Aligned silver nanorod arrays for surface-enhanced Raman scattering

Silver nanorods were prepared by a seed-mediated growth approach, and self-assembled into two-dimensional ordered arrays on glass substrates. The polarization-dependent optical responses of the rods were measured, which indicated ordered alignment. These arrays were evaluated as potential surface-enhanced Raman spectroscopy (SERS) substrates using trans-bis(4-pyridyl)ethylene molecules. The SERS signals were observed to be enhanced with the increase of the aspect ratio of the Ag nanorod, and this was mainly attributed to the local field enhancement. The lateral arrangement of the Ag nanorod arrays was also partially responsible for the SERS enhancement.     

Silver nanorod arrays as a surface-enhanced Raman scattering substrate for foodborne pathogenic bacteria detection

Surface-enhanced Raman scattering (SERS) using novel silver nanorod array substrates has been used for the detection of pathogenic bacteria. The substrate consists of a base layer of 500 nm silver film on a glass slide and a layer of silver nanorod array with a length of approximately 1 microm produced by the oblique angle deposition method at a vapor incident angle of 86 degrees . Spectra from whole cell bacteria, Generic Escherichia coli, E. coli O157:H7, E. coli DH 5alpha, Staphylococcus aureus, S. epidermidis, and Salmonella typhimurium, and bacteria mixtures have been obtained. This SERS active substrate can detect spectral differences between Gram types, different species, their mixture, and strains. Principal component analysis (PCA) has been applied to classify the spectra. Viable and nonviable cells have also been examined, and significantly reduced SERS responses were observed for nonviable cells. SERS detection of bacteria at the single cell level, excited at low incident laser power (12 micro W) and short collection time (10 s), has also been demonstrated. These results indicate that the SERS-active silver nanorod array substrate is a potential analytical sensor for rapid identification of microorganisms with a minimum of sample preparation.     

Linker-molecule-free gold nanorod layer-by-layer films for surface-enhanced Raman scattering

This paper reports a methodology for synthesizing and ordering gold nanorods into two-dimensional arrays at a water/hexane interface. This preparation method allows the systematic control of the nanoparticle film thickness. An investigation into the thickness-dependent surface-enhanced Raman scattering (SERS) of the adsorbed molecules revealed the nanorod (NR) films to have 1 order of magnitude stronger SERS enhancement than the nanosphere (NS) under similar experimental conditions. The exposed surface areas of the prepared NR and NS films were analyzed using electrochemical methods, and it was found that they had comparable exposed surface areas. Therefore, the order of magnitude difference in the enhancement factor was not due to the differences in surface area but to their intrinsic difference in the optical coupling of each film. The difference was attributed to the high density of junction points with the NR films in comparison with the corresponding NS films. Scanning emission microscopy showed that the NR films have line contacts with each other but the NS films have point contacts, which can explain the difference in SERS intensity between the NR and NS films.     

Aligned silver nanorod arrays as substrates for surface-enhanced infrared absorption spectroscopy

Preferentially aligned silver nanorod arrays prepared by oblique angle vapor deposition were evaluated as substrates for surface-enhanced infrared absorption (SEIRA) spectroscopy. These nanorod arrays have an irregular surface lattice and are composed of tilted, cylindrically shaped nanorods that have an average length of 868 nm +/- 95 nm and an average diameter of 99 nm +/- 29 nm. The overall enhancement factor for chemisorbed organic films of para-nitrobenzoic acid (PNBA) deposited onto the Ag nanorod arrays analyzed by external reflection SEIRA was calculated to be 31 +/- 9 compared to infrared reflection-absorption spectroscopy (IRRAS) obtained from a 500 nm Ag film substrate. This enhancement is attributed to the unique optical properties of the nanorod arrays as well as the increased surface area provided by the nanorod substrate. SEIRA reflection-absorbance intensity was observed with both p- and s-polarized incident radiation with angles of incidence ranging from 25 degrees to 80 degrees . The largest intensity was achieved with p-polarization and incident angles larger than 75 degrees . Polarization-dependent ultraviolet/visible/near-infrared (UV/Vis/NIR) spectra of the nanorod arrays demonstrate that the red-shifted surface plasmon peaks of the elongated nanorods may be partially responsible for the observed SEIRA response. The SEIRA detection limit for the Ag nanorod arrays was estimated to be 0.08 ng/cm(2). Surface-enhanced Raman scattering (SERS) and SEIRA analysis of chemisorbed PNBA utilizing the same nanorod substrate is demonstrated.     

Nanofabrication of densely packed metal-polymer arrays for surface-enhanced Raman spectrometry

A key element to improve the analytical capabilities of surface-enhanced Raman spectroscopy (SERS) resides in the performance characteristics of the SERS-active substrate. Variables such as shape, size, and homogeneous distribution of the metal nanoparticles throughout the substrate surface are important in the design of more analytically sensitive and reliable substrates. Electron-beam lithography (EBL) has emerged as a powerful tool for the systematic fabrication of substrates with periodic nanoscale features. EBL also allows the rational design of nanoscale features that are optimized to the frequency of the Raman laser source. In this work, the efficiency of EBL fabricated substrates are studied by measuring the relative SERS signals of Rhodamine 6G and 1,10-phenanthro-line adsorbed on a series of cubic, elliptical, and hexagonal nanopatterned pillars of ma-N 2403 directly coated by physical vapor deposition with 25 nm films of Ag or Au. The raw analyte SERS signals, and signals normalized to metal nanoparticle surface area or numbers of loci, are used to study the effects of nanoparticle morphology on the performance of a rapidly created, diverse collection of substrates. For the excitation wavelength used, the nanoparticle size, geometry, and orientation of the particle primary axis relative to the excitation polarization vector, and particularly the density of nanoparticles, are shown to strongly influence substrate performance. A correlation between the inverse of the magnitude of the laser backscatter passed by the spectrometer and SERS activities of the various substrate patterns is also noted and provides a simple means to evaluate possible efficient coupling of the excitation radiation to localized surface plasmons for Raman enhancement.     

Carbon nanowalls amplify the surface-enhanced Raman scattering from Ag nanoparticles

We report surface-enhanced Raman scattering (SERS) from Ag nanoparticles decorated on thin carbon nanowalls (CNWs) grown by microwave plasma chemical vapor deposition. The Ag morphology is controlled by exposing the CNWs to oxygen plasma and through the electrodeposition process by varying the number of deposition cycles. The SERS substrates are capable of detecting low concentrations of rhodamine 6G and bovine serum albumin, showing much higher Raman enhancement than ordinary planar HOPG with Ag decoration. The major factors contributing to this behavior include: high density of Ag nanoparticles, large surface area, high surface roughness, and the underlying presence of vertically oriented CNWs. The relatively simple procedure of substrate preparation and nanoparticle decoration suggests that this is a promising approach for fabricating ultrasensitive SERS substrates for biological and chemical detection at the single-molecule level, while also enabling the study of fundamental SERS phenomena.     

Characterization of the Ag mediated surface-enhanced Raman spectroscopy of saxitoxin

The rapid detection and quantification of saxitoxin (STX) is reported using surface-enhanced Raman spectroscopy (SERS) with a colloidal hydrosol of silver nanoparticles. Under the conditions of our experiments, the limit of detection (LD) for STX using SERS is 3 nM, with a limit of quantification (LQ) of 20 nM. It is shown that the SERS method is rapid, with spectra being collected in as little as 5 seconds total integration time for a 40 nM STX sample. In order to improve the signal-to-noise ratio, SERS spectra were generally collected with a total integration time of 1 minute (6 accumulations of 10 seconds each), with no need for extensive sample work-up or substrate preparation. Based on these results, the SERS technique shows great promise for the future detection and quantification of STX molecules in aqueous solutions.     

An effective three-dimensional surface-enhanced Raman scattering substrate based on oblique Si nanowire arrays decorated with Ag nanoparticles

Silicon nanowire arrays (SiNWAs) decorated with metallic nanoparticle heterostructures feature promising applications in surface-enhanced Raman scattering (SERS). However, the densely arranged SiNWAs are usually inconvenient for the following decoration of metallic nanoparticles, and only the top area of silicon nanowires (SiNWs) contributes to the SERS detection. To improve the utilization of the heterostructure, herein, oblique SiNWAs were grown separately, and Ag nanoparticles (AgNPs) were uniformly deposited by magnetron sputtering to get the three-dimensional (3D) SiNWAs decorated with AgNPs (AgNPs-SiNWAs) SERS substrate. The large open surfaces of oblique SiNWs would create more surface area available for the formation of hotspots and improve the adsorption and excitation of analyte molecules on the wire. The optimized AgNPs-SiNWAs substrate exhibits high sensitivity in detecting chemical molecule Rhodamine 6G, and the detection limit can reach 1 × 10^?10 M. More importantly, the substrate also can be used as an effective DNA sensor for label-free DNA detection.     

Facile fabrication of gold nanoparticle arrays for efficient surface-enhanced Raman scattering

An effective and facile method for the fabrication of a surface-enhanced Raman scattering (SERS)-active film with closely packed gold nanoparticle (AuNP) arrays is proposed by self-assembly of different sizes (16, 25, 40 and 70?nm) of AuNPs at a toluene/water interface with ethanol as the inducer. The as-prepared AuNP arrays exhibit efficient Raman scattering enhancement, and the enhancement factors estimated using p-aminothiophenol as a probe molecule range from 10(5) to 10(7). This is attributed to the coupling electromagnetic SERS enhancement mechanism with additional localization field within closely packed AuNPs, which have greater SERS activity and reproducibility than that on aggregates and on self-assembled monolayers of isolated AuNPs on glass.     

Integrate silver colloids with silicon nanowire arrays for surface-enhanced Raman scattering

A facile method to prepare uniform and reproducible surface-enhanced Raman scattering (SERS) substrates is presented. Quasi-spherical silver colloids prepared by microwave heating and wafer-scale uniform silicon nanowire (SiNW) arrays fabricated via wet chemical etching were united together as SERS substrates. The novel SERS substrates displayed stronger Raman enhancement than conventional silver colloids as well as outstanding uniformity and reproducibility in our experiments. In addition, it was found that the cross section of SiNW arrays possessed stronger enhancement activity than the front side. The enhancement effects of two adjacent SiNWs (as a simplification of SiNW arrays) were evaluated by the finite difference time domain (FDTD) method.     

Ag nanowire/nanoparticle-decorated MoS2 monolayers for surface-enhanced Raman scattering applications

Nano Research - Developing well-defined nanostructures with superior surface-enhanced Raman scattering (SERS) performance is a critical and highly desirable goal for the practical applications of...     

Characterization of novel Ag on TiO2 films for surface-enhanced Raman scattering

Novel Ag on TiO2 films are generated by semiconductor photocatalysis and characterized by ultraviolet-visible (UV/Vis) spectroscopy, scanning electron microscopy (SEM), and atomic force microscopy (AFM), as well as assessed for surface-enhanced Raman scattering (SERS) activity. The nature and thickness of the photodeposited Ag, and thus the degree of SERS activity, is controlled by the time of exposure of the TiO2 film to UV light. All such films exhibit the optical characteristics (lambda(max) congruent with 390 nm) of small (< 20 nm) Ag particles, although this feature becomes less prominent as the film becomes thicker. The films comprise quite large (> 40 nm) Ag islands that grow and merge with increasing levels of Ag photodeposition. Tested with a benzotriazole dye probe, the films are SERS active, exhibiting activity similar to that of 6-nm-thick vapor-deposited films. The Ag/TiO2 films exhibit a lower residual standard deviation (approximately 25%) compared with Ag vapor-deposited films (approximately 45%), which is, however, still unacceptable for quantitative work. The sample-to-sample variance could be reduced significantly (< 7%) by spinning the film during the SERS measurement. The Ag/TiO2 films are mechanically robust and resistant to removal and damage by scratching, unlike the Ag vapor-deposited films. The Ag/TiO2 films also exhibit no obvious loss of SERS activity when stored in the dark under otherwise ambient conditions. The possible extension of this simple, effective method of producing Ag films for SERS, to metals other than Ag and to semiconductors other than TiO2, is briefly discussed.     

Dynamic rastering surface-enhanced Raman scattering (SERS) measurements on silver nanorod substrates

Surface-enhanced Raman spectra of a thiol-modified biotin derivative on oblique-angle-deposited silver nanorod (AgNR) array substrates were measured using both static and rotating rastering methods. We find that the rotating rastering method has a strong tendency to decrease the point-to-point relative standard deviation (RSD) compared to static measurements as well as decrease the effects of cumulative excitation exposure. The AgNR substrates treated with the modified biotin typically demonstrate intra-substrate RSDs of <10%, with an average RSD of ～3% when the rastering radius r=1 mm. The quantitative studies on the relationship between rastering radius, sampling area, and rastering frequency show that only the rastering radius appears to have significant effect on the measured RSD. Our results demonstrate that under the proper measurement and sample preparation conditions, the Ag nanorod substrates are very uniform.     

Self-assembly nanoparticle based tripetaloid structure arrays as surface-enhanced Raman scattering substrates

This paper reports a novel highly ordered tripetaloid structure array (TPSA) which performs very well as an active surface-enhanced Raman scattering (SERS) substrate. The TPSA is easily fabricated by anisotropic etching of a self-assembly silica-nanoparticle bilayer and a subsequent metal deposition step, with notable uniformity and reproducibility. Electromagnetic simulation indicates that the narrow inter-gaps and edge protrusions in the TPSA act as hot spots. In addition, the peak electromagnetic field intensity in the inter-gaps changes slightly and periodically as the polarization of the incident light varies from 0°?to 360°. SERS experiments show that the SERS enhancement factor (EF) of a Au-film-covered TPSA is 12 times higher than that of regular Au-film-over-nanoparticles, and not sensitive to the polarization of the incident light. The spatially averaged EF of the TPSA is as high as 5.7?×?10(6), and the local EF of its hot spots is much higher.     

Dispersible gold nanorod dimers with sub-5 nm gaps as local amplifiers for surface-enhanced Raman scattering

We report the synthesis of solution-dispersible, 35 nm diameter gold nanorod dimers with gaps as small as ～2 nm for surface-enhanced Raman scattering (SERS). Using on-wire lithography (OWL), we prepared tailorable dimers in high yield and high monodispersity (～96% dimers) that produce both large and reproducible SERS signals with enhancement factors of (6.8 ± 0.7) × 10(8) for single dimers in air and 1.2 × 10(6) for ensemble-averaged solution measurements. Furthermore, we show that these structures, which are the smallest ever made by OWL, can be used to detect molecules on flat surfaces and in aqueous solutions. When combined, these attributes with respect to sensitivity, reproducibility, and tailorability lead to a novel and powerful local amplification system for SERS applications.     

Probing intrinsic and extrinsic components in single osteosarcoma cells by near-infrared surface-enhanced Raman scattering

We report on the capabilities of near-infrared surface-enhanced Raman scattering (SERS) using gold nanoparticles to obtain detailed chemical information with high spatial resolution from within single cancer cells, living or fixed. Colloidal gold particles, 60 nm in size, were introduced into live human osteosarcoma cells by endocytosis by adding them to the growth medium. Rapid SERS mapping of cells indicated that not only could rich vibrational spectra be obtained from intrinsic cellular constituents both in the cytoplasm and nucleus and but also the distribution of extrinsic molecules introduced into the cells, in this case, rhodamine 6G could be characterized, suggesting that the intracellular distribution of chemotherapeutic agents could potentially be measured by this technique. We show that the SERS signal intensity from the cellular components increases and more spectral detail is acquired from dried cells when compared with hydrated cells in buffer. The data also show spectral fluctuations, mainly in intensity but also in peak position, which are dependent upon the intensity of the excitation light and are probably due to diffusion of molecules on the surface of the gold nanoparticles. A detailed understanding of the origins of these effects is still not complete, but the ability to acquire very sensitive SERS inside living cancer cells indicates the potential of this technique as a useful tool in biomedicine.     

Inverted size-dependence of surface-enhanced Raman scattering on gold nanohole and nanodisk arrays

Surface-enhanced Raman scattering (SERS) on gold nanohole and nanodisk arrays with precisely controlled size and spacing fabricated via electron beam lithography was investigated. These nanostructures exhibit strong SERS signals at 785 nm excitation but not at 514 nm. When the edge-to-edge distance is maintained, enhancement increases for nanoholes but decreases for nanodisks as diameter is increased. It is shown that the observed enhancement results from the local surface plasmon resonance wavelength shifts to the near-infrared regime as nanohole diameter increases. The large tolerance on dimensions and the empty space confined by nanoholes suggest promise for their use as a functional component in sensing, spectroscopy, and photonic devices.     

ZnO nanorod arrays for photoelectrochemical cells

The splitting of water using photoelectrochemical (PEC) cells to produce hydrogen is one of the most sustainable forms of energy production and more and more 1-D nanostructrues semiconductors used as photoelectrodes have been studied extensively. However, it is not clear whether the photoconversion efficiencies of such nanostructure devices are limited by the architectures of the 1-D electrodes. Here, we explore the effect of the architecture like the length and width of ZnO nanorods on the PEC cells performance for the first time. The as-prepared nanorods have diameters of 40-50 nm and lengths of 400-800 nm. Preliminary measurements exhibit that the resulting electrodes have promising PEC properties. Mott-Schottky measurements give a flat-band potential of +0.10 V, a carrier density of 3.7 x 10(17) cm(-3), and a space-charge layer of 26 nm. The photocurrent of 800 nm-long nanorods shows 10 times higher than that of 400 nm-long ones, and an encouraging maximum photoconversion efficiency of 0.25% is obtained under illumination of 100 mW/cm2 (AM 1.5), which is among the highest reported for an undoped ZnO photoelectrode to date.