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.     

Silver nanoparticles deposited on anodic aluminum oxide template using magnetron sputtering for surface-enhanced Raman scattering substrate

Low-cost and highly sensitive surface-enhanced Raman scattering (SERS) substrates have been fabricated by a simple anodizing process and a magnetron sputtering deposition. The substrates, which consist of silver nanoparticles embedded on anodic aluminum oxide (AAO) templates, are investigated by a scanning electron microscope and a confocal Raman spectroscopy. The SERS activities are demonstrated by Raman scattering from adsorbed solutions of methylene blue and pyridine on the SERS substrate surface. The most optimized SERS substrate contains the silver nanoparticles, with a size distribution of 10-30 nm, deposited on the AAO template. From a calculation, the SERS enhancement factor is as high as 8.5 × 10⁷, which suggests strong potentials for direct applications in the chemical detection and analyses.     

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.     

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.

     

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.     

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.     

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).     

A facile synthesis of silver nanoparticle with SERS and antimicrobial activity using Bacillus subtilis exopolysaccharides

In this study, we report a facile synthesis of silver nanoparticle having SERS and antimicrobial activity using bacterial exopolysaccharide (EPS). Bacillus subtilis (MTCC 2422) was grown in nutrient broth and the extracellular EPS secreted by the organism was extracted and purified. The purified EPS was used for the synthesis of silver nanoparticles. The kinetics of silver nanoparticle synthesis was deduced by varying the exposure time and the concentration of EPS. The rate constant (k) for the synthesis of silver nanoparticle was calculated from the slope of ln(A^∞ ? A^t) versus time plot. The k value was found to be 3.49 × 10^?3, 5.81 × 10^?3 and 5.03 × 10^?3 per min for particle synthesis using 2, 5 and 10 mg/mL EPS, respectively. The nanoparticles synthesised had an average particle size of 5.18 ± 1.49 nm, 1.96 ± 0.77 nm and 2.08 ± 0.88 nm for 2, 5 and 10 mg/mL EPS, respectively. The synthesised particles were characterised using UV-Vis absorbance spectroscopy, high-resolution transmission electron microscopy (HRTEM) attached to EDS (energy dispersive spectroscopy), Fourier transform infrared spectroscopy (FTIR), surface enhanced Raman spectroscopy (SERS) and zeta potential analyser. To our knowledge, this is the first study to report SERS activity of microbial Bacillus subtilis EPS-based synthesis of silver nanoparticle. HRTEM images showed silver nanoparticle entrapped in polysaccharide nanocages. Silver nanoparticle showed higher adherence towards the bacterial surface, with good bactericidal activity against Pseudomonas aeroginosa and Staphylococcus aureus.     

SERS effects in silver-decorated cylindrical nanopores

Optimization of pore diameter, the placement of nanoparticles, and the transmission of surface-enhanced Raman scattering (SERS) substrates are found to be very critical for achieving high SERS activity in porous alumina-membrane-based substrates. SERS substrates with a pore diameter of 355 nm incorporating silver nanoparticles show very high SERS activity with enhancement factors of 10(10) .     

Silver nanoclusters films for single molecule detection using Surface Enhanced Raman Scattering (SERS)

A highly efficient Surface Enhanced Raman Scattering (SERS) substrate was prepared using a nanocluster deposition system that enabled detection of Crystal Violet molecules down to a single molecule level. The large SERS signal enhancement can be attributed to the presence of nano gaps on the surface of the nanoclusters which create abundant hot spots for electric field enhancement. Observed variations in the Raman peaks at very low molar concentrations in the range 4 × 10⁻¹⁴–3.2 × 10⁻¹⁸ M suggest that the spectra are due to a single molecule. Possible mechanisms for ultrahigh SERS sensitivity of the substrates are discussed. These substrates take the detection limit of CV down by two orders of magnitude as compared to those reported in literature.     

Metal-coated magnetic nanoparticles for surface enhanced Raman scattering studies

We report the optimization and usage of surfactantless, water dispersible Ag and Au-coated g\boldsymbol\gamma–Fe₂_{\boldsymbol 2}O₃_{\boldsymbol 3} nanoparticles for applications in surface-enhanced Raman scattering (SERS). These nanoparticles, with plasmonic as well as super paramagnetic properties exhibit Raman enhancement factors of the order of 10⁶ (10⁵) for Ag (Au) coating, which are on par with the conventional Ag and Au nanoparticles. Raman markers like 2-naphthalenethiol, rhodamine-B and rhodamine-6G have been adsorbed to these nanoparticles and tested for nonresonant SERS at low concentrations. Further, to confirm the robustness of Ag-coated nanoparticles, we have performed temperature-dependent SERS in the temperature range of 77–473 K. The adsorbed molecules exhibit stable SERS spectra except at temperatures $\boldsymbol >$\boldsymbol >323 K, where the thermal desorption of test molecule (naphthalenethiol) were evident. The magnetic properties of these nanoparticles combined with SERS provide a wide range of applications.     

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.     

Tunable and highly reproducible surface-enhanced Raman scattering substrates made from large-scale nanoparticle arrays based on periodically poled LiNbO3 templates

Abstract

This work describes novel surface-enhanced Raman scattering (SERS) substrates based on ferroelectric periodically poled LiNbO₃ templates. The templates comprise silver nanoparticles (AgNPs), the size and position of which are tailored by ferroelectric lithography. The substrate has uniform and large sampling areas that show SERS effective with excellent signal reproducibility, for which the fabrication protocol is advantageous in its simplicity. We demonstrate ferroelectric-based SERS substrates with particle sizes ranging from 30 to 70 nm and present tunable SERS effect from Raman active 4-mercaptopyridine molecules attached to AgNPs when excited by a laser source at 514 nm.     

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.     

Differentiation of bacteria cell wall using Raman scattering enhanced by nanoparticle array

We have fabricated surface-enhanced Raman scattering (SERS) substrates based on arrays of silver nanoparticles grown on porous anodic alumina templates. Using this nanotechnology platform, label-free and high-speed detection of bacteria are achieved. SERS spectra of various bacteria including Staphylococcus Aureus (Gram-positive bacterium), Klebsiella Pneumoniae (Gram-negative bacterium), and Mycobacterium Smegmatis (Mycobacterium) were recorded. The highly reproducible SERS-based technological platform is capable of differentiating different kinds of bacteria by PCA, LDA, clustering analysis, and SVM methods, which provides promising opportunity for biosensing of clinical microbes.     

Gold/palladium and silver/palladium colloids as novel metallic substrates for surface-enhanced Raman scattering

New surface-enhanced Raman scattering (SERS) substrates, composed of gold or silver colloidal nanoparticles doped with palladium, were prepared. These novel colloids are stable and maintain a satisfactory SERS efficiency, even after long aging. The interest in doping the coinage metal nanoparticles with palladium is due to the well-known catalytic activity of this metal. Transmission electron microscopy (TEM) and ultraviolet-visible absorption spectroscopy were used to characterize the shape and size of the metal particles. It was found that these bimetallic colloidal nanoparticles have a core-shell structure, with gold or silver coated with palladium clusters.     

Stability of Ag nanoparticles fabricated by electron beam lithography

The stability of silver nanoparticles on indium tin oxide coated glass substrates under atmospheric condition was investigated. These nanoparticles were fabricated using electron beam lithography. Energy dispersive spectroscopy analysis revealed a high concentration of sulfur in the silver nanoparticles exposed to laboratory air for 12 weeks at room temperature. Morphological changes in the silver nanoparticles were also observed for nanoparticles stored under the same conditions. In contrast, silver nanoparticles kept in vacuum did not show chemical or morphological changes after 12 weeks. The present work clearly shows the need to consider ambient exposure when using Ag nanoparticles for sensors.     

Role of the micro- and nanostructure in the performance of surface-enhanced Raman scattering substrates assembled from gold nanoparticles

Highly active and stable substrates for surface-enhanced Raman scattering (SERS) can be fabricated by using colloidal crystals to template gold nanoparticles into structured porous films. The structure-dependent performance of these SERS substrates was systematically characterized with cyanide in continuous flow microfluidic chambers. A matrix of experiments was designed to isolate the SERS contributions arising from nano- and microscale porosity, long-range ordering of the micropores, and the thickness of the nanoparticle layer. The SERS results were compared to the substrate structure observed by scanning electron microscopy (SEM) and optical microscopy to correlate substrate structure to SERS performance. The Raman peak intensity was consistently highest for nanoporous substrates with three-dimensionally ordered micropores, and decreases if the micropores are not ordered or not templated. Removing the nanoscale porosity by fusion of the nanoparticles (without removing the large micropores) leads to a drastic plunge in substrate performance. The peak intensity does not strongly correlate to the thickness of the nanoparticle films. The results make possible the efficient controlled fabrication of stable, reproducible, and highly active substrates for SERS based chemical sensors with continuous sampling.     

Spherical Nanoparticle Arrays with Tunable Nanogaps and Their Hydrophobicity Enhanced Rapid SERS Detection by Localized Concentration of Droplet Evaporation

Periodic hexagonal spherical nanoparticle arrays are fabricated by a sacrificial colloidal monolayer template route by chemical deposition and further physical deposition. The regular network‐structured arrays are first templated by colloidal monolayers and then they are changed to novel periodic spherical nanoparticle arrays by further sputtering deposition due to multiple direction deposition and shadow effect between adjacent nanoparticles. The nanogaps between two adjacent spherical nanoparticles can be well tuned by controlling deposition time. Such periodic nanoparticle arrays with gold coatings demonstrate a very stable and high sensitive surface‐enhanced Raman scattering spectroscopy (SERS) performance. The periodic nanoparticle arrays with 10 nm gaps display much stronger SERS enhancement due to electromagnetic coupling. The chemically modified nanoparticle arrays show good hydrophobicity, which shorten process of detecting probe molecules using them as SERS‐active substrates by localized concentration of droplet evaporation and a low detection limit of 10⁻¹² m R6G can be achieved without solution wasting in a short time. The hydrophobic substrate offers a simple, convenient, and economical method to examine SERS performance by rapid concentration of solution on it and it is highly helpful to improve its practical applications in portable Raman detecting devices to detect organic molecules.     

Highly reproducible solid-phase extraction membrane for removal and surface-enhanced Raman scattering detection of antibiotics

A disposable solid-phase extraction (SPE) membrane was developed for rapid removal and sensitive surface-enhanced Raman scattering (SERS) detection of antibiotics in water samples. The membrane was fabricated on commercially available SPE column by filtration of the activated carbon modified with silver nanoparticles (Ag NPs/AC). The prepared SPE membrane exhibited outstanding preconcentration ability due to the high adsorption properties of AC, and excellent ability to enhance Raman signal resulting from “hot spots” between the embedded Ag NPs, improving the sensitivity of SERS detection. A detection limit (LOD) of 5.0?×?10^?11 and 1.6?×?10^?10 M was achieved for rhodamine 6G and p-aminothiophenol. In addition, the membrane exhibited high reproducibility with spot-to-spot variation in SERS spectral intensity less than 15%. Based on the membrane, the qualitative and quantitative analysis of the antibiotics in aqueous solution was accomplished with the LOD at nM level, demonstrating the feasibility of the disposable SPE membrane for in situ rapid preconcentration and detection.