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.     

Silver-embedded zeolite crystals as substrates for surface-enhanced Raman scattering

This paper reports the preparation of a type of Ag-embedded zeolite crystals as surface-enhanced Raman spectroscopy (SERS) substrates by chemical reduction of Ag⁺-exchanged ZSM-5. Ag⁺ ions were loaded into the zeolite framework by ion exchange. Then the exchanged-Ag⁺ ions were reduced and metallic silver clusters formed inside the zeolite channel. The resulting Ag-embedded zeolite crystals are characterized by using a number of techniques including X-ray diffraction, scanning electron microscopy, and X-ray photoelectron spectroscopy to confirm silver formed inside the crystal channel. The fabricated Ag-embedded ZSM-5 zeolite substrates displayed strong and reproducible SERS activity for different Raman probe molecules such as Tris(2,2′-bipyridyl) ruthenium(II) chloride (RuBpy) and rhodamine 6G (R6G). Since silver embedded into the zeolite channel without changing the crystal surface property, the Ag–ZSM-5 zeolite crystal can be used to prepare different SERS-active substrate (SERS-tags), in which different probe molecules may be detected. Such Ag-embedded zeolite substrate would be useful in chemical and biological sensing and in the development of SERS-based analytical devices.     

Plasma reduction of silver compounds for fabrication of surface-enhanced Raman scattering substrates

Several silver compounds were reduced by low-pressure air plasma to produce porous nanostructured surfaces as surface-enhanced Raman scattering (SERS) substrates. This method is advantageous because substrates are easy to prepare and the silver metal surface is inherently clean without spectroscopic background. Silver compounds were melted into 1-2 mm slugs on quartz slides and plasma treated for different lengths of time. Silver chloride was found to be the best compound to make reproducible and stable SERS substrates. SERS activity of the substrates was tested using L-tryptophan, 4-mercaptobenzoic acid, and adenine.     

Novel Ag-Cu substrates for surface-enhanced Raman scattering

Ag dendrites were deposited on rough Cu plate by a simple galvanic displacement process between Ag ion and Cu under room temperature. Surface-enhanced Raman scattering (SERS) performances have been studied using Rhodamine 6G (R6G) probe molecules on this kind of Ag-Cu substrates. The high SERS enhancements are attributed to the highly branched Ag dendritic nanostructures and Ag nanoparticles formed on the trunks, branches, and even leaves.     

Silver nanowire layer-by-layer films as substrates for surface-enhanced Raman scattering

In this paper, the fabrication of highly stable, surface-enhanced Raman scattering (SERS) active dendrimer/silver nanowire layer-by-layer (LBL) films is reported. Ag nanowires, approximately 100 nm in diameter, were produced in solution and transferred, using the LBL technique, onto a single fifth-generation DAB-Am dendrimer layer on a glass substrate. The Ag nanowires, and the resulting LBL films were characterized using UV-visible surface plasmon absorbance, while the LBL films were further characterized by atomic force microscopy measurements and surface-enhanced Raman and resonance Raman scattering of several analytes. The dendrimer was found to effectively immobilize the Ag nanowires with increased control over spacing and aggregation of the particles. These films are shown to be excellent substrates for SERS/SERRS measurements, demonstrating significant enhancement, and trace detection capability. Several trial analytes were tested using a variety of excitation energies, and results confirmed effective enhancement of Raman signals throughout the visible range (442-785 nm) with different molecules. Analytes were deposited onto the enhancing Ag nanowire LBL films surface using both casting and Langmuir-Blodgett monolayer transferring techniques.     

Silver-coated zeolite crystal films as surface-enhanced Raman scattering substrates

Silver-coated zeolite A and zeolite NaX crystal films prepared by vacuum deposition were investigated as surface-enhanced Raman scattering (SERS) substrates. The substrates were active for the enhancement of Raman scattering from uranyl ions. A detection limit of 10(-5) M for uranyl was obtained using silver-coated zeolite A films. One advantage of these zeolite-based substrates is that the negatively charged microporous framework provides the selectivity for adsorption based on static electric charges. The SERS effects of positively charged uranyl ions and neutrally charged benzoic acid were compared. For the zeolite A substrate, there was a 100-times-greater sensitivity.     

Silver clusters onto nanosized colloidal silica as novel surface-enhanced Raman scattering active substrates

A new method is proposed for obtaining surface-enhanced Raman scattering (SERS)-active substrates by photochemical reduction of silver nitrate onto colloidal silica. Transmission electron microscopy (TEM) and UV-visible absorption spectroscopy are employed to investigate the nanoscale structure of the materials. High quality SERS spectra are obtained from different organic ligands to check the efficiency of these substrates. A marked stability of the colloidal suspension is ensured by the scarce tendency of the Ag-doped silica particles to aggregate by either aging or adsorption of ligand.     

Shape-controlled synthesis and application in surface-enhanced Raman scattering of novel palladium nanoparticles

Palladium nanoparticles (PdNPs), as a platinum substitute, have opened many new opportunities for future catalytic applications, especially in fuel cell reactions, because of its comparable catalytic properties. In the present study, a simple and “green” procedure to the synthesis of PdNPs with cauliflower-like and polyhedron-like shapes is demonstrated. The novel PdNPs were prepared by the reduction of palladium chloride with ascorbic acid in the presence of chitosan served as a capping agent, whose shapes can be effectively controlled by varying reaction temperatures. Surface-enhanced Raman scattering (SERS) investigation demonstrated that the more irregular PdNPs have the stronger SERS activities. We believe that the PdNPs with unique shapes may find practical applications for electronics, photonics, fuel cells, and biofuel cells.     

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 nanocrystal-modified silicon nanowires as substrates for surface-enhanced Raman and hyper-Raman scattering

Metal catalyzed, CVD-grown silicon nanowires decorated by chemical assembly of closely spaced Ag nanocrystals were modified with the well-known "silver mirror" reaction and investigated as substrates for surface-enhanced Raman (SERS) and hyper-Raman (SEHRS) spectroscopy. Four chromophores were examined: Rhodamine 6G, crystal violet, a cyanine dye, and a cationic donor-acceptor substituted stilbene. After soaking the substrates overnight in 10(-4) M aqueous chromophore solutions, all four chromophores gave good-quality SERS spectra in < or =60 s using <1 microW of 458-nm cw laser power, and SEHRS spectra are obtained in < or =120 s using <1 mW of mode-locked 916-nm laser power. Results from this substrate are compared with those on colloidal silver nanoparticles deposited as a film, as well as surfaces grown by the silver mirror reaction.     

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.     

A novel method for fabricating the surface-enhanced Raman scattering substrates and its enhanced properties

We have got large area surface-enhanced Raman scattering (SERS) substrates with uniform high enhancement factors by the so-called moulage method for the first time. A silver film (99.99%) with several millimeters thickness was thermally evaporated on the porous anodic alumina templates and the SERS substrate was got after moving off the templates. Surface-enhanced Raman scattering spectra of pyridine (0.01 Mol/L) were measured under 632.8 nm excitation. The experimental enhancement factors were more than 10(5) and S/N(p-p) around 100 was obtained. We have compared the SERS spectra of pyridine collected from different locations on the same SERS substrate and different substrates, which illustrate the well uniform enhance properties and the reproducibility of this method, respectively. The comparison of the SERS spectra, obtained from the SERS substrates and Ag film evaporated directly on glass slide, have proved that the electromagnetic coupling between two adjacent nanoparticles was important to the SERS effect. We also used rhodamine 6G as the probe molecules and found that the different molecules were very sensitive to the morphology of the SERS substrates.     

A nanoforest structure for practical surface-enhanced Raman scattering substrates

A nanoforest structure for surface-enhanced Raman scattering (SERS) active substrates is fabricated and analyzed. The detailed morphology of the resulting structure can be easily controlled by modifying the process parameters such as initial gold layer thickness and etching time. The applicability of the nanoforest substrate as a label-free SERS immunosensor is demonstrated using influenza A virus subtype H1N1. Selective binding of the H1N1 surface antigen and the anti-H1 antibody is directly detected by the SERS signal differences. Simple fabrication and high throughput with strong in-plane hot-spots imply that the nanoforest structure can be a practical sensing component of a chip-based SERS sensing system.     

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.     

New strategy for ready application of surface-enhanced resonance Raman scattering/surface-enhanced Raman scattering to chemical analysis of organic films on dielectric substrates

Dropping of appropriately concentrated AgNO3 and NaBH4 solutions, as well as laser-ablated Ag sols, onto organic molecules results in the formation of aggregated Ag nanoparticles that can induce surface-enhanced Raman scattering (SERS) for the molecules. The addition of flocculating agents such as alkali halides can further increase the Raman signals. We demonstrate in this work that Raman spectra can be obtained even for 0.01 monolayers of R6G on Si simply by spreading silver nanoparticles and/or fabricating Ag nanoparticles and nanoaggregates at the gaps and vacant sites of R6G molecules. The application prospect of the present methodology is extremely high, not only because of its simplicity but also because of the fact that the observation of vibrational spectra is one of the most incisive methods for understanding the chemical and physical phenomena on a variety of surfaces.     

Preparation of silver nanoparticles by photo-reduction for surface-enhanced Raman scattering

A substrate for surface-enhanced Raman scattering (SERS) has been developed. Based on the surface-catalyzed reduction of Ag⁺ by citrate on the silver nanoparticles surface under light irradiation, small silver seeds on a quartz slide can be enlarged. The optical properties and characteristics of the silver films have been investigated by ultraviolet-visible spectroscopy, scan electron microscope and atomic force microscopy (AFM). The results indicate that the particle size and shape are different at different reduction time. At the first 3 h, some triangular and hexagonal nanoparticles formed; with the reduction proceeding, the shape of the silver particles became irregular and the size became larger. The silver films obtained are very suitable as SERS active substrate. The relationship between SERS intensity and the reduction time has been investigated for 1,4-bis[2-(4-pyridyl)ethenyl]-benzene molecule adsorbed on the silver film. The SERS intensity reached a maximum at 8 h reduction. The AFM measurements indicate that roughness features with an average size of 100 nm are present on the surface, which yielded the strongest SERS signal. Pyridine was used as a probe molecule to investigate the enhancement factor (EF) of the silver films. According to the formalism of Tian and co-workers, the EF of the silver films is estimated to be 3.4 × 10⁵. The silver film that can remain active for more than 50 days would seem to be suitable for various analytical applications.     

Angle-resolved surface-enhanced Raman scattering on metallic nanostructured plasmonic crystals

Surface-enhanced Raman scattering is an ideal tool for identifying molecules from the "fingerprint" of their molecular bonds; unfortunately, this process lacks a full microscopic understanding and, practically, is plagued with irreproducibility. Using nanostructured metal surfaces, we demonstrate strong correlations between plasmon resonances and Raman enhancements. Evidence for simultaneous ingoing and outgoing resonances in wavelength and angle sheds new light on the Raman enhancement process, allowing optimization of a new generation of reproducible Raman substrates.     

Preparation of tetrapod-like nanostructure array and used as the surface-enhanced Raman scattering substrates

Nanostructure surface composed of tetrapod-like structure with the period of about 2 microm has been made by simple nanoprinted method, the collodion was poured directly on the surface of the template and tore off after it became solidification, and then a layer of gold was sputtered on the collodion surface. The electric field distributions of the tetrapod-like structure with different size and period have been simulated using finite element method. Surface-enhanced Raman spectra mapping image gotten from the substrates illustrated the uniform enhancement property of it. The diluted aqueous solution of Rhodamine 6G (50 nM) was used to test the enhanced property of substrates for trace detection and good quality spectra has been gotten. The spectra of melamine with the concentration of 1 mg/L (7.9 microM) on the substrates were gotten to show the enhanced ability for molecule with small Raman scattering cross section.     

Metallic nanocrystals near ultrasmooth metallic films for surface-enhanced Raman scattering application

We studied the effect of the substrate on the surface-enhanced Raman scattering (SERS) signals of metallic nanocrystal films by making a direct comparison between cases with metallic and semiconducting substrate surfaces. Ag nanoparticles smaller than 10?nm were synthesized and uniform arrays were formed on both ultrasmooth metallic and Si surfaces. These substrates provide reproducible SERS signals with high enhancement factors over large areas. Moreover, a SERS signal about one order of magnitude higher was obtained in the metallic surface case as compared with the Si substrate case, which is attributed to stronger plasmon coupling between the nanoparticles and their charge-conjugate images in the underlying metallic surface. The interpretation of our experimental results was confirmed by our finite difference time domain calculations. The dependence of the interaction between the nanoparticles and the substrate surface on the direction of the incident electromagnetic field is also discussed.