New surface-enhanced Raman spectroscopy substrates via self-assembly of silver nanoparticles for perchlorate detection in water

Perchlorate (ClO4-) has recently emerged as a widespread contaminant in drinking water and groundwater supplies in the United States, and a need exists for rapid detection and monitoring of this contaminant. In this study, surface-enhanced Raman spectroscopy (SERS) was studied as a means of ClO4- detection, and new sol-gel-based SERS substrates were developed by self-assembly of silver colloidal nanoparticles with various functionalized silane reagents. These substrate materials were tailored to allow detection of ClO4- in water with improved sorptivity, stability, and sensitivity and with the ability to detect ClO4- at concentrations as low as 10(-6) M (or 100 microg/L) with good reproducibility. Similar techniques were used to fabricate capillary SERS flow cells by assembling functionalized silver nanoparticles capable of attracting ClO4- to the SERS surface or the internal wall of glass capillaries. These capillary flow cells could be readily configured to allow for in situ, nondestructive detection of ClO4- via fiber optics.     

AuNRs@ZIF-8的制备及其表面增强拉曼散射光谱研究

表面增强拉曼光谱(Surface enhanced Raman spectroscopy, SERS)是一种分子光谱,具有快速、高灵敏和指纹识别的特性,在分析化学、生物医学等领域有着重要的应用。然而,在溶液样品中一些检测分子很难被SERS基底所吸附,导致分子拉曼信号增强困难。为此,本文提出了一种ZIF-8材料包覆金纳米棒(AuNRs)的核壳结构(AuNRs@ZIF-8)来实现拉曼信号增强,既可利用金纳米颗粒的表面等离激元增强特性,又可利用ZIF-8这种多孔MOFs材料的吸附性能,从而实现溶液样品的高灵敏拉曼检测。我们首先采用晶种法制备了均一性良好的AuNRs,然后对其进行聚乙烯吡咯烷酮(PVP)修饰,最后加入金属有机框架ZIF-8前驱体,得到AuNRs@ZIF-8核壳纳米结构。该结构对罗丹明(R6G)的SERS检测灵敏度很高,检测限可低至10⁻⁹ mol/L,并且线性关系和均一性均良好。此外,我们通过测试该结构吸收R6G前后的UV-Vis吸收光谱进一步证实了核壳纳米结构的生成和对目标分子的有效吸附。

     

Characterization of silane-modified immobilized gold colloids as a substrate for surface-enhanced Raman spectroscopy

Immobilized gold colloid particles coated with a C-18 alkylsilane layer have been characterized as a substrate for surface-enhanced Raman scattering (SERS) studies of adsorption onto hydrophobic surfaces. Atomic force microscopy images, optical extinction spectra, and SERS measurements are reported as a function of accumulation of gold colloid on glass. As the metal particles become increasingly aggregated on the surface, the SERS enhancement increases until the plasmon resonance shifts to wavelengths longer than the excitation laser. The gold colloid substrates are stable and exhibit reproducible SERS enhancement. When octadecyltrimethoxysilane is self-assembled over the gold, the metal surface is protected from exposure to solution-phase species, as evidenced by the inhibition of chemisorption of a disulfide reagent to the overcoated gold surface. The results show that interactions with gold can be blocked by a silane layer so as not to significantly influence physisorption of molecules at the C-18/solution interface. The SERS enhancement from these C-18-overcoated gold substrates is reproducible for different films prepared from the same colloidal suspension; the substrates are also stable with time and upon exposure to laser irradiation.     

Guided-mode-resonance-coupled plasmonic-active SiO(2) nanotubes for surface enhanced Raman spectroscopy

We demonstrate a surface enhanced Raman scattering (SERS) substrate by integrating plasmonic-active SiO(2) nanotubes into Si(3)N(4) gratings. First, the dielectric grating that is working under guided mode resonance (GMR) provides enhanced electric field for localized surface plasmon polaritons on the surface of metallic nanoparticles. Second, we use SiO(2) nanotubes with densely assembled silver nanoparticles to provide a large amount of "hot spots" without significantly damping the GMR mode of the grating. Experimental measurement on Rhodamine-6G shows a constant enhancement factor of 8?～?10 in addition to the existing SERS effect across the entire surface of the SiO(2) nanotubes.     

Multilayer enhanced gold film over nanostructure surface-enhanced Raman substrates

We have developed a novel class of gold multilayer, surface-enhanced Raman scattering (SERS) substrates that are capable of enhancing SERS signals by 15.3-fold over conventional gold film over nanostructure (GFON) SERS substrates, making them comparable in sensitivity to optimized silver film over nanostructure (SFON) substrates, while providing the long-term stability obtained from gold. They are fabricated by depositing 10 A thick silver oxide islands on conventional GFON substrates, followed by deposition of a second continuous gold layer. The silver oxide layer acts as a dielectric spacer between the two continuous gold films and produces significantly enhanced SERS signals, as compared to optimized single layer substrates of the same geometry or comparable substrates prepared by deposition of silver islands that are not oxidized. In addition to the enhanced sensitivity of these multilayer substrates, they also exhibit long SERS active shelf-lives (i.e., months), with no measurable degradation in SERS enhancement, and relative standard deviations in SERS enhancement of less than 5.2% across the substrate's surface.     

Optical properties of surface-enhanced Raman-active capture matrices

Silver and gold colloidal particles can be immobilized on amine-derivatized magnetic microparticles. Once immobilized, the colloidal particles can be reacted with thiols to form a self-assembled monolayer (SAM). Earlier it was shown that the resultant derivatized magnetic microparticles, i.e., capture matrices, are surface-enhanced Raman (SERS) active and that they can be used to extract trace amounts of analyte from an aqueous sample. In this investigation, the optical properties of the capture matrices are examined. Imaging of these magnetic microparticles shows that the immobilized silver/gold colloidal particles exhibit blinking behavior. An increase in the SERS signals due to the SAM and the continuum is observed with constant laser illumination of these magnetic microparticles. Such an increase can be used to improve sensitivity. This increase in signal is attributed to the electromagnetic enhancement mechanism (EEM).     

Novel method for preparing controllable and stable silver particle films for surface-enhanced Raman scattering spectroscopy

A new surface-enhanced Raman scattering (SERS) active substrate has been developed based on our previous study. Small silver nanoparticles on a quartz slide can be enlarged by using a mixture of commercially available reagents called Silver Enhancer and Initiator. The optical properties and characteristics of the new substrate have been investigated by ultraviolet-visible (UV-Vis) spectroscopy and atomic force microscopy (AFM). The results indicate that the small silver nanoparticles grow and some silver aggregates emerge on the quartz slide after the slide is immersed into the Silver Enhancer and Initiator Mixture (SEIM). The average diameter of the silver nanoparticles on the substrate becomes approximately double after the immersion into SEIM for 20 s. 1,4-bis[2-(4-pyridyl)ethenyl]-benzene (BPENB) was used as a Raman probe to evaluate the enhancement ability of the new silver substrate. It has been found that the SERS intensity can be increased about 10 times by using the substrate treated by SEIM compared with that without being treated by SEIM. Interestingly enough, the SERS enhancement increases with time. This may be due to the reorganization of silver nanoparticles on the quartz surface. The new substrate can remain active for more than 90 days. The adsorption mode of BPENB on the new substrate and the dependence of the BPENB configurations on the concentration of BPENB in methanol solution have also been investigated by SERS or UV-Vis spectroscopy. The SERS spectra of a self-assembled monolayer (SAM) BPENB film adsorbed on a silver substrate treated by SEIM show that BPENB molecules are chemically absorbed through the Ag-N bond. Consequently, a nearly perpendicular orientation of BPENB on the silver surface is proposed. The SERS spectra of BPENB SAMs on the new substrates fabricated from methanol solutions with different concentrations are compared. The concentration dependence of the SERS spectra reveals that the BPENB molecules are adsorbed on the silver film as monomers when the film is prepared from the solution with a lower concentration (<4 x 10(-6) M) and as aggregates when it is prepared from the solution with a higher concentration (>1 x 10(-5) M).     

Surface-enhanced Raman scattering dendritic substrates fabricated by deposition of gold and silver on silicon

This paper reports a study on the preparation of gold nanoparticles and silver dendrites on silicon substrates by immersion plating. Firstly, gold was deposited onto silicon wafer from HF aqueous solution containing HAuCl4. Then, the silicon wafer deposited gold was dipped into HF aqueous solution of AgNO3 to form silver coating gold film. Scanning electron microscopy reveals a uniform gold film consisted of gold nanoparticles and rough silver coating gold film containing uniform dendritic structures on silicon surface. By SERS (surface-enhanced Raman scattering) measurements, the fabricated gold and silver coating gold substrates activity toward SERS is assessed. The SERS spectra of crystal violet on the fabricated substrates reflect the different SERS activities on gold nanoparticles film and silver coating gold dendrites film. Compared with pure gold film on silicon, the film of silver coating gold dendrites film significantly increased the SERS intensity. As the fabrication process is very simple, cost-effective and reproducible, and the fabricated silver coating gold substrate is of excellent enhancement ability, spatial uniformity and good stability.     

Ultraviolet-visible and surface-enhanced Raman scattering spectroscopy studies on self-assembled metalloporphyrin films on organic monolayer-modified ultra-thin silver substrates

A self-assembled monolayer (SAM) film of 5,10,15,20-tetra-(para-chlorophenyl)-porphyrin terbium (or lutetium) hydroxy compound (TbOH/LuOH) fabricated on a silver substrate premodified with a SAM of 4-mercaptopyridine (PySH) was studied by ultraviolet-visible (UV-Vis) spectroscopy and surface-enhanced Raman scattering (SERS) spectroscopy. PySH can modify the substrate and deliver its pyridyl group pointing out from the silver surface. Thus, we can investigate the effects of the central metals of the metalloporphyrins in the formation of the composite films. For the TbOH-PySH composite film, a new absorption band arising from TbOH appears at 425 nm, and a band at 512 nm due to the PySH-modified silver substrate shifts to a longer wavelength (538 nm). The results suggest that TbOH is successfully assembled on the top of PySH-modified silver film and that there is an interaction between TbOH and PySH in the film. The frequency shifts and relative intensity changes of bands due to PySH in the SERS spectra imply the coordination of the pyridyl group on Tb in the SAM. As for the LuOH-PySH composite film, its SERS spectrum shows bands arising from both the LuOH and PySH moieties, indicating that LuOH is assembled on the PySH-modified silver film. Furthermore, a band at 1221 cm(-1) due to the in-plane C-H bending mode of PySH disappears, implying that the pyridyl moiety of PySH becomes more parallel to the silver surface upon the formation of the LuOH-PySH composite film. Additionally, an absorption band at 515 nm shifts to a longer wavelength (541 nm) and becomes broad upon the formation of the composite film, suggesting an interaction between LuOH and PySH in the film. By comparing the spectral changes between the two self-assembled composite films, we find that the central metal is crucial in the formation of the composite films. The structure and orientation of the composite films depend on the central metal of the metalloporphyrin compounds.     

Surface-enhanced Raman spectroscopy biosensors: excitation spectroscopy for optimisation of substrates fabricated by nanosphere lithography

In the 28 years since its discovery, surface-enhanced Raman scattering (SERS) has progressed from model system studies of pyridine on a roughened silver electrode to state-of-the-art surface science studies and real-world sensing applications. Each year, the number of SERS publications increases as nanoscale material design techniques advance and the importance of trace analyte detection increases. To achieve the lowest limits of detection, both the relationship between surface nanostructure and laser excitation wavelength and the analyte-surface binding chemistry must be carefully optimised. This work exploits the highly tunable nature of nanoparticle optical properties to establish the optimisation conditions. Two methods are used to study the optimised conditions of the SERS substrate: plasmon-sampled and wavelength-scanned surfaced Raman excitation spectroscopy (SERES). The SERS enhancement condition is optimised when the energy of the localised surface plasmon resonance of the nanostructures lies between the energy of the excitation wavelength and the energy of the vibration band of interest. These optimised conditions enabled the development of SERS-based sensors for the detection of a Bacillus anthracis biomarker and glucose in a serum-protein matrix.     

Fabrication of large area nanoprism arrays and their application for surface enhanced Raman spectroscopy

This work demonstrates the fabrication of metallic nanoprism (triangular nanostructure) arrays using a low-cost and high-throughput process. In the method, the triangular structure is defined by the shadow of a pyramid during angle evaporation of a metal etching mask. The pyramids were created by nanoimprint lithography in polymethylmethacrylate (PMMA) using a mould having an inverse-pyramid-shaped hole array formed by KOH wet etching of silicon. Silver and gold nanoprism arrays with a period of 200?nm and an edge length of 100?nm have been fabricated and used as effective substrates for surface enhanced Raman spectroscopy (SERS) detection of rhodamine 6G (R6G) molecules. Numerical calculations confirmed the great enhancement of electric field near the sharp nanoprism corners, as well as the detrimental effect of the chromium adhesion layer on localized surface plasmon resonance. The current method can also be used to fabricate non-equilateral nanoprism and three-dimensional (3D) nanopyramid arrays, and it can be readily extended to other metals.     

Competitive Reaction Pathway for Site‐Selective Conjugation of Raman Dyes to Hotspots on Gold Nanorods for Greatly Enhanced SERS Performance

Common methods to prepare SERS (surface‐enhanced Raman scattering) probes rely on random conjugation of Raman dyes onto metal nanostructures, but most of the Raman dyes are not located at Raman‐intense electromagnetic hotspots thus not contributing to SERS enhancement substantially. Herein, a competitive reaction between transverse gold overgrowth and dye conjugation is described to achieve site selective conjugation of Raman dyes to the hotspots (ends) on gold nanorods (GNRs). The preferential overgrowth on the nanorod side surface creates a barrier to prevent the Raman dyes from binding to the side surface except the ends of the GNRs, where the highest SERS enhancement factors are expected. The SERS enhancement observed from this special structure is dozens of times larger than that from conjugates synthesized by conventional methods. This simple and powerful strategy to prepare SERS probes can be extended to different anisotropic metal nanostructures with electromagnetic hotspots and has immense potential in in‐depth SERS‐based biological imaging and single‐molecule detection.     

Surface-enhanced Raman spectroscopy studies of orderly arranged silica nanospheres-synthesis,characterization and dye detection

Silica nanospheres have been explored much for drug delivery, photocatalysis, sensors and energy storage applications. It also acts as a template for Surface-Enhanced Raman Spectroscopy (SERS) substrates. Uniform nanostructures at low cost with high reproducibility are the major challenges in SERS substrate fabrication. In the present work, silica nanospheres were synthesized using stober method and deposited on to glass slides using Vertical deposition techniques. Different size/thickness of Silver (Ag) nanoparticles were deposited onto silica thin films using sputter deposition technique. The monodispersity of silica nanospheres and size of silver nanoparticles (10 nm, 20 nm and 30 nm) were confirmed by FESEM analysis. The structural properties were confirmed through XRD. UV–Vis analysis revealed that the plasmonic properties of Ag@SiO₂ give high surface plasmons for 30 nm thickness of silver. The binding energy of Ag@SiO₂ confirmed through XPS spectrum. The fabricated SERS substrates were used to detect Rhodamine 6G (R6G), Methylene blue (MB), Methylene violet (MV) and Methyl orange dyes as an analyte molecule with a limit of detection at about 10^?11 mol/L. The addition of SiO₂ nanospheres decreases the Ag oxidation rate and increases their stability. The maximum enhancement factor (1.5?×?10⁷) achieved for 30nm thickness of Ag@SiO₂. The results and technique establish the potential applications and reproducible SERS substrate.

     

Gold nanolenses generated by laser ablation-efficient enhancing structure for surface enhanced Raman scattering analytics and sensing

Nanoaggregates formed by metal spheres of different radii and interparticle distances represent finite, deterministic, self-similar systems that efficiently concentrate optical fields and act as "nanolenses". Here we verify experimentally the theoretical concept of nanolenses and explore their potential as enhancing nanostructures in surface enhanced Raman scattering (SERS). Self-similar structures formed by gold nanospheres of different sizes are generated by laser ablation from solid gold into water. These nanolenses exhibit SERS enhancement factors on the order of 10(9). The "chemically clean" preparation process provides several advantages over chemically prepared nanoaggregates and makes the stable and biocompatible gold nanolenses potent enhancing structures for various analytical and sensing applications.     

Plasmonic Amplifiers: Engineering Giant Light Enhancements by Tuning Resonances in Multiscale Plasmonic Nanostructures

The unique ability of plasmonic nanostructures to guide, enhance, and manipulate subwavelength light offers multiple novel applications in chemical and biological sensing, imaging, and photonic microcircuitry. Here the reproducible, giant light amplification in multiscale plasmonic structures is demonstrated. These structures combine strongly coupled components of different dimensions and topologies that resonate at the same optical frequency. A light amplifier is constructed using a silver mirror carrying light‐enhancing surface plasmons, dielectric gratings forming distributed Bragg cavities on top of the mirror, and gold nanoparticle arrays self‐assembled into the grating grooves. By tuning the resonances of the individual components to the same frequency, multiple enhancement of the light intensity in the nanometer gaps between the particles is achieved. Using a monolayer of benzenethiol molecules on this structure, an average SERS enhancement factor <EF> ～10⁸ is obtained, and the maximum enhancement in the interparticle hot‐spots is ～3 × 10¹⁰, in good agreement with FDTD calculations. The high enhancement factor, large density of well‐ordered hot‐spots, and good fidelity of the SERS signal make this design a promising platform for quantitative SERS sensing, optical detection, efficient solid state lighting, advanced photovoltaics, and other emerging photonic applications.     

Non-lithographic SERS substrates: tailoring surface chemistry for Au nanoparticle cluster assembly

Near‐field plasmonic coupling and local field enhancement in metal nanoarchitectures, such as arrangements of nanoparticle clusters, have application in many technologies from medical diagnostics, solar cells, to sensors. Although nanoparticle‐based cluster assemblies have exhibited signal enhancements in surface‐enhanced Raman scattering (SERS) sensors, it is challenging to achieve high reproducibility in SERS response using low‐cost fabrication methods. Here an innovative method is developed for fabricating self‐organized clusters of metal nanoparticles on diblock copolymer thin films as SERS‐active structures. Monodisperse, colloidal gold nanoparticles are attached via a crosslinking reaction on self‐organized chemically functionalized poly(methyl methacrylate) domains on polystyrene‐block‐poly(methyl methacrylate) templates. Thereby nanoparticle clusters with sub‐10‐nanometer interparticle spacing are achieved. Varying the molar concentration of functional chemical groups and crosslinking agent during the assembly process is found to affect the agglomeration of Au nanoparticles into clusters. Samples with a high surface coverage of nanoparticle cluster assemblies yield relative enhancement factors on the order of 10⁹ while simultaneously producing uniform signal enhancements in point‐to‐point measurements across each sample. High enhancement factors are associated with the narrow gap between nanoparticles assembled in clusters in full‐wave electromagnetic simulations. Reusability for small‐molecule detection is also demonstrated. Thus it is shown that the combination of high signal enhancement and reproducibility is achievable using a completely non‐lithographic fabrication process, thereby producing SERS substrates having high performance at low cost.     

Hot-spot engineering in polygonal nanofinger assemblies for surface enhanced Raman spectroscopy

Multiparticle assemblies of nanoscale structures are the fundamental building blocks for powerful plasmonic devices. Here we show the controlled formation of polygonal metal nanostructure assemblies, including digon, trigon, tetragon, pentagon, and hexagon arrays, which were formed on top of predefined flexible polymer pillars that undergo self-coalescence, analogous to finger closing, with the aid of microcapillary forces. This hybrid approach of combining top-down fabrication with self-assembly enables the formation of complex nanoplasmonic structures with sub-nanometer gaps between gold nanoparticles. On comparison of the polygon-shaped assemblies, the symmetry dependence of the nanoplasmonic structures was determined for application to surface enhanced Raman spectroscopy (SERS), with the pentagonal assembly having the largest Raman enhancement for the tested molecules. Electromagnetic simulations of the polygonal structures were performed to visualize the field enhancements of the hot spots so as to guide the rational design of optimal SERS structures.     

Surface-enhanced Raman spectroscopy of self-assembled monolayers: sandwich architecture and nanoparticle shape dependence

Surface enhanced Raman scattering (SERS) spectra of 4-mercaptobenzoic acid (4-MBA) self-assembled monolayers (SAMs) on gold substrates is presented for SAMs onto which gold nanoparticles of various shapes have been electrostatically immobilized. SERS spectra of 4-MBA SAMs are enhanced in the presence of immobilized gold nanocrystals by a factor of 10(7)-10(9) relative to 4-MBA in solution. Large enhancement factors are a likely result of plasmon coupling between the nanoparticles (localized surface plasmon) and the smooth gold substrate (surface plasmon polariton), creating large localized electromagnetic fields at their interface, where 4-MBA molecules reside in this sandwich architecture. Moreover, enhancement factors depend on nanoparticle shape and vary by a factor of 10(2). This SERS geometry offers large surface enhancements for molecules adsorbed onto planar substrates and could be quite useful for determining chemical information for poor Raman scatterers from assays on 2-D substrates.     

Gold nanorods with finely tunable longitudinal surface plasmon resonance as SERS substrates

Advances in nanophotonics have shown the potential of colloidal metal nanoparticles with sharp tips, such as rods, to focalize plasmonic electromagnetic fields. We report on the synthesis of Au nanorods via a seed mediated approach and the influence of silver ions on the aspect ratio of the Au nanorods. The longitudinal surface plasmon resonance (LSPR) of the Au nanorods was successfully tuned with the concentration of silver ions. The surface enhanced Raman scattering (SERS) effect of 2-aminothiophenol (2-ATP) as a probe molecule on Au nanorods was systematically studied by varying the longitudinal surface plasmon resonance of the nanorods. The highest electromagnetic enhancement was observed when the longitudinal surface plasmon resonance of the Au nanorods overlapped with the laser excitation wavelength. The variation of the SERS enhancement factor with the longitudinal surface plasmon resonance and laser excitation lines is also discussed in detail.     

Raman spectroscopic detection for perchlorate at low concentrations

Perchlorate (ClO4-) has recently emerged as a widespread environmental contaminant found in groundwater and surface water, and there is a great need for rapid detection and monitoring of this contaminant. In this study, we explore the use of surface-enhanced (SERS) and normal Raman spectroscopy for detecting ClO4- at low concentrations. We found that ClO4- is SERS active and, for the first time, were able to detect ClO4- at concentrations as low as 10(-6)-10(-7) M (or 10-100 microg/L) through the application of silver SERS substrates or selective sorbents such as bifunctional anion-exchange resins. The use of selective sorbents greatly enhanced the reproducibility and sensitivity of ClO4- detection by normal Raman spectroscopy. Further exploration and research may allow application of these techniques for in situ, real-time detection and monitoring of ClO4- in environmental samples at even lower concentrations.