Tapered Fiber Probe Modified by Ag Nanoparticles for SERS Detection

A tapered optical fiber fabricated by a simple chemical etching method and modified with Ag nanoparticles (AgNPs) by chemical deposition was evaluated for surface-enhanced Raman scattering (SERS). The fiber probe was used for SERS measurements in both direct and remote scattering modes, yielding desired performance in both scattering configurations. The state of the obtained AgNPs made a significant contribution to the high sensitivity of SERS to Rhodamine 6G (R6G) molecules (down to a concentration of 10^?7 M), and the substrate had an analyst enhancement factor (AEF) on the order of ～10⁸. Meanwhile, the SERS intensity during the evaporation process was investigated, showing a good stability at the later stage of the evaporation process. The fiber SERS probes demonstrated good reproducibility with the average relative standard deviation (RSD) values being less than 0.2 for the major Raman peaks.     

A Study on the Morphology of the Silver Nanoparticles Deposited on the n-Type Porous Silicon Prepared Under Different Illumination Types

In this study, the influence of n-type porous Si (n-PS) morphology properties and the performance of Ag nanoparticles (AgNPs)/n-PS Raman substrate were investigated. Two kinds of n-PS morphology (macro n-PS and mud n-PS) structures were fabricated by laser-assisted etching (LAE) process and ordinary light-assisted etching (OLAE) process, respectively. A simple and cost-effective immersion plating process of n-PS in 0.01 M concentration of AgNO₃ for 16-min immersion time was used to synthesize AgNPs. The morphological properties of the deposited AgNPs on the macro n-PS layer showed that the deposition process is concentrated on the pore wall with a little density, while for mud n-PS, the AgNP layer is mainly composed of high-density uniformly distributed spherical particles located over the mud surface. Surface-enhanced Raman scattering (SERS) process of AgNPs/n-PS revealed strong dependence on the morphology and the density of AgNPs. Enhancement factor (EF) of Raman signal of AgNPs/mud n-PS substrate is three orders of magnitude higher than that of AgNPs/macro n-PS substrate of about 1.6 × 10¹¹ and 8.2 × 10⁸, respectively.     

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.     

Trace-Level Detection of Explosive Molecules with Triangular Silver Nanoplates-Based SERS Substrates

We report a simple route to design highly sensitive triangular silver nanoplates (TSNPs)-based SERS substrate for the trace-level detection of explosive molecules. The size-dependent localized surface plasmon resonance (LSPR) tunability for the synthesis of TSNPs is achieved by controlling reaction kinetics and seed volume in a modified seed-mediated approach. The computed extinction spectra of TSNP, using the finite-difference time-domain (FDTD) method, are in excellent agreement with the experimental results, therefore assisting further in the investigation of the plasmonic properties of TSNP. The higher electric field enhancement offered by TSNP is systematically investigated by performing the FDTD simulations for various sizes and corner rounding of TSNP. The FDTD results show that the dipolar plasmon resonance wavelength, size, and corner rounding of TSNP are the principal contributing factors for designing the high-performance SERS substrate. Herein, we have used a portable Raman system for the SERS-based detection of three important explosive molecules: picric acid (PA), ammonium nitrate (AN), and 2, 4-dinitrotoluene (DNT). The TSNP-based SERS substrates display excellent intensity enhancement factors of?~?10⁷ for rhodamine 6G (R6G) and PA and?~?10⁵ for AN. The high sensitivity of SERS substrate with limit-of-detection (LOD) of value 2.3?×?10^?11 M for PA and 3.1?×?10^?8 M for AN and effective batch-to-batch reproducibility for DNT, thus offering its potentials for field detection of explosive molecules at trace-level.

     

Diagonally Aligned Squared Metal Nano-pillar with Increased Hotspot Density as a Highly Reproducible SERS Substrate

Metal nanostructure on dielectric substrate with increased hotspot density has drawn considerable research interest in recent years toward the study of surface-enhanced Raman spectroscopy (SERS). In this paper, we report the fabrication of a diagonally aligned squared metal nano-pillar (SMNP) on a dielectric substrate and revealed it as an efficient SERS substrate with increased hotspot density for sensing of Raman active materials. Due to dipolar coupling and lightening rod effect between the neighboring nano-pillars, the localized surface plasmon resonance (LSPR) field intensity increased significantly in the space between two neighboring SMNP which would lead to the enhancement of SERS signal. The SMNP has been fabricated using electron beam lithographic (EBL) technique with hotspot density of 2.45 × 10⁷/mm². With the designed SERS substrate an average enhancement factor (EF) of 3.27 × 10⁸ has been observed with relative standard deviation of ～13 %.     

Optical Properties of Noncontinuous Gold Shell Engineered on Silica Mesosphere

The optical properties of individual noncontinuous shells with different gold coverage are investigated by the single-particle dark field scattering measurements and single-particle surface-enhanced Raman scattering (SERS) measurements at different excitation wavelengths. By controlling the growth of gold seeds, multi-metallic nanogaps/crevices with different optical responses are assembled on silica mesospheres forming noncontinuous shells that can be confirmed through the transmission electron microscope images. We find the surface plasmon resonance of single shell red-shifts from 510 to 680 nm with the increase of gold coverage. At the excitation of 532 and 785 nm, the best enhancements about 2.0?×?10⁵ and 1.1?×?10⁷ are obtained on spheres with ～60 and 83 % gold coverage, respectively. The weak polarization-dependent SERS indicates that the enhancement is from the multi-gaps on single noncontinuous shell. This optical tunable and SERS active noncontinuous gold shell can be applied in biosensing, ultra trace detection, and molecule analysis needing multi-wavelengths excitation.     

Direct Electrodeposition of Hollowed Ag Nanostructures on ITO Glass for Reproducible SERS Application

Hollowed Ag nanostructures are, for the first time, electrodeposited on ITO glass without use of surfactant. The hollowed Ag nanostructure was investigated via a collaboration of scanning electron microscopy (SEM), XRD, X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HRTEM), XRD, and UV-vis. Results exhibited that the formation of the hollowed Ag nanostructure can be interpreted as the synergy effect of twin defect and low nucleation driving force. Surface-enhanced Raman scattering (SERS) spectra of rhodamine 6G and adenine molecules adsorbed on the surface of these Ag nanostructures were recorded. The smallest RSD of 1651 cm^?1 Raman bands of rhodamine 6G was 14.7 %, indicating that the hollowed Ag nanostructures can be utilized for reproducible SERS application. Through comparison, it was found the good crystallinity was beneficial for SERS.     

Surface-Enhanced Raman Scattering in Tunable Bimetallic Core-Shell

In this paper, optical properties of multilayer spherical core-shell nanoparticles based on quasi-static approach and plasmon hybridization theory are investigated. Calculations show that light absorption spectrum of bimetallic multilayer core-shell has three intense plasmon resonance peaks, which are more suitable for multiplex biosensing based on surface-enhanced Raman scattering (SERS) and localized surface plasmon resonance (LSPR). The plasmon resonance peaks in bimetal nanshells are optimized by tuning the geometrical parameters. In addition, the optimal geometry is discussed to obtain the Raman enhancement factor in bimetallic multilayer nanoshell. SERS enhancement factor is calculated with consideration of dampings due to both the electron scattering and the radiation at the boundary and modified Drude model in dielectric function of bimetallic nanoshell. It is shown that bimetallic nanoshell with the small size exhibits strong SERS enhancement factor (~6.63 × 10⁵) with additional collision dampings and ~2.9 × 10⁹ with modified Drude model which are suitable for biosensing applications. In addition, any variation in blood concentration and oxygen level can be detected by this bimetallic core-shell nanoparticle with sensitivity of Δλ/Δn = 264.91 nm/RIU.     

Therapeutic prognosis of prostate cancer using surface-enhanced Raman scattering of patient urine and multivariate statistical analysis

Surface-enhanced Raman scattering (SERS) is highly sensitive and label-free analytical technique based on Raman spectroscopy aided by field-multiplying plasmonic nanostructures. We report the use of SERS measurements of patient urine in conjunction with biostatistical algorithms to assess the treatment response of prostate cancer (PCa) in 12 recurrent (Re) and 63 nonrecurrent (NRe) patient cohorts. Multiple Raman spectra are collected from each urine sample using monodisperse silver nanoparticles (AgNPs) for Raman signal enhancement. Genetic algorithms-partial least squares-linear discriminant analysis (GA-PLS-LDA) was employed to analyze the Raman spectra. Comprehensive GA-PLS-LDA analyses of these Raman spectral features (p = 3.50 × 10⁻¹⁶ ) yield an accuracy of 86.6%, sensitivity of 86.0%, and specificity 87.1% in differentiating the Re and NRe cohorts. Our study suggests that SERS combined with multivariate GA-PLS-LDA algorithm can potentially be used to detect and monitor the risk of PCa relapse and to aid with decision-making for optimal intermediate secondary therapy to recurred patients.     

A Rapid Surface-Enhanced Raman Scattering Method for the Determination of Trace Hg2+ Using Rhodamine 6G-Aggregated Nanosilver as Probe

In pH 6.0 Na₂HPO₄-NaH₂PO₄ buffer solution and in the presence of cetyltrimethyl ammonium bromide, nanosilver particles were aggregated to a stable suspension. Therein, rhodamine 6G (Rh6G) exhibited three strong surface-enhanced Raman scattering (SERS) peaks at 613, 1,363, and 1,510 cm^?1, and their SERS intensities were enhanced when the concentration of Rh6G increased. In the presence of Hg²⁺, the SERS intensity decreased greatly owing to formation of stable Rh6G-HgBr ₄ ^2? ternary association complex molecules as well as its particles. In the optimal condition, the decreased SERS intensity at 613 cm^?1 responds linearly with the concentration of Hg²⁺ over 25–2,000 nmol/L. Thus, a new sensitive SERS method has been proposed for the determination of trace Hg²⁺ in the water sample, with satisfactory results.     

表面等离子体-拉曼散射双模式复合生物芯片

本文提出了复合表面等离子体(SPR)无标记检测及表面增强拉曼散射(SERS)的显微成像技术.证明了双模式SPR-SERS生物芯片的可实施性,即在同一芯片上实现了表面等离子共振和表面增强拉曼显微检测.鉴于双模芯片的高保真性,基于显微技术的高精准、多通道无标记检测技术有望在临床医学检测中得以广泛应用.     

Individual Split Au Square Nanorings for Surface-Enhanced Raman and Hyper-Raman Scattering

In this paper, individual split Au square nanorings were numerically proposed as novel substrates for surface-enhanced Raman and hyper-Raman scattering (SERS and SEHRS) simultaneously. The peak wavelengths of their localized surface plasmon resonance (LSPR) fall in the near-infrared and visible light regions, respectively, which are able to be finely tuned to match well with the wavelengths of the incident laser and hyper-Raman scattered light beams. Their SEHRS and SERS performances along with electromagnetic (EM) field distributions are numerically investigated by finite element method. With the enhancement of near electric-fields generated by LSPRs, the maximum SEHRS and SERS enhancement factors are demonstrated to reach 1.22?×?10¹² and 10⁸, respectively. Meanwhile, the corresponding SERS-based refractive index (RI) sensitivity factor reaches as high as 258 nm/RIU and 893 nm/RIU, at visible and near-infrared wavelengths, respectively. The proposed structure holds great promise both for developing SEHRS- and SERS-based RI sensing substrates, which shows strong potential applications in nanosensing and enhanced Raman scattering.

     

Preparation,Optimization, and Characterization of SERS Sensor Substrates Based on Two-Dimensional Structures of Gold Colloid

Generally, the immobilization of two-dimensional nanoparticles in immersion procedures is time-consuming (over 24 h). In this paper, we report a very effective and simple method to fabricate two-dimensional gold nanoparticle patterns over large areas with high regularity for surface-enhanced Raman scattering (SERS). We achieved a highly sensitive SERS colloid surface by optimizing temperature and immersion time. The surfaces were characterized by X-ray photoelectron spectroscopy, UV–Vis, atomic force microscopy, and scanning electron microscopy. The SERS activity of surfaces was compared by using two techniques: “dip” and “dip and dry” in an aqueous solution of 10⁻⁶ M crystal violet. The influence of the morphology of the surface was investigated with both the dip and dip and dry techniques.     

Plasmonic Coupling Effect in Ag Nanocap–Nanohole Pairs for Surface-Enhanced Raman Scattering

A plasmonic coupling structure composed of Ag nanocap–nanohole pairs was fabricated through a novel and facile method. Both surface-enhanced Raman scattering (SERS) measurements and numerical simulations show that the cap-hole system produces much larger electric field enhancement and SERS signal than the isolated structures, which is due to the plasmonic coupling effect between the gap of the cap and the hole. Additionally, the plasmonic enhancement is sensitive to the gap size, which can be controlled by the Ag layer thickness during the evaporation process. A maximum enhancement factor of 1.1×10⁸ can be obtained with optimized gap size.     

Structural,Optical and Micro-Raman Scattering Studies of Nanosized Copper Ion (Cu+) Exchanged Soda Lime Glasses

Copper nanoclusters embedded in soda lime glass are prepared by ion exchanged method. The ion exchanged glasses are annealed in air for 1 h at different temperature. These samples exhibit surface plasmon and surface enhancement effect. UV-visible optical absorption spectroscopic analysis shows the signature of the copper nanocluster in the ion exchanged glasses. Surface-enhanced Raman spectroscopy (SERS) technique is used to characterize the copper ion exchanged and annealed glasses. Additional results are obtained by SERS for optimizing the SERS substrate. The highest Raman enhancement is obtained for substrates with high cluster size. The micro-Raman scattering spectroscopic images of ion exchanged and different temperature annealed glasses support the optical absorption spectroscopy results.     

A Sensitive SERS Quantitative Analysis Method for Amino Acids Using Ruhemann’s Purple as Molecular Probe in Triangle Nanosilver Sol Substrate

The stable silver nanotriangle (AgNT) sol was prepared by reduction of silver ions with sodium borohydride in the presence of H₂O₂ and sodium citrate. Under the action of NaCl, AgNTs were aggregated to a highly surface-enhanced Raman scattering (SERS) active substrate. In pH 6.0 Na₂HPO₄-NaH₂PO₄ buffer solution (PBS) at 80 °C water bath, ninhydrin reacted with amino acids to form blue-violet complex Ruhemann’s purple (RP), and the RP molecules adsorbed on the aggregated AgNT surfaces that exhibited a strong SERS peak at 657 cm^?1. The peak was linear to amino acid concentration in the range of 0.7–99.8 μmol/L, with a detection limit (DL) of 0.5 μmol/L. This SERS method was applied to detect amino acid in samples, with satisfactory results. In addition, the analytical system was also investigated by resonance Rayleigh scattering (RRS), absorption, and electron microscope techniques.     

Double-Layered Metal Nano-Strip Antennas for Sensing Applications

A coupled plasmonic system based on double-layered metal nano-strips for sensing applications is investigated by means of mode analysis and two-dimensional finite-difference time-domain simulations. The nano-strips act as optical antennas through constructive interference of short-range surface plasmon polaritons, thus increasing their scattering cross-section and optical field enhancement. Near-field modulation by optical trapped metal nanoparticles (NPs) is also demonstrated. Our results reveal that the device exhibits a refractive index sensitivity of ～200 nm/RIU, and a maximum surface-enhanced Raman scattering (SERS) factor of 10⁹–10¹⁰ from metal NPs trapped in the near-field region. The proposed device shows reasonable figure-of-merit and is ready for integration with common optofluidic biosensors.     

Gold Micro-Flowers: One-Step Fabrication of Efficient, Highly Reproducible Surface-Enhanced Raman Spectroscopy Platform

We present a new method enabling simultaneous synthesis and deposition of gold micro-flowers (AuMFs) on solid substrates in a one-pot process that uses two reagents, auric acid and hydroxylamine hydrochloride, in aqueous reaction mixture. The AuMFs deposited onto the substrate form mechanically stable gold layer of expanded nanostructured surface. The morphology of the AuMFs depends on and can be controlled by the composition of the reaction solution as well as by the reaction time. The nanostructured metallic layers obtained with our method are employed as efficient platforms for chemical and biological sensing based on surface-enhanced Raman spectroscopy (SERS). SERS spectra recorded by such platforms for p-mercaptobenzoic acid and phage lambda exhibit enhancement factors above 10⁶ and excellent reproducibility.     

A new silver nanochain SERS analytical platform to detect trace hexametaphosphate with a rhodamine S molecular probe

Using AgNO₃ as the precursor, stable silver nanochain (AgNC) sols, orange‐red in color, were prepared using hydrazine hydrate. A strong surface plasmon resonance Rayleigh scattering (RRS) peak occurred at 420 nm plus two surface plasmon resonance (SPR) absorption peaks at 410 nm and 510 nm. Rhodamine S (RhS) cationic dye was absorbed on the as‐prepared AgNC substrate to obtain a RhS–AgNC surface‐enhanced Raman scattering (SERS) nanoprobe that exhibited a strong SERS peak at 1506 cm^–1 and a strong RRS peak at 375 nm. Upon addition of the analyte sodium hexametaphosphate (HP), it reacted with RhS, which resulted in a decrease in the SERS and RRS peaks that was studied in detail. The decreased SERS and RRS intensities correlated linearly with HP concentration in the range of 0.0125–0.3 µmol/L and 0.05–1.0 µmol/L, with a detection limit of 6 nmol/L and 20 nmol/L HP respectively. Due to advantages of high sensitivity, good selectivity and simple operation, the RhS molecular probes were used to determine HP concentration in real samples. Copyright © 2015 John Wiley & Sons, Ltd.     

Ag-Cu Nanoparticles Encaptured by Graphene with Magnetron Sputtering and CVD for Surface-Enhanced Raman Scattering

An efficient surface-enhanced Raman scattering (SERS) substrate has been developed based on Ag-Cu nanoparticle-decorated graphene. The Ag-Cu-graphene (Ag-Cu@G) hybrid structure was prepared by magnetron sputtering for Ag and Cu film and chemical vapor deposition (CVD) for graphene, which avoided defects produced by graphene transferring process. The hybrid materials were confirmed by scanning electron microscopy (SEM), atomic force microscopy (AFM), energy dispersive spectroscopy (EDS), and Raman spectroscopy. With R6G as analyst molecule, the enhancement factor (EF) of the order of 10⁶ for Ag-Cu@G sample was obtained. Meanwhile, the substrates had stable enhanced SERS signals after 78-day exposure in air, which could be explained by the fact that the graphene is efficient at maintaining chemical and optical stability. The formation of graphene can contribute a stabilization and fluorescence quenching effect. Moreover, the electromagnetic distribution based on AFM images was simulated by finite difference time domain (FDTD) method.