Plasmonic Interaction Between Silver Nano-Cubes and a Silver Ground Plane Studied by Surface-Enhanced Raman Scattering

The plasmonic interaction between silver nano-cubes and a silver ground plane with and without a dielectric spacer is studied for surface-enhanced Raman scattering (SERS) for rhodamine 6G (R6G) molecules absorbed onto the silver nano-cubes. Experimental results show that the composite substrates made from silver nano-cubes and the silver ground plane produce a stronger SERS signal than by the cubes alone, due to the plasmonic interaction between the cubes and the film. Numerical simulation is used to verify the plasmonic enhancement of the composite substrate and is consistent with the experimental results. The lowest concentration of R6G molecules which can be detected with the composite substrate is about 10⁻¹¹ M with our setup.     

Contrast Enhancement in Fluorescence Microscope by Plasmonic Coupling

A fluorescence microscope taking advantage of plasmonic coupling is in-proof demonstrated. Silver nano-wires and nano-particles are chosen as the metallic nano-objects, which are put on a silver film with the Rhodamine B-doped PMMA film as the spacer. Plasmonic coupling between the metallic nano-objects and the Ag film will induce either fluorescence quenching or enhancement dependent on the thickness of the spacer layer, which both enhance the contrast of the fluorescence images. Our experiment provides a feasible method to enhance the contrast of fluorescence microscope, which has potential applications in fluorescence-based imaging or sensing.     

Mechanistic Insights into Interaction of Humic Acid with Silver Nanoparticles

Humic acid (HA) is one of the major components of the natural organic matter present in the environment that alters the fate and behavior of silver nanoparticles (Ag NPs). Transformation of Ag NPs happens upon interaction with HA, thereby, changing both physical and chemical properties. Fluorescence spectroscopy and scanning electron microscopy (SEM) were used to analyze the interaction of Ag NPs with HA. In pH and time-dependent studies, the near field electro dynamical environment of Ag NPs influenced the fluorescence of HA, indicated by fluorescence enhancement. SEM revealed not only morphological changes, but also significant reduction in size of Ag NPs after interaction with HA. Based on these studies, a probable mechanism was proposed for the interaction of HA with Ag NPs, suggesting the possible transformation that these nanoparticles can undergo in the environment.     

Spectral Investigations on the Fluorescence Quenching of 1,4-dihydroxy-2,3-dimethylanthracene-9,10-dione by Plasmonic Silver Nanoparticles

Silver nanoparticles (Ag NPs) of different sizes have been prepared by Lee and Meisel’s method using trisodium citrate as reducing agent under ultra sonication. Optical absorption and fluorescence emission techniques were employed to investigate the interaction of 1,4-dihydroxy-2,3-dimethyl anthracene-9,10-dione (DHDMAD) with silver nanoparticles. In fluorescence spectroscopic study, we used the DHDMAD and Ag NPs as component molecules for construction of Förster Resonance Energy Transfer (FRET), whereas DHDMAD serve as donor and Ag NPs as acceptor. The surface plasmon resonance (SPR) peak of the prepared silver colloidal solution was observed from 419 nm to 437 nm. The synthesized silver nanoparticles at different heating time intervals were spherical in shape about the size of 25 nm and 55 nm. The fluorescence interaction between silver nanoparticles and DHDMAD confirms the FRET mechanism. According to Förster theory, the distance between silver nanoparticles and DHDMAD and the critical energy transfer distance were calculated and it is increase with heating time.     

Influence of SiO<Subscript>2</Subscript> Spacer Layer Thickness on Performance of Plasmonic Textured Silicon Solar Cell

We investigated the effect of SiO₂ spacer layer thickness between the textured silicon surface and silver nanoparticles (Ag NPs) on solar cell performance using quantum efficiency analysis. Separation of Ag NPs from high index silicon with SiO₂ layer led to modified absorption and scattering cross-sections due to graded refractive index medium. The forward scattering from Ag NPs is very sensitive to SiO₂ layer thickness in plasmonic silicon cell performance due to the evanescent character of generated near-fields around the NPs. With the optimized ～30–40 nm SiO₂ spacer layer, we observed an enhancement of solar cell efficiency from ～8.7 to ～10 %, which is due to the photocurrent enhancement in the off-resonance surface plasmon region. We also estimated minority carrier diffusion lengths (L _eff) from internal quantum efficiency data, which are also sensitive to SiO₂ spacer layer thickness. We observed that the L _eff values are enhanced from ～356 to ～420 μm after placing Ag NPs on ～40 nm spacer layer due to improved forward (angular) scattering of light from the Ag NPs into silicon.     

Silver binding toPseudomonas aeruginosa azurin

Summary The interaction between azurin and silver ions was investigated, by means of ultraviolet, fluorescence and atomic absorption spectroscopies, as a function of the redox state of the protein. The Ag(I) ion has a very low affinity for oxidized azurin. Interestingly, the affinity is much higher for reduced azurin; in this case Ag(I) completely displaces the Cu(I) ion from the native binding site. The effect is very specific for silver ions since other ions, such as Hg(II), Ni(II) and Cd(II), do not produce the same effect. Treatment of reduced and oxidized azurin with excess Ag(I) (2-8-fold stoichiometric) shows that there is a second binding site for silver ions on the protein which can also bind Cu(II) and Hg(II) with comparable affinities.     

Quantifying the Usefulness of Oxide-Encapsulated Silver Nanoparticles in Semiconducting Films

Incorporating plasmonic nanoparticles (NPs) in an organic solar cell (OSC) can improve device performance. In our simulation studies, at NP resonance, absorption in poly(3-hexythiophene)/phenyl-C61-butyric acid methyl ester (P3HT/PCBM) can be increased by encapsulating 50 nm Ag NPs with Al₂O₃, HfO₂, MoO₃, and SiO₂. At Ag NP resonance, when the oxide thickness is significant enough, oxides with high relative permittivity induces a higher electric field enhancement at the metal/dielectric interface. This is translated to improved absorption in the polymer layer. By integrating against AM1.5G, overall absorption in P3HT/PCBM is improved when incorporating Ag NPs encapsulated with a thin oxide shell into the polymer film. However, polymeric absorption loss is induced for oxide-encapsulated Ag NPs if MoO₃ and SiO₂ shells are more than 5 nm. For Al₂O₃ and HfO₂, Ag NPs should not be encapsulated with shells thicker than 10 nm. Modeling studies are also extended to absorption in a CH₃NH₃PbI₃ perovskite layer. It is revealed that both Al₂O₃ and HfO₂ have an optimal shell thickness of about 20 nm to ensure maximum absorption in CH₃NH₃PbI₃. The results can be utilized as a useful guideline when designing photovoltaics from an optical point of view.     

Near-Infrared Fluorescence Enhancement Using Silver Island Films

Near-infrared (near-IR) excitation produces little background signal from biological molecules, making near-IR fluorescence technology highly useful in proteomic and genomic applications. To increase the emissions of near-IR fluorophores, we examined the use of metal-enhanced fluorescence on these longer wavelength dyes. IRDye^®700- and IRDye^®800-labeled DNA oligonucleotides and proteins were spotted onto silver island film (SIF)-coated glass slides, and analyzed using a LI-COR Odyssey^® IR imaging system. We observed more than 18-fold enhancement of the IRDye^®700 and 15-fold enhancement of the IRDye^®800-labeled DNA oligonucleotides when spotted on SIF-coated surfaces compared with uncoated surfaces. We also demonstrated that the enhanced emissions produced on the SIF-coated slides remained linear over several orders of magnitude, that the emissions remained reproducible across a slide surface, and that the SIF-coated slide remained effective at enhancing emissions after 9 months of storage. Our results indicate that SIF-coated glass slides are effective at enhancing near-IR fluorescence and could be developed into an effective tool to aid in molecular biological applications.     

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%.

     

Surface Plasmon Enhancement at a Liquid–Metal–Liquid Interface

Herein, we report the first experimental demonstration of surface plasmon enhancement at a liquid–metal–liquid interface using a pseudo-Kretschmann geometry. Pumping gold nanoparticle clusters at the interface of a p-xylene–water mixture, we were able to measure a fluorescence enhancement of three orders of magnitude in Rose Bengal at an excitation wavelength of 532 nm. The observed increase is due to the local electric field enhancement and the reduction of the fluorescence lifetime of dye molecules in the close vicinity of the metal surface. Theoretical modeling using the T-matrix method of the electric field intensity enhancement of emulated surfaces supports the experimental results. This new approach will open a new road for the study of dynamic systems using plasmonics.     

Enhancing the Surface-State Emission in Trap-Rich CdS Nanocrystals by Silver Nanoparticles

It is well known that surface plasmon resonance (SPR) can selectively enhance the photoluminescence (PL) from nearby chromophores with a single emission peak at an appropriate distance. Here, we combine white light-emitting CdS quantum dot nanocrystals containing band-edge and surface-state emissions simultaneously with Ag nanoparticles and study the interaction between them. It is found that the surface-state emission is always enhanced while the band-edge emission quenched regardless of the SPR wavelength of Ag nanoparticles. This phenomenon reveals that the SPR of Ag nanoparticles is not enhancing the emission from a wavelength-matched state. We propose that the surface plasmon of Ag nanoparticles is first excited by the energy of the band-edge emission and then the excited energetic electrons transfer to the surface-state of CdS. Through this energy transfer process, the surface-state emission is enhanced and band-edge emission quenched. This investigation can not only deliver understanding of the complicated interaction between metallic nanoparticles and nearby multi-emission-peak contained chromophores, but it also has potential applications in tuning the color temperature of white light-emitting materials.     

Ag Nanostructures Produced by Glancing Angle Deposition with Remarkable Refractive Index Sensitivity

Glancing angle deposition is a powerful method for direct fabrication of nanostructures on various substrates. In this research, GLAD method has been used to fabricate Ag nanostructures with columnar morphology for refractive index sensing applications. The morphology and plasmonic properties of the nanostructures are controlled by changing deposition parameters such as glancing angle, speed of azimuthal rotation of the substrate, and the height of deposited nanostructures. The results show that increasing the deposition thickness from 200 to 500 nm leads to narrowing the plasmonic peak, which mainly relates to increment of the distance between larger nanostructures. By changing the glancing angle between 86° to 80°, the narrowest plasmonic peak corresponding to the greatest sensitivity has been obtained for the film deposited at the angle of 82°. Also, increment of the rotation speed of the samples leads to narrowing of the plasmonic peaks. By measuring the refractive index sensitivity (RIS) of the nanostructures, a best sensitivity of 154 nm/RIU has been obtained. Finally, we investigated the stability of Ag nanostructures in deionized water by introducing a new stabilizing technique in which a thin Au layer is coated on the Ag nanostructures. This technique has the merits of simultaneously protecting the Ag nanostructures against oxidation and keeping their refractive index sensitivity high enough for long time usages.     

Dipole Decay Rates Engineering via Silver Nanocones

A full control of the interaction between confined plasmons and point sources of radiation is a central issue in molecular plasmonics. In this paper, a theoretical contribution towards a physical understanding on the localized surface plasmons excited into metallic nanocones by a point dipole is given. A numerical approach based on the discrete dipole approximation is applied to determine the modifications of the dipole decay rates for varying geometrical parameters of the dipole-metal nanoparticle system. Results declare the centrality of the cone aperture to control the plasmon resonances and to handle the effects it induces on the lifetime of a point emitter. A full spectral tuning of the resonances in the decay rates can be achieved by operating on a unique spatial degree of freedom: by tailoring the aperture alone, total decay rates 10⁵ times higher than the free-space value can be obtained at short distances from the metal in a large region of the spectral range. Quite unexpectedly, size dependence of the antenna is found to have a marginal role if only a lifetime manipulation is desired. It becomes, instead, a crucial aspect of the problem when large quantum yields are required. Results presented in this work shed light on spontaneous emission modification due to interaction with plasmonic nanocones of different shapes and are relevant for a number of applications in the fields of nanoplasmonics and fluorescence microscopy.     

DNA Detection Based on Localized Surface Plasmon Resonance Spectroscopy of Ag@Au Biocomposite Nanoparticles

Noble metal nanoparticles (NPs) have attracted much attention due to their unique physical and chemical properties such as tunable surface plasmonics, high-efficiency electrochemical sensing, and enhanced fluorescence. We produced two biosensor chips consisting of Ag@Au bimetallic nanoparticles (BNPs) on a carbon thin film by simple RF-sputtering and RF-plasma-enhanced chemical vapor co-deposition. We deposited Au NPs with average size of 4 nm (Au₁ NPs) or 11 nm (Au₂ NPs) on a sensor chip consisting of Ag NPs with mean size of 15 nm, and we investigated the effect of shell size (Au NPs) on the chemical activities of the resulting Ag@Au₁ BNPs and Ag@Au₂ BNPs. We estimated the average size and morphology of Ag@Au BNPs by scanning electron microscopy (SEM) and atomic force microscopy (AFM) images. X-ray diffraction (XRD) patterns revealed that Ag NPs and Au NPs had face-centered cubic (FCC) structure. We studied aging of the biosensor chips consisting of Ag@Au BNPs by localized surface plasmon resonance (LSPR) spectroscopy for up to 3 months. UV–visible aging of the prepared samples indicated that Ag@Au₁ BNPs, which corresponded to Ag NPs covered with smaller Au NPs, were more chemically active than Ag@Au₂ BNPs. Furthermore, we evaluated changes in the LSPR absorption peaks of Ag@Au₁ BNPs and bare Ag NPs in the presence of a DNA primer decamer at fM concentrations, to find that Ag@Au₁ BNPs were more sensitive biosensor chips within a short response time as compared to bare Ag NPs.

     

Investigating Fluorescence Quenching of ZnS Quantum Dots by Silver Nanoparticles

Water dispersible zinc sulfide quantum dots (ZnS QDs) with an average diameter of 2.9 nm were synthesized in an environment friendly method using chitosan as stabilizing agent. These nanocrystals displayed characteristic absorption and emission spectra having an absorbance edge at 300 nm and emission maxima (λ _emission) at 427 nm. Citrate-capped silver nanoparticles (Ag NPs) of ca. 37-nm diameter were prepared by modified Turkevich process. The fluorescence of ZnS QDs was significantly quenched in presence of Ag NPs in a concentration-dependent manner with K _sv value of 9 × 10⁹ M⁻¹. The quenching mechanism was analyzed using Stern–Volmer plot which indicated mixed nature of quenching. Static mechanism was evident from the formation of electrostatic complex between positively charged ZnS QDs and negatively charged Ag NPs as confirmed by absorbance study. Due to excellent overlap between ZnS QDs emission and surface plasmon resonance band of Ag NPs, the role of energy transfer process as an additional quenching mechanism was investigated by time-resolved fluorescence measurements. Time-correlated single-photon counting study demonstrated decrease in average lifetime of ZnS QDs fluorescence in presence of Ag NPs. The corresponding F?rster distance for the present QD–NP pair was calculated to be 18.4 nm.     

Silver nanoclusters stabilized with denatured fish sperm DNA and the application on trace mercury ions detection

In this study, fluorescent silver nanoclusters (Ag NCs) were synthesized using denatured fish sperm DNA as the template. In contrast to other methods, this method did not use artificial DNA as the template. After their reaction with denatured fish sperm DNA, Ag⁺ ions were reduced by NaBH₄ to form Ag NCs. The Ag NCs showed a strong fluorescence emission at 650 nm when excited at 585 nm. The fluorescence intensity increased fourfold at pH 3.78, controlled with Britton–Robinson buffer solution. The fluorescence of the Ag NCs was quenched in the presence of trace mercury ions (Hg²⁺) in a weakly acidic medium and nitrogen atmosphere. The extent of the fluorescence quenching of Ag NCs strongly depends on the Hg²⁺ ion concentration over a linear range from 2.0 nmol L^?1 to 3.0 μmol L^?1. The detection limit (3σ/k) for Hg²⁺ was 0.7 nmol L^?1. Thus, a sensitive and rapid method was developed for the detection of Hg²⁺ ions.     

Luminescence Enhancement of Carboxyl-Coated CdTe Quantum Dots by Silver Nanoparticles

Metallic nanoparticles (NPs) have been used to improve the sensibility of biosensors and bioassays either by enhancing radiative emission or inducing quenching process on fluorescent probes. The aim of this research was to study the interaction of silver and silver-pectin NPs with water-dispersed carboxyl-coated cadmium telluride (CdTe) quantum dots (QDs). Metallic NPs were observed to change the emission of these fluorophores through local field effects. In a solution-base platform, an increase of 82 % was observed for the CdTe emission due to the interaction of QDs and silver-pectin NPs. QDs interaction with silver NPs without pectin was also investigated and a smaller emission enhancement of 20 % was detected. We observed that the NPs’ nature and QDs’ surface charge and concentration are important parameters for NPs-QDs interaction. Moreover, the presence of the pectin polymer shows to be a key component to the observed fluorescence enhancement.     

Synthesis of Peptide Mediated Au Core–Ag Shell Nanoparticles as Surface-Enhanced Raman Scattering Labels

As the fundamental understanding of metal–light interactions gains solid grounds, further research has been devoted to construct novel structures that take full advantage of such unique interactions, which is called plasmonics. In this report, the preparation of Au–Ag core–shell structures obtained by coating the Au surface with peptide and Raman reporter molecule and depositing an Ag layer on it is reported. The prepared Au–Ag NPs are tested for their surface-enhanced Raman scattering (SERS) performance. The negatively charged peptides with three different lengths, which are 3 (P1), 15 (P2), and 21 (P3) amino acid long, were chemically attached to 13 nm AuNPs along with Raman reporter molecule, carboxytetramethylrhodamine, and these modified AuNPs were coated with three different shell thickness of Ag metal. The prepared Au–Ag NPs were tested for their SERS performance and found that the Au–Ag NPs prepared with P2 and thickest shell performs best as SERS label.     

Optimization of Dielectric-Coated Silver Nanoparticle Films for Plasmonic-Enhanced Light Trapping in Thin Film Silicon Solar Cells

Surface plasmonic-enhanced light trapping from metal nanoparticles is a promising way of increasing the light absorption in the active silicon layer and, therefore, the photocurrent of the silicon solar cells. In this paper, we applied silver nanoparticles on the rear side of polycrystalline silicon thin film solar cell and systematically studied the dielectric environment effect on the absorption and short-circuit current density (Jsc) of the device. Three different dielectric layers, magnesium fluoride (MgF₂, n?=?1.4), tantalum pentoxide (Ta₂O₅, n?=?2.2), and titanium dioxide (TiO₂, n?=?2.6), were investigated. Experimentally, we found that higher refractive index dielectric coatings results in a redshift of the main plasmonic extinction peak and higher modes were excited within the spectral region that is of interest in our thin film solar cell application. The optical characterization shows that nanoparticles coated with highest refractive index dielectric TiO₂ provides highest absorption enhancement 75.6 %; however, from the external quantum efficiency characterization, highest short-circuit current density Jsc enhancement of 45.8 % was achieved by coating the nanoparticles with lower refractive index MgF₂. We also further optimize the thickness of MgF₂ and a final 50.2 % Jsc enhancement was achieved with a 210-nm MgF₂ coating and a back reflector.     

Highest Efficiency Plasmonic Polycrystalline Silicon Thin-Film Solar Cells by Optimization of Plasmonic Nanoparticle Fabrication

Excitation of surface plasmons in metallic nanoparticles is a promising method for increasing the light absorption in solar cells and hence the cell photocurrent. Comprehensive optimization of a nanoparticle fabrication process for enhanced performance of polycrystalline silicon thin-film solar cells is presented. Three factors were studied: the Ag precursor film thickness, annealing temperature and time. The thickness of the precursor film was 10, 14 and 20 nm; annealing temperature was 190, 200, 230 and 260 °C; and annealing time was varied between 20 and 95 min. Performance enhancement due to light-scattering by nanoparticles was calculated by comparing absorption, short-circuit current density and energy conversion efficiency in solar cells with and without nanoparticles formed under different process conditions. Nanoparticles formed from 14-nm-thick Ag precursor film annealed at 230 °C for 53 min result in the highest absorption enhancement in the 700–1,100 nm wavelength range, in the highest enhancement of total short-circuit current density. The highest photocurrent enhancement was 33.5 %, which was achieved by the cell with the highest absorption enhancement in the 700–1,100 nm range. The plasmonic cell efficiency of 5.32 % was achieved without a back reflector and 5.95 % with the back reflector; which is the highest reported efficiency for plasmonic thin-film solar cells.