Controlled fabrication of surface-enhanced-Raman scattering-active silver nanostructures on polypyrrole films

Different kinds of silver nanostructures have been deposited on the surface of the polypyrrole (PPy) films by silver-mirror reaction. The morphology of silver nanostructures can be controlled by modulating the reaction conditions. The application of the as-prepared PPy–silver composites in surface-enhanced Raman scattering (SERS) was studied using 4-mercaptopyridine (4-Mpy) as probe molecules. The results showed that PPy–silver composites exhibited excellence SERS ability and could be used as SERS-active substrates for detection of trace molecules.     

Fabrication of high performance surface enhanced Raman scattering substrates by a solid-state ionics method

Silver nanostructures were prepared by a solid-state ionics method using fast ionic conductor RbAg(4)I(5) films under a direct current electric field (DCEF). The surface morphology of the silver nanostructures grown under different constant current fields was characterized by scanning electron microscopy (SEM). Rhodamine 6G (R6G) aqueous solutions were used as probe molecules to detect the Raman enhancement performance of the silver nanostructure substrates. The effect of external electric field current intensity on the surface morphology of the silver nanostructures during the preparation was studied in detail. The enhancement effect of the silver nanostructure surface enhanced Raman scattering (SERS) substrates with different surface morphologies toward R6G was determined. We found that disordered silver nanowires (DSNW), ordered silver nanowires (OSNW), densely arranged silver nanobamboo arrays (SNBA) and compactly arranged silver nanobud clusters (SNBC) were respectively obtained when the constant current intensity was 3?μA, 5?μA, 8?μA and 12?μA under the same vacuum evaporation plating conditions. The limiting concentrations of R6G for these SERS substrates were found to be 10(-7)?mol?l(-1), 10(-13)?mol?l(-1), 10(-13)?mol?l(-1) and 10(-16)?mol?l(-1), respectively.     

Trinitrotoluene explosive lights up ultrahigh Raman scattering of nonresonant molecule on a top-closed silver nanotube array

The highest Raman enhancement factors are obtained in a double resonance: molecular electronic resonance and plasmon resonance with a "hot spot" in surface-enhanced Raman scattering (SERS). However, for most molecules of interest the double resonance is not realized with the excitation frequencies normally used in Raman. The latter may limit the practical applications of SERS for trace analysis. Here, we report that Raman-inactive trinitrotoluene (TNT) lights up the ultrahigh Raman scattering of off-resonated p-aminobenzenethiol (PABT) through the formation of charge-transfer TNT-PABT complex on the top-closed flexible silver nanotube array. Raman hot spots can spontaneously form in a reversible way by the self-approaching of flexible nanotubes driven through the capillary force of solvent evaporation. Meanwhile, the PABT-TNT-PABT bridges between self-approaching silver nanotubes possibly form by the specific complexing and zwitterion interactions, and the resultant chromophores can absorb the visible light that matches with the incident laser and the localized surface plasmon of a silver nanotube array. The multiple spectral resonances lead to the huge enhancement of Raman signals of PABT molecules due to the presence of ultratrace TNT. The enhancement effect is repeatedly renewable by the reconstruction of molecular bridges and can selectively detect TNT with a limit of 1.5 × 10(-17) M. The results in this report provide the simple and supersensitive approach to the detection of TNT explosives and the possibility of building a robust Raman-based assay platform.     

Highly Surface‐roughened “Flower‐like” Silver Nanoparticles for Extremely Sensitive Substrates of Surface‐enhanced Raman Scattering

Surface‐enhanced Raman scattering (SERS) is a new optical spectroscopic analysis technique with potential for highly sensitive detection of molecules. Recently, many efforts have been made to find SERS substrates with high sensitivity and reproducibility. In this Research News article, we provide a focused review on the synthesis of monodispersed silver particles with a novel, highly roughened, “flower‐like” morphology by reducing silver nitrate with ascorbic acid in aqueous solutions. The nanometer‐scale surface roughness of the particles can provide several hot spots on a single particle, which significantly increases SERS enhancement. The incident polarization‐dependent SERS of individual particles is also studied. Although the different “hot spots” on a single particle can have a strong polarization dependency, the total Raman signals from an individual particle usually have no obvious polarization dependency. Moreover, these flower‐like silver particles can be measured by SERS with high enhancement several times, which indicates the high stability of the hot spots. Hence, the flower‐like silver particles here can serve as highly sensitive and reproducible SERS substrates.     

Controlled Assembly of Highly Raman‐Enhancing Silver Nanocap Arrays Templated by Porous Anodic Alumina Membranes

A convenient nanoscale technique is reported for the fabrication of highly ordered hemispherical silver nanocap arrays templated by porous anodic alumina (PAA) membranes as robust and cost‐efficient surface‐enhanced Raman scattering (SERS) substrates. This geometry produces a high Raman signal due to its periodic hexagonal arrangements and control of the gap between the nanostructures in the sub‐10‐nm regime. The surface structure can be tuned further to optimize the enhancement factor according to optional PAA fabrication and silver deposition parameters. Finite‐difference time‐domain calculations indicate that the structure may possess excellent SERS characteristics due to the high density and abundance of hot spots.     

Non-linear and resonance effects in carbon nanotube structures

In this paper, we report on Raman scattering and Surface Enhanced Raman Scattering (SERS) studies of single walled carbon nanotubes (SWNTs) and carbon nanotube/conjugated polymers composites. We demonstrate that under SERS conditions we induce an abnormal anti-Stokes Raman emission, that can be interpreted as being due to a “single-beam pumped” Coherent Anti-Stokes Raman Scattering (CARS) effect. We also investigate in detail the anti-Stokes/Stokes (aS/S) intensity ratios of the radial breathing modes (RBMs) of SWNTs as a function of several parameters. From calculations, we show that resonance phenomena mostly explain the aS/S intensity ratio anomalies, but only at low frequencies. In addition, we describe results obtained with polymers like poly(bithiophene) (PBTh) polymerized on carbon nanotube thin films which exhibit also an amplification of its high frequency Raman modes in the anti-Stokes branch, generated by the plasmon excitation of metallic tubes. This phenomenon occurs in several other materials such as composites based on SWNTs and conjugated polymers such as poly(3,4-ethylenedioxythiophene) (PEDOT) and polyparaphenylene-vinylene (PPV) for modes located around 1500 cm⁻¹.     

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.     

Structural and Optical Properties and Emerging Applications of Metal Nanomaterials

Nanomaterials possess intriguing optical properties that depend sensitively on size, shape, and material content of the structures. Controlling such structural characteristics of the nanostructures allows the tailoring of their physical and chemical properties, e.g. optical, electronic, and catalytic, to achieve what is desired lot specific applications of interest. This review will cover the development of various shapes for silver and gold nanomaterials with emphasis on their relation to optical properties. Examples of various modern synthetic methods and characterization techniques are highlighted. The influence of the metal nanomaterial＇s shape and optical absorption on surface enhanced Raman scattering （SERS） and a final note on new emerging applications of metal nanostructures are also discussed.     

Bio-imaging, detection and analysis by using nanostructures as SERS substrates

Surface-enhanced Raman scattering (SERS) is a phenomenon that occurs on nanoscale-roughed metallic surface. The magnitude of the Raman scattering signal can be greatly enhanced when the scatterer is placed in the very close vicinity of the surface, which enables this phenomenon to be a highly sensitive analytical technique. SERS inherits the general strongpoint of conventional Raman spectroscopy and overcomes the inherently small cross section problem of a Raman scattering. It is a sensitive and nondestructive spectroscopic method for biological samples, and can be exploited either for the delivery of molecular structural information or for the detection of trace levels of analytes. Therefore, SERS has long been regarded as a powerful tool in biomedical research. Metallic nanostructure plays a key role in all the biomedical applications of SERS because the enhanced Raman signal can only be obtained on the surface of a finely divided substrate. This review focuses on progress made in the use of SERS as an analytical technique in bio-imaging, analysis and detection. Recent progress in the fabrication of SERS active nanostructures is also highlighted.     

High-density silver nanoparticle film with temperature-controllable interparticle spacing for a tunable surface enhanced Raman scattering substrate

The formation of high-density silver nanoparticles and a novel method to precisely control the spacing between nanoparticles by temperature are demonstrated for a tunable surface enhanced Raman scattering substrates. The high-density nanoparticle thin film is accomplished by self-assembling through the Langmuir-Blodgett (LB) technique on a water surface and transferring the particle monolayer to a temperature-responsive polymer membrane. The temperature-responsive polymer membrane allows producing a dynamic surface enhanced Raman scattering substrate. The plasmon peak of the silver nanoparticle film red shifts up to 110 nm with increasing temperature. The high-density particle film serves as an excellent substrate for surface-enhanced Raman spectroscopy (SERS), and the scattering signal enhancement factor can be dynamically tuned by the thermally activated SERS substrate. The SERS spectra of Rhodamine 6G on a high-density silver particle film at various temperatures is characterized to demonstrate the tunable plasmon coupling between high-density nanoparticles.     

Volume‐Enhanced Raman Scattering Detection of Viruses

Virus detection and analysis are of critical importance in biological fields and medicine. Surface‐enhanced Raman scattering (SERS) has shown great promise in small molecule and even single molecule detection, and can provide fingerprint signals of molecules. Despite the powerful detection capabilities of SERS, the size discrepancy between the SERS “hot spots” (generally, <10 nm) and viruses (usually, sub‐100 nm) yields poor detection reliability of viruses. Inspired by the concept of molecular imprinting, a volume‐enhanced Raman scattering (VERS) substrate composed of hollow nanocones at the bottom of microbowls (HNCMB) is developed. The hollow nanocones of the resulting VERS substrates serve a twofold purpose: 1) extending the region of Raman signal enhancement from the nanocone surface (e.g., surface “hot spots”) to the hollow area within the cone (e.g., volume “hot spots”)—a novel method of Raman signal enhancement, and 2) directing analyte such as viruses of a wide range of sizes to those VERS “hot spots” while simultaneously increasing the surface area contributing to SERS. Using HNCMB VERS substrates, greatly improved Raman signals of single viruses are demonstrated, an achievement with important implications in disease diagnostics and monitoring, biomedical fields, as well as in clinical treatment.     

Near-Field Surface-Enhanced Raman Imaging of Dye-Labeled DNA with 100-nm Resolution

Raman chemical imaging on a scale of 100 nm is demonstrated for the first time. This is made possible by the combination of scanning near-field optical microscopy (SNOM or NSOM) and surface-enhanced Raman scattering (SERS), using brilliant cresyl blue (BCB)-labeled DNA as a sample. SERS substrates were produced by evaporating silver layers on Teflon nanospheres. The near-field SERS spectra were measured with an exposure time of 60 s and yielded good signal-to-noise ratios (25:1). The distinction between reflected light from the excitation laser and Raman scattered light allows the local sample reflectivity to be separated from the signal of the adsorbed DNA molecules. This is of general importance to correct for topographic coupling that often occurs in near-field optical imaging. The presented data show a lateral dependence of the Raman signals that points to special surface sites with particularly high SERS enhancement.     

Single-molecule detection using surface-enhanced resonance Raman scattering and Langmuir-Blodgett monolayers

The Langmuir-Blodgett (LB) technique has been used to obtain spatially resolved surface-enhanced resonance Raman scattering (SERRS) spectra of single dye molecules dispersed in the matrix of a fatty acid. The experimental results presented here mimic the original electrochemical surface-enhanced Raman scattering (SERS) work where the background bulk water did not interfere with the detection of the SERS signal of molecules adsorbed onto the rough silver electrode. LB monolayers of the dye in fatty acid have been fabricated on silver island films with a concentration, in average, of one probe molecule per micrometer square. The properties of single-molecule spectroscopy were investigated using micro-Raman including mapping and global images. Blinking of the SERRS signal was also observed.     

Uniform Microgels Containing Agglomerates of Silver Nanocubes for Molecular Size‐Selectivity and High SERS Activity

Surface‐enhanced Raman scattering (SERS) is a promising technique for molecular analysis as the molecular fingerprints (Raman spectra) are amplified to detectable levels compared with common spectroscopy. Metal nanostructures localize electromagnetic field on their surfaces, which can lead to dramatic increase of Raman intensity of molecules adsorbed. However, the metal surfaces are prone to contamination, thereby requiring pretreatment of samples to remove adhesive molecules. To avoid the pretreatment and potentially achieve point‐of‐care (POC) analysis, we have developed SERS‐active microgels using the droplet‐microfluidic system. As the microgels are composed of water‐swollen network with consistent mesh size, they selectively allow diffusion of molecules smaller than the mesh, thereby excluding large adhesives. To render the microgels highly SERS‐active, we destabilize silver nanocubes to form agglomerates, which are embedded in the matrix of microgels. The nanogaps in the agglomerates provide high sensitivity in Raman measurement and size‐selective permeability of the microgel matrix obviates the pretreatment of samples. To validate the functions, we demonstrate the direct detection of Aspirin dissolved in whole blood without any pretreatment.     

Room-temperature synthesis of flowerlike Ag nanostructures consisting of single crystalline Ag nanoplates

We demonstrate a simple wet-chemical route for the high-yield synthesis of flowerlike silver nanostructures consisting of single crystalline Ag nanoplates by mixing AgNO₃ and p-phenylenediamine (PPD) in the presence of polyvinylpyrrolidone (PVP) at room temperature. PPD serves both as a reducing agent, and as an architecture soft template with PVP to the formation of such Ag nanostructures. It is found that the presence of PVP has a significant effect on the formation and growth of these novel nanostructures. The flowerlike silver nanostructures could serve as highly sensitive and reproductive surface-enhanced Raman scattering (SERS) substrates for chemical and biological detection.     

低对称性SiO2/Ag核壳复合纳米结构的银镜反应制备及表面增强拉曼散射活性研究

利用银镜反应在自组装的SiO2纳米粒子单层膜上制备了低对称性的SiO2/Ag核壳复合纳米结构.通过透射电镜(TEM)、扫描电镜(SEM)和紫外-可见分光光度计(UV-Vis)对核壳复合纳米结构的表面形貌和光学性质进行了表征.以亚甲基蓝作为探针分子,研究了低对称性SiO2/Ag核壳复合纳米结构的表面增强拉曼散射(SERS)活性.     

Hierarchical silver nanodendrites: One-step preparation and application for SERS

Without using any other reducing reagents or templates, a one-step approach for synthesizing dendritic Ag nanostructure by the treatment of sliver ions only in the presence of silk fibroin biomacromolecule is described. The morphology and structure of as-prepared silver nanodendrite are characterized, and its application for surface-enhanced Raman scattering (SERS) is also investigated. It has been found that the morphology of as-prepared Ag dendrite is dependent on the reaction duration, but not the concentration of sliver ions in the reaction process. SERS study shows that the silver nanodendrites give an intensive and enhanced Raman scattering when pyridine is used as a probing molecule. It is suggested that silk fibroin provides dual reductant and structure-directing roles to promote sliver ions forming shape-controlled nanostructures in high yield.     

Nanowires enabling signal-enhanced nanoscale Raman spectroscopy

Silicon nanowires grown by the vapor-liquid-solid (VLS) mechanism catalyzed by gold show gold caps (droplets) approximately 20-500 nm in diameter with a half spherical towards almost spherical shape. These gold droplets are well suited to exploit the surface-enhanced Raman scattering (SERS) effect and could be used for tip-enhanced Raman spectroscopy (TERS). The gold droplet of a nanowire attached to an atomic force microscopy (AFM) tip could locally enhance the Raman signal and increase the spatial resolution. Used as a SERS template, an ensemble of self-organizing nanowires grown bottom up on a silicon substrate could allow highly sensitive signal-enhanced Raman spectroscopy of materials that show a characteristic Raman signature. A combination of a nanowire-based TERS probe and a nanowire-based SERS substrate promises optimized signal enhancement so that the detection of highly dilute species, even single molecules or single bacteria or DNA strands, and other soft matter is within reach. Potential applications of this novel nanowire-based SERS and TERS solution lie in the fields of biomedical and life sciences, as well as security and solid-state research such as silicon technology.     

Surface-enhanced Raman scattering of rhodamine 6G on nanowire arrays decorated with gold nanoparticles

We investigate the surface-enhanced Raman scattering (SERS) of rhodamine 6G (R6G) adsorbed on Au nanoparticles attached to InP nanowires. We find that nanowire arrays act as frameworks for effective SERS substrates with a significantly higher Raman signal sensitivity than a planar framework of Au nanoparticles adsorbed two-dimensionally on a flat surface. The SERS signal displays a clear polarization-dependent effect when the nanowires are arranged in a row. We also find that the SERS signal increases with time during continuous laser illumination. The plasmon-enhanced optical forces between Au nanoparticles may either move pairs of nanoparticles closer together or attract adsorbed molecules by moving them to the junctions of Au nanoparticle aggregates. Such effects by plasmon optical forces may cause the observed increase of the SERS signal with continuous laser illumination.     

Surface-enhanced Raman scattering substrate of silver nanoparticles depositing on AAO template fabricated by magnetron sputtering

In this report, we describe a fabrication process of low-cost and highly sensitive SERS substrates by using a simple anodizing setup and a low-energy magnetron sputtering method. The structure of the SERS substrates consists of silver nanoparticles deposited on a layer of anodic aluminum oxide (AAO) template. The fabricated SERS substrates are investigated by a scanning electron microscope (SEM), a transmission electron microscope (TEM), and a confocal Raman spectroscope. We have verified from the surface morphology that the fabricated SERS substrates consist of high-density round-shape silver nanoparticles where their size distribution ranges from 10 to 30 nm on the top and the bottom of nanopores. The surface-enhanced Raman scattering activities of these nanostructures are demonstrated using methylene blue (MB) as probing molecules. The detection limit of 10⁻⁸ M can be achieved from this SERS substrate.