红外光区．金纳米棒这一独特的光学性质在生物和化学传感方面有着广泛而重要的应用前景．     

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%.

     

Comparative Study on the Uniform Energy Deposition Achievable via Optimized Plasmonic Nanoresonator Distributions

Plasmonic nanoresonators of core–shell composition and nanorod shape were optimized to tune their absorption cross-section maximum to the central wavelength of a short laser pulse. The number density distribution of randomly located nanoresonators along a laser pulse-length scaled target was numerically optimized to maximize the absorptance with the criterion of minimal absorption difference between neighboring layers illuminated by two counter-propagating laser pulses. Wide Gaussian number density distribution of core–shell nanoparticles and nanorods enabled to improve the absorptance with low standard deviation; however, the energy deposited until the overlap of the two laser pulses exhibited a considerable standard deviation. Successive adjustment resulted in narrower Gaussian number density distributions that made it possible to ensure almost uniform distribution of the deposited energy integrated until the maximal overlap of the two laser pulses. While for core–shell nanoparticles the standard deviation of absorptance could be preserved, for the nanorods it was compromised. Considering the larger and polarization independent absorption cross-section as well as the simultaneously achievable smaller standard deviation of absorptance and deposited energy distribution, the core–shell nanoparticles outperform the nanorods both in optimized and adjusted nanoresonator distributions. Exception is the standard deviation of deposited energy distribution considered for the complete layers that is smaller in the adjusted nanorod distribution. Optimization of both nanoresonator distributions has potential applications, where efficient and uniform energy deposition is crucial, including biomedical applications, phase transitions, and even fusion.

     

Cellular-Like Gold Nanofeet: Synthesis, Functionalization, and Surface Enhanced Fluorescence Detection for Mercury Contaminations

The novel cellular-like gold nanofeet (CGNF) with movable gold core, which are derived from gold/silver core shell nanorods, have been generated by galvanic reaction protocol at room temperature. The optical property based on localized surface plasmon resonance (LSPR) has been evaluated in comparison with solid gold nanofeet, suggesting that obviously high LSPR sensitivity of CGNF contributes to enhancing optical effect for detection of analytes. In contrast with superquenching properties of nanogold for fluorescence detection of pollutants, highly sensitive detection of heavy metal contaminations, e.g., mercury ions, have been implemented via DNA functionalized silica-coated CGNF on the basis of surface enhanced fluorescence (SEF) approach.     

Correlating Metal-Enhanced Fluorescence and Structural Properties in Ag@SiO2 Core-Shell Nanoparticles

Metal@silica concentric nanoparticles capable of metal-enhanced fluorescence (MEF) represent a powerful means to improve the brightness and stability of encapsulated organic fluorophores and are finding numerous applications in biology, analytical chemistry, and medical diagnostics. The rational design of MEF-enabled labels and sensors often involves comparing fluorescence enhancement factors (EF) between nanostructures having different structural properties (e.g., metal core diameter, silica shell thickness, extent of spectral overlap between plasmon band and fluorophore). Accurate determination of EFs requires the measurement of fluorescence emission intensity in the presence and absence of the plasmonic core while minimizing the impact of physical and chemical artifacts (e.g., signal variations due to scattering, adsorption, sedimentation). In this work, Ag@SiO₂@SiO₂ + x (where x is fluorescein, eosin, or rhodamine B) nanostructures were synthesized with excellent control of core size, silica spacer shell thickness and fluorophore concentration. Using UV-VIS spectrometry, spectrofluorimetry, time-resolved fluorometry, and transmission electron microscopy, we investigated the influence of these key structural factors on fluorescence emission intensity, and the results were used to develop a generalized methodology for the determination of fluorescence enhancement factors in Ag@SiO₂ core-shell nanoparticles. This methodology should be of general importance to designing MEF-enabled nanostructures, sensors, and related analytical techniques.

     

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.