Tunable Plasmonic Silver Nanodomes for Surface-Enhanced Raman Scattering

Surface-enhanced Raman scattering (SERS) is an emerging analytical method used in biological and non-biological structure characterization. Since the nanostructure plasmonic properties is a significant factor for SERS performance, nanostructure fabrication with tunable plasmonic properties are crucial in SERS studies. In this study, a novel method for fabrication of tunable plasmonic silver nanodomes (AgNDs) is presented. The convective-assembly method is preferred for the deposition of latex particles uniformly on a regular glass slide and used as a template for polydimethylsiloxane (PDMS) to prepare nanovoids on a PDMS surface. The obtained nanovoids on the PDMS are used as a mold for AgNDs fabrication. The nanovoids are filled with Ag deposition by the electrochemical method to obtain metallic AgNDs. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) are used for characterization of the structural properties of all fabricated AgNDs. The optical properties of AgNDs are characterized with the evaluation of SERS activity of 4-aminothiphonel and rhodamine 6G. In addition to experimental characterizations, the finite difference time domain (FDTD) method is used for the theoretical plasmonic properties calculation of the AgNDs. The experimental and theoretical results show that the SERS performance of AgNDs is strongly dependent on the heights and diameters of the AgNDs.     

Metallic Core-Shell Photonic Crystals for Surface-Enhanced Raman Scattering (SERS)

Plasmonics - Metallic core-shell substrate is specially used to serve ultrasensitive molecular detection down to concentration of micromolar level based on surface-enhanced Raman spectroscopy...     

表面增强拉曼散射机理研究进展

简要回顾表面增强拉曼散射（Surface—enhanced Raman Scattering,SERS）的发展历史,主要综述近年来SERS物理增强机理及理论计算方面的研究进展,并对SERS机理理论研究发展作了展望。     

Individual Ag Nanowire Dimer for Surface-Enhanced Raman Scattering

We have investigated the polarization-dependent surface-enhanced Raman scattering (SERS) of an individual Ag nanowire (AgNW) dimer, which contains two parallel closely packed AgNWs with very different lengths. Similar cos² θ dependence of signal intensities with respect to the polarization angle θ of the incident laser was observed from the dimeric part and the parts of the body as well as the tip of the longer AgNW. The dimeric part was demonstrated to exhibit the strongest SERS effect. The results agree well with our numerical simulations of the electric field distributions using finite element method. The SERS enhancement mechanisms at different parts of the dimer were also discussed which are different in origin.     

Silver Nanoparticles and Nanorings for Surface-Enhanced Raman Scattering

Silver (Ag) nanoparticles (NPs) and Ag nanorings (NRs) have been fabricated. Due to the inherent features of Ag NPs and Ag NRs, strong electromagnetic (EM) near-field distributions were expected, and hence surface-enhanced Raman scattering (SERS) activity was demonstrated. Size and interparticle gaps distribution of Ag NPs were estimated to be 48.14?±?10.14 nm and 14.11?±?5.24 nm respectively along with estimated coverage density of?~?4?×?10¹⁰ cm^?2. On the other hand, Ag NRs were found to consist of Ag clusters and of various shapes and sizes, instead of a perfect ring structure. High-resolution FESEM revealed that the individual constituent clusters were different from each other, particularly in terms of size and shape in addition to the cases how such clusters were connected to form the edge of the NR. However, the coverage density of Ag NRs was estimated to be?~?5.6?×?10⁶ cm^?2. Based on the scenarios, it was speculated that the local EM near-field distribution would excel and thus led to enhanced SERS signals. SERS enhancement of R6G was estimated as high as 2.18?×?10⁴ and 2.78?×?10⁴ at 610 cm^?1 (C???C ring bending mode in phenyl rings) for Ag NPs and Ag NRs respectively. FDTD analysis was carried out to elucidate the EM near-field distributions.

Graphical abstract

Ag NPs and Ag NRs from an ultrathin layer of Ag on ZnO/Glass (middle pane) confirming high EF of R6G adsorbed on Ag NRs (right pane) and Ag NPs (left pane) supported by corresponding EM near-field distributions.

     

Peptide-Guided Surface-Enhanced Raman Scattering Probes for Localized Cell Composition Analysis

The ability to control the localization of surface-enhanced Raman scattering (SERS) nanoparticle probes in bacterial cells is critical to the development of analytical techniques that can nondestructively determine cell composition and phenotype. Here, selective localization of SERS probes was achieved at the outer bacterial membrane by using silver nanoparticles functionalized with synthetic hydrophobic peptides.     

Single-Molecule Imaging and Spectroscopy Using Fluorescence and Surface-Enhanced Raman Scattering

We extended single molecule fluorescence imaging and time-resolved fluorometry from the green to the violet-excitation regime to find feasibility of detecting and identifying fluorescent analogs of nucleic-acid bases at the single-molecule level. Using violet excitation, we observed fluorescent spotsfrom single complexes composed of a nucleotide analogue and the Klenow fragmentof DNA polymerase I. Also, we implemented Raman imaging and spectroscopy of adenine molecules adsorbed on Ag colloidal nanoparticles to find feasibility of identifying nucleic-acid bases at the single-molecule level. Surface enhanced Raman scattering (SERS) of adenine molecules showed an intermittent on-and-off behavior called blinking. The observation of blinking provides substantial evidence for detecting single adenine molecules.     

Surface-Enhanced Raman Scattering (SERS) on 1D Nano-gratings

Surface-enhanced Raman scattering (SERS) enhancement factor (EF) is among the major applications of surface plasmon polaritons (SPP’s). In this work, the SERS EF of 1D rectangular and sinusoidal-shaped gold (Au) grating structures has been designed and optimized on Au film using COMSOL multiphysics (5.3a) RF module taking glass as substrate. The 1D grating models are simulated by variation in slit width ranging 200–600 nm while other parameters including periodicity of 700 nm and Au film thickness of 50 nm remained fixed. In order to study the several phenomena including enhanced optical transmission and SERS EF, the transmission and electric field spectra have been obtained from both types of grating structures. In agreement with fundamental plasmonic mode, the slit width of two-thirds of the periodicity found to be optimum for SERS EF. Remarkable value of SERS EF is obtained in the case of a sinusoidal Au grating device (6.4 × 10⁹) which is calculated to be five times that of the rectangular grating (1.2 × 10⁹). These devices are also the fingerprints of molecules, hence find applications in biosensing, pollution control, and chemical and food industry.

     

Optical Fiber-Based Surface-Enhanced Raman Scattering Sensor Using Au Nanovoid Arrays

Plasmonic properties of gold nanovoid array substrates for fiber-based surface-enhanced Raman scattering (SERS) sensing are studied numerically and experimentally. In the nanovoid arrays, each void has openings on both sides, bottom hole facing the fiber tip for introducing incident light and collecting scattered light and the top hole exposed to the analyte solution for interrogating analyte molecules in the voids. Electromagnetic field modes are confined strongly in and around these nanovoids, acting as localized plasmon resonators. The enhanced electric field extends hundreds of nanometers into the voids, resulting in a large SERS-active zone several orders of magnitude larger than nanoparticle-based structures. The effect of structural parameters of the nanovoid arrays, including void diameter, Au film thickness, and bottom hole diameter, on electric field confinement in the voids is investigated using three-dimensional finite difference time domain simulation. Au nanovoid arrays are fabricated using a scalable, inexpensive nanosphere lithography fabrication method. The largest SERS signal is realized by tuning the localized plasmon resonance peak of Au nanovoid arrays to the laser excitation wavelength. Multiplexed detection capability with the fiber-based SERS sensor using Au nanovoid arrays is demonstrated by measuring the Raman spectrum of a mixture solution of diethylthiatricarbocyanine and crystal violet.     

Surface-Enhanced Raman Scattering from Individual Au Nanoparticles on Au Films

We investigated the effect of optical thick metal films on the surface-enhanced Raman scattering (SERS) activity of individual Au nanoparticle (NP) monomers and dimers. The film presence is revealed to be positive for the SERS activity of individual NP monomers, while it is not always positive for the electromagnetic enhancement at hot spots for SERS of the dimer, which is explained well by our numerical simulations. The polarized SERS signals from the NP dimer are elucidated well in terms of the plasmon hybridization of the dimer. SERS contributions both from individual NP surfaces and the junction between the NP and its supporting substrate were discussed as well.     

Individual Split Au Square Nanorings for Surface-Enhanced Raman and Hyper-Raman Scattering

In this paper, individual split Au square nanorings were numerically proposed as novel substrates for surface-enhanced Raman and hyper-Raman scattering (SERS and SEHRS) simultaneously. The peak wavelengths of their localized surface plasmon resonance (LSPR) fall in the near-infrared and visible light regions, respectively, which are able to be finely tuned to match well with the wavelengths of the incident laser and hyper-Raman scattered light beams. Their SEHRS and SERS performances along with electromagnetic (EM) field distributions are numerically investigated by finite element method. With the enhancement of near electric-fields generated by LSPRs, the maximum SEHRS and SERS enhancement factors are demonstrated to reach 1.22?×?10¹² and 10⁸, respectively. Meanwhile, the corresponding SERS-based refractive index (RI) sensitivity factor reaches as high as 258 nm/RIU and 893 nm/RIU, at visible and near-infrared wavelengths, respectively. The proposed structure holds great promise both for developing SEHRS- and SERS-based RI sensing substrates, which shows strong potential applications in nanosensing and enhanced Raman scattering.

     

Amplification of Surface-Enhanced Raman Scattering in Photonic Crystal Fiber Using Offset Launch Method

In this paper, we report the amplification effect of surface-enhanced Raman scattering (SERS) in a solid-core photonic crystal fiber. Gold nanoparticles (AuNPs) are self-assembled on the inner walls of the cladding air holes through a multilayered deposition procedure. Offset launch method is for the first time employed to introduce extra enhancement in the intensity of SERS signals, as compared to the conventional core launch method. A theoretical analysis on modal field distribution for both launching conditions is carried out to account for such improvement. It shows that by adjusting the launching position of laser beam from the solid fiber core to an air hole in the cladding, overlap of the excited mode with AuNPs has been increased significantly. The SERS probe is demonstrated to achieve a detection limit as low as 10^?7 M in concentration, which shows a competitive performance for molecule analysis.     

Effect of Interparticle Field Enhancement in Self-Assembled Silver Aggregates on Surface-Enhanced Raman Scattering

The presence of so-called hot spots, regions with strongly enhanced electromagnetic field, is a critical property of a substrate enabling detection of surface-enhanced Raman scattering (SERS) signals at high enhancement levels. In this work, the effect of interparticle field enhancement on SERS signals was investigated comparing SERS spectra of ethylenediaminetetraacetic-disodium salt in the chemically produced colloids with isolated and aggregated silver nanoparticles using 473 and 532-nm wavelength excitation. The presence of aggregates in the colloidal solution resulted in SERS spectra that were insensitive to wavelength excitation and much richer in structural information and of higher resolution than the corresponding SERS spectra for the colloid with isolated nanoparticles. The experimental SERS spectra were found to be consistent with the finite-difference time-domain simulation results that explored the electromagnetic response of the isolated and aggregated nanoparticles. These results provide more evidence to suggest that the aggregate formation offers favorable electromagnetic properties increasing sensitivity of Raman spectroscopy.     

Interface-Induced Ag Monolayer Film for Surface-Enhanced Raman Scattering Detection of Water-Insoluble Enrofloxacin

Water-insoluble molecules usually show poor surface-enhanced Raman scattering (SERS) signals, because they are hardly adsorbed on the surface of most commonly used SERS substrates, such as aqueous Ag or Au colloids. In this work, a highly sensitive and reproducible Ag monolayer film (Ag MLF) SERS substrate prepared by self-assembly of Ag nanoparticles (Ag NPs) on water/oil interface can realize the trace SERS detection of water-insoluble enrofloxacin. The positively charged phase transfer catalyst can transfer the negatively charged Ag nanoparticles in aqueous solution to the water/oil interface. At the same time, the water-insoluble enrofloxacin can also be attracted to the interface because of its lipophilic group. The type/volume of the oil phase and phase transfer catalyst and the vortex mixing time were all optimized to maximize the SERS effect of Ag MLF. Results showed that trace water-insoluble enrofloxacin can be identified by Ag MLF and its detection sensitivity was significantly improved. The proposed novel Ag MLF can be further applied to detect other water-insoluble molecules in SERS.

     

Surface Plasmon Resonances of Metallic Nanostars/Nanoflowers for Surface-Enhanced Raman Scattering

We investigate theoretically the optical properties associated to plasmon resonances of metal nanowires with cross section given by low-order Chebyshev nanoparticles (like rounded-tip nanostars or nanoflowers). The impact of the nanoflower shape is analyzed for varying symmetry and deformation parameter through the spectral dependence of resonances and their corresponding near field distributions. Large field intensity enhancements are obtained at the gaps between petals, apart from the tips themselves, which make these nanostars/nanoflowers specially suitable to host molecules for surface-enhanced Raman scattering sensing applications.     

Nanoparticle Surface-Enhanced Raman Scattering of Bacteriorhodopsin Stabilized by Amphipol A8-35

Surface-enhanced Raman spectroscopy (SERS) has developed dramatically since its discovery in the 1970s, because of its power as an analytical tool for selective sensing of molecules adsorbed onto noble metal nanoparticles (NPs) and nanostructures, including at the single-molecule (SM) level. Despite the high importance of membrane proteins (MPs), SERS application to MPs has not really been studied, due to the great handling difficulties resulting from the amphiphilic nature of MPs. The ability of amphipols (APols) to trap MPs and keep them soluble, stable, and functional opens up onto highly interesting applications for SERS studies, possibly at the SM level. This seems to be feasible since single APol-trapped MPs can fit into gaps between noble metal NPs, or in other gap-containing SERS substrates, whereby the enhancement of Raman scattering signal may be sufficient for SM sensitivity. The goal of the present study is to give a proof of concept of SERS with APol-stabilized MPs, using bacteriorhodopsin (BR) as a model. BR trapped by APol A8-35 remains functional even after partial drying at a low humidity. A dried mixture of silver Lee–Meisel colloid NPs and BR/A8-35 complexes give rise to SERS with an average enhancement factor in excess of 10². SERS spectra resemble non-SERS spectra of a dried sample of BR/APol complexes.     

Tunable Surface-Enhanced Raman Spectroscopy via Plasmonic Coupling Between Nanodot-Arrayed Ag Film and Ag Nanocube

Herein, a flexible surface-enhanced Raman spectroscopy (SERS) substrate composed of nanodot-arrayed Ag film and Ag nanocubes was fabricated through a simple method. The large-area nanodot-arrayed Ag film was produced at low cost and high reproducibility. The experimental results show that the coupled structure produces a much stronger SERS signal than the Ag nanocube alone and the isolated nanodot-arrayed Ag film. Furthermore, the coupling effect is sensitive to geometrical parameter of the period of the dot-array. Numerical simulations are performed to verify the electric field enhancement of the composite SERS substrate and support the experimental results.     

Phase-Transfer Identification of Core-Shell Structures in Bimetallic Nanoparticles

On the basis of a combination of previously published experimental procedures, ultraviolet–visible spectroscopy, transmission electron microscopy, and energy-dispersive X-ray measurements, a systematic investigation was carried out on the phase-transfer characteristics of different bimetallic nanoparticles (Ag–Au, Ag–Pt, Ag–Ru, Au–Pt, Au–Ru, and Pt–Ru) formed by the seed-mediated growth reactions. The different phase-transfer characteristics of the monometallic nanoparticles of Au, Ag, Pt, and Ru were used to form the basis of differentiation between various possible structures existing in the bimetallic systems (core-shell particles or a physical mixture of nanoparticles). The experimental results indicate clearly the formation of core-shell nanoparticles of Ag–Au, Ag–Pt, Ru–Ag, Pt–Au, Au–Ru, and Pt–Ru when the nanoparticles of the first metal were used as the seeds in the seed-mediated growth reactions. However, when the order of the synthesis was reversed using the nanoparticles of the second metal as the seeds, only a physical mixture of the two metal nanoparticles was obtained instead.Parts of the data on Au–Ru and Ag–Pt systems have been published in Analytica Chimica Acta (2005, 537, 279–284) and Journal of Physical Chemistry B (2005, 109, 5468–5472), respectively.     

Ag-Cu Nanoparticles Encaptured by Graphene with Magnetron Sputtering and CVD for Surface-Enhanced Raman Scattering

An efficient surface-enhanced Raman scattering (SERS) substrate has been developed based on Ag-Cu nanoparticle-decorated graphene. The Ag-Cu-graphene (Ag-Cu@G) hybrid structure was prepared by magnetron sputtering for Ag and Cu film and chemical vapor deposition (CVD) for graphene, which avoided defects produced by graphene transferring process. The hybrid materials were confirmed by scanning electron microscopy (SEM), atomic force microscopy (AFM), energy dispersive spectroscopy (EDS), and Raman spectroscopy. With R6G as analyst molecule, the enhancement factor (EF) of the order of 10⁶ for Ag-Cu@G sample was obtained. Meanwhile, the substrates had stable enhanced SERS signals after 78-day exposure in air, which could be explained by the fact that the graphene is efficient at maintaining chemical and optical stability. The formation of graphene can contribute a stabilization and fluorescence quenching effect. Moreover, the electromagnetic distribution based on AFM images was simulated by finite difference time domain (FDTD) method.     

Study of Surface-Enhanced Raman Scattering of Plasmonic Coupled Biomolecule: Role of Multi-Layered Nanosphere

Plasmonics - In this communication, we study the surface enhanced Raman scattering (SERS) by a molecule which is adsorbed on a trilayer (Ag@SiO2@Ag) spherical shaped metallic nanostructure. We have...