In situ Raman scattering study on a controllable plasmon-driven surface catalysis reaction on Ag nanoparticle arrays

Control of the plasmon-driven chemical reaction for the transformation of 4-nitrobenzenethiol to p,p'-dimercaptoazobenzene by Ag nanoparticle arrays was studied. The Ag nanoparticle arrays were fabricated by means of nanosphere lithography. By changing the PS particle size, the localized surface plasmon resonance (LSPR) peaks of the Ag nanoparticle arrays can be tailored from 460 to 560 nm. The controlled reaction process was monitored by in situ surface-enhanced Raman scattering. The reaction can be dramatically influenced by varying the duration of laser exposure, Ag nanoparticle size, laser power and laser excitation wavelength. The maximum reaction speed was achieved when the LSPR wavelength of the Ag nanoparticle arrays matched the laser excitation wavelength. The experimental results reveal that the strong LSPR can effectively drive the transfer of the 'hot' electrons that decay from the plasmon to the reactants. The experimental results were confirmed by theoretical calculations.     

Surface-enhanced Raman scattering of crystal violets from periodic array of gold nanocylinders

The periodic arrays of gold nanocylinder with 121?nm in diameter, 6.3?nm in gap, and 34?nm in thickness are fabricated on glass by electron-beam lithography and lift-off techniques. Some crystal violet molecules are coated on the array by using the dipping and drawing method. In addition, the surface-enhanced Raman scattering (SERS) spectra of these samples with and without gold nanocylinder arrays are characterized specifically. The largest enhancement factor is obtained when the excitation wavelength corresponds to the peak wavelength of localized surface plasmon resonance (LSPR). The density functional theory and the finite-difference time-domain method are used for the calculations of the extinction spectrum of the arrays and Raman spectra of the crystal violet, respectively. These results unambiguously demonstrate that the periodic arrays of gold nanocylinder have good and effective surface-enhanced properties for Raman scattering of crystal violets, and they also show that the excitation wavelength corresponding to the peak one of the LSPR is one of the major reasons causing SERS.     

Combined antenna and localized plasmon resonance in Raman scattering from random arrays of silver-coated, vertically aligned multiwalled carbon nanotubes

The electric field enhancement associated with detailed structure within novel optical antenna nanostructures is modeled using the surface integral equation technique in the context of surface-enhanced Raman scattering (SERS). The antennae comprise random arrays of vertically aligned, multiwalled carbon nanotubes dressed with highly granular Ag. Different types of "hot-spot" underpinning the SERS are identified, but contrasting characteristics are revealed. Those at the outer edges of the Ag grains are antenna driven with field enhancement amplified in antenna antinodes while intergrain hotspots are largely independent of antenna activity. Hot-spots between the tops of antennae leaning towards each other also appear to benefit from antenna amplification.     

Silver-island films as substrates for enhanced Raman scattering: effect of deposition rate on intensity.

The relationship between surface-enhanced resonance Raman scattering (SERRS) intensity and the rate of deposition during silver-island film preparation was examined, using zinc tetraphenylporphine (ZnTPP) as the adsorbate. The effect of the deposition rate on the optical properties of the films at specific wavelengths was also analyzed. The data show that the film extinction (the term extinction is used rather than absorption because the spectra have not been corrected for reflection or scattering losses) increases exponentially at 514 and 458 nm as the deposition rate is decreased. SERRS intensities also increase exponentially at these two excitation wavelengths with a decrease in the deposition rate. The optical density is linearly related to the SERRS intensity, and maximal enhancement is observed for films with the greatest extinction at these excitation wavelengths. In contrast, neither the extinction at 406 nm nor the SERRS scattering intensities resulting from excitation at this wavelength differ substantially. The surface-enhanced Raman scattering (SERS) intensity and the electronic spectra of 4,4'-bipyridine (BP) adsorbed onto silver films as a function deposition rate were also examined. The behavior of the nonresonantly enhanced BP is comparable to that of the resonantly enhanced ZnTPP samples. The effects of the surface morphology, as determined from transmission electron micrographs of the films at various deposition rates, on the corresponding electronic spectra and SERS/SERRS spectra are described.     

Tailoring plasmonic nanostructures for optimal SERS sensing of small molecules and large microorganisms

Local electric fields can be tuned dramatically by varying the diameter of quasi-3D gold plasmonic nanostructure arrays, as indicated by 3D finite-difference time-domain calculations. Utilizing quasi-3D arrays that exhibit a maximum electric field intensity (i.e., a "hot" spot) either at the bottom (gold nanodisks) or on the top (gold film patterned with nanoholes), the optimal surface-enhanced Raman scattering (SERS) sensitivity for the detection of small molecules or large microorganisms can be achieved. The precisely fabricated and optimized SERS-active quasi-3D nanostructure arrays make it possible to quantitatively and reproducibly detect chemical and biological species using SERS, leading to a new sensing platform with molecular specificity based on SERS for many important applications.     

Enhanced Raman scattering in a colloidal crystal observed by a tunable laser light source

The Raman scattering intensity was measured for a colloidal crystal composed of polystyrene micro spheres and a polymer gel with a tunable continuous-wave dye laser as an excitation light source. Enhancement of the Raman scattering caused by both the electric field enhancement at the excitation frequency and the increase in the local photon density of states at the scattering frequency was expected. The observed Raman scattering intensity as a function of the excitation frequency showed a reasonable agreement with the theoretical prediction.     

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.     

Genetically engineered plasmonic nanoarrays

In the present Letter, we demonstrate how the design of metallic nanoparticle arrays with large electric field enhancement can be performed using the basic paradigm of engineering, namely the optimization of a well-defined objective function. Such optimization is carried out by coupling a genetic algorithm with the analytical multiparticle Mie theory. General design criteria for best enhancement of electric fields are obtained, unveiling the fundamental interplay between the near-field plasmonic and radiative photonic coupling. Our optimization approach is experimentally validated by surface-enhanced Raman scattering measurements, which demonstrate how genetically optimized arrays, fabricated using electron beam lithography, lead to order of ten improvement of Raman enhancement over nanoparticle dimer antennas, and order of one hundred improvement over optimal nanoparticle gratings. A rigorous design of nanoparticle arrays with optimal field enhancement is essential to the engineering of numerous nanoscale optical devices such as plasmon-enhanced biosensors, photodetectors, light sources and more efficient nonlinear optical elements for on chip integration.     

Surface plasmon-enhanced nanopillar photodetectors

We demonstrate nanopillar-(NP) based plasmon-enhanced photodetectors (NP-PEPDs) operating in the near-infrared spectral regime. A novel fabrication technique produces subwavelength elongated nanoholes in a metal surface self-aligned to patterned NP arrays that acts as a 2D plasmonic crystal. Surface plasmon Polariton Bloch waves (SPP-BWs) are excited by the metal nanohole array resulting in electric field intensity "hot spots" in the NP. The NP periodicity determines the peak responsivity wavelength while the nanohole asymmetry produces polarization-dependent coupling of the SPP-BW modes. Resulting photodetectors have 0.28 A/W responsivity peaked at 1100 nm at a reverse bias of -5 V. Designs for further increasing the optical coupling efficiency into the nanopillar are explored. This technology has potential applications for plasmonically enhanced focal plane arrays and plasmonic photovoltaics.     

The controlled fabrication and geometry tunable optics of gold nanotube arrays

Arrays of vertically aligned gold nanotubes are fabricated over several square centimetres which display a geometry tunable plasmonic extinction peak at visible wavelengths and at normal incidence. The fabrication method gives control over nanotube dimensions with inner core diameters of 15-30 nm, wall thicknesses of 5-15 nm and nanotube lengths of up to 300 nm. It is possible to tune the position of the extinction peak through the wavelength range 600-900 nm by varying the inner core diameter and wall thickness. The experimental data are in agreement with numerical modelling of the optical properties which further reveal highly localized and enhanced electric fields around the nanotubes. The tunable nature of the optical response exhibited by such structures could be important for various label-free sensing applications based on both refractive index sensing and surface-enhanced Raman scattering.     

Optical Properties of Copper-Doped Lithium Niobate Crystals

We have studied the optical properties of copper-doped lithium niobate crystals using semiconductor light-emitting diodes and lasers emitting in the visible and ultraviolet spectral regions as excitation sources. The results demonstrate that, at an excitation frequency approaching the frequency of electronic absorption in copper ions, there is discrete resonance Raman scattering in the form of a frequency comb. The observed Raman satellites of discrete light scattering are due to polar longitudinal A₁ optical modes of the lithium niobate single crystal. Under excitation by a light-emitting diode with a wavelength of 520 nm, we observe a sharp increase in discrete light scattering intensity in comparison with the photoluminescence excited by shorter wavelength excitation sources.     

Ag nanorod arrays tailored for surface-enhanced Raman imaging in the near-infrared region

Using a dynamic oblique angle deposition technique, we demonstrate the direct formation of Ag nanorods with quasi-parallel major axes on a template layer of oxide having a strongly anisotropic surface morphology. The optical properties of the nanorods are tuned by varying the deposition conditions without any pre-?or post-treatment, and the resulting Ag nanorod arrays exhibit high surface-enhanced Raman scattering (SERS) activity. In addition to high macroscopic uniformity over a large area, our nanorod arrays contain a high density of isolated nanorods. Using the optimum Ag nanorod arrays, the SERS imaging of the microdroplets of a rhodamine 6G solution is successfully demonstrated. The space resolution of the imaging is of the order of at least a few μm. These features are suitable for the SERS imaging of biomaterials.     

Fabrication of Ag–ZnO NRs SERS substrates for abamectin detection: the effect of Ag sputtering times and ZnO sol concentrations in seed layer preparation on SERS performance

Journal of Materials Science: Materials in Electronics - In this study, a surface-enhanced Raman scattering (SERS) substrate based on uniform silver nanoparticles/ZnO nanorods arrays (Ag–ZnO...     

Use of an additive noise to transfer spatial information from a laser to a stimulated Raman beam

A spatial signal cannot be converted from a laser wavelength to a stimulated Raman scattering wavelength if the laser intensity is too weak to obtain the stimulated Raman. The addition of high intensity spatial noise can help the Raman excitation if averaging occurs in the nonlinear system to restore the spatial signal. In order to have a sufficient quality of spatial information transfer, optimization of the noise intensity dependent on the signal intensity must be carried out. A model based on this idea is studied.     

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.     

The IP₆ micelle-stabilized small Ag cluster for synthesizing Ag-Au alloy nanoparticles and the tunable surface plasmon resonance effect

The stable small Ag seeds (size in diameter < 10 nm) were obtained in the presence of inositol hexakisphosphoric (IP?) micelles. Then Ag-Au bimetallic nanoparticles were synthesized through a replacement reaction with the rapid interdiffusion process between such small Ag seeds in nanoclusters and HAuCl?. Adjusting the dosage of HAuCl? resulted in different products, which possessed unique surface plasmon resonances (SPR). The morphologies of the as-made nanoparticles were observed using transmission electron microscopy and field emission scanning electron microscopy and their compositions were determined by energy-dispersive x-ray spectroscopy. Among them, the Ag-Au alloy nanoparticles with the cauliflower-like structure had a suitable SPR for highly sensitive Raman detection application as a surface-enhanced Raman scattering (SERS) substrate with a long-term stability of six months.     

SERS detection of biomolecules using lithographed nanoparticles towards a reproducible SERS biosensor

In this paper we highlight the accurate spectral detection of bovine serum albumin and ribonuclease-A using a surface-enhanced Raman scattering (SERS) substrate based on gold nanocylinders obtained by electron-beam lithography (EBL). The nanocylinders have diameters from 100 to 180 nm with a gap of 200 nm. We demonstrate that optimizing the size and the shape of the lithographed gold nanocylinders, we can obtain SERS spectra of proteins at low concentration. This SERS study enabled us to estimate high enhancement factors (10(5) for BSA and 10(7) for RNase-A) of important bands in the protein Raman spectrum measured for 1 mM concentration. We demonstrate that, to reach the highest enhancement, it is necessary to optimize the SERS signal and that the main parameter of optimization is the LSPR position. The LSPR have to be suitably located between the laser excitation wavelength, which is 632.8 nm, and the position of the considered Raman band. Our study underlines the efficiency of gold nanocylinder arrays in the spectral detection of proteins.     

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.     

Surface-enhanced Raman scattering on single-wall carbon nanotubes

Exploiting the effect of surface-enhanced Raman scattering (SERS), the Raman signal of single-wall carbon nanotubes (SWNTs) can be enhanced by up to 14 orders of magnitude when the tubes are in contact with silver or gold nanostructures and Raman scattering takes place predominantly in the enhanced local optical fields of the nanostructures. Such a level of enhancement offers exciting opportunities for ultrasensitive Raman studies on SWNTs and allows resonant and non-resonant Raman experiments to be done on single SWNTs at relatively high signal levels. Since the optical fields are highly localized within so-called "hot spots" on fractal silver colloidal clusters, lateral confinement of the Raman scattering can be as small as 5 nm, allowing spectroscopic selection of a single nanotube from a larger population. Moreover, since SWNTs are very stable "artificial molecules" with a high aspect ratio and a strong electron-phonon coupling, they are unique "test molecules" for investigating the SERS effect itself and for probing the "electromagnetic field contribution" and "charge transfer contribution" to the effect. SERS is also a powerful tool for monitoring the "chemical" interaction between the nanotube and the metal nanostructure.     

Bright Surface‐Enhanced Raman Scattering with Fluorescence Quenching from Silica Encapsulated J‐Aggregate Coated Gold Nanoparticles

Plexitonic nanoparticles offer variable optical properties through tunable excitations, in addition to electric field enhancements that far exceed molecular resonators. This study demonstrates a way to design an ultrabright surface‐enhanced Raman spectroscopy (SERS) signal while simultaneously quenching the fluorescence background through silica encapsulation of the semiconductor–metal composite nanoparticles. Using a multistep approach, a J‐aggregate‐forming organic dye is assembled on the surface of gold nanoparticles using a cationic linker. Excitonic resonance of the J‐aggregate–metal system shows an enhanced SERS signal at an appropriate excitation wavelength. Further encapsulation of the decorated particles in silica shows a significant reduction in the fluorescence signal of the Raman spectra (5× reduction) and an increase in Raman scattering (7× enhancement) when compared to phospholipid encapsulation. This reduction in fluorescence is important for maximizing the useful SERS enhancement from the particle, which shows a signal increase on the order of 10⁴ times greater than J‐aggregated dye in solution and 24 times greater than Oxonica S421 SERS tag. The silica layer also serves to promote colloidal stability. The combination of reduced fluorescence background, enhanced SERS intensity, and temporal stability makes these particles highly distinguishable with potential to enable high‐throughput applications such as SERS flow cytometry.