ABSTRACT: Simple wet chemistry has been applied to control the vertical growth of gold nanowires on a glass substrate. As a consequence, the longitudinal localized surface plasmon band position can be tuned from 656 to 1477 nm in a few minutes by simply controlling the growth rate and time. This allowed us to select the optimum conditions for maximum electromagnetic enhancement and performance in surface enhanced Raman scattering (SERS) detection. SERS measurements confirmed the uniform and reproducible distribution of the nanowires on the substrate, with the subsequent high reproducibility of hot spot formation. Detection of malachite green in water and of 1-naphthalenethiol from the gas phase are demonstrated as proof-of-concept applications of these three-dimensional SERS substrates.
Project description:The development of high-quality flexible surface-enhanced Raman spectroscopy (SERS) substrates is crucial for developing rapid SERS analysis in situ. Silver nanowire membranes as novel flexible substrates could benefit from the high collection efficiency of analytes by wrapping complex surfaces or wiping the surfaces of samples. However, their low SERS performance impedes further applications of silver nanowire membranes in analyte detection. Herein, we report an ultra-high-sensitivity silver nanowire membrane synthesized by a simple and time-saving cyclic voltammetry (CV) method. After CV treatment, a part of the silver nanowires on the silver nanowire membrane turned into small nanoparticles and nanorods. This nanostructure's reconstitution increased the analytical enhancement factor of silver nanowire membranes by 14.4 times. Scanning and transmission electron microscopy, UV-vis spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy were employed to investigate the transformation in the membrane nanostructure. The CV-treated substrates exhibited high surface-enhanced Raman activity and good temporal stability. The limits of detection (LODs) for <i>p</i>-aminothiophenol, crystal violet, tetramethylthiuram disulfide, sodium perchlorate, malachite green, fluoranthene, and potassium nitrate are 3.7 × 10<sup>-12</sup> M, 5.1 × 10<sup>-11</sup> M, 5.4 × 10<sup>-11</sup> M, 6.3 × 10<sup>-9</sup> M, 0.00693 ng, 0.0810 ng, and 0.0273 ng on this substrate, respectively. Additionally, the developed substrate is feasible for the detection of crystal violet in real samples. These results certify that CV-treated substrates possess broad application prospects in on-site SERS analysis.
Project description:The use of SERS for real-world bioanalytical applications represents a concrete opportunity, which, however, is being largely delayed by the inadequacy of existing substrates used to collect SERS spectra. In particular, the main bottleneck is their poor usability, as in the case of unsupported noble metal colloidal nanoparticles or because of the need for complex or highly specialized fabrication procedures, especially in view of a large-scale commercial diffusion. In this work, we introduce a graphene paper-supported plasmonic substrate for biodetection as obtained by a simple and rapid aerosol deposition patterning of silver nanowires. This substrate is compatible with the analysis of small (2 μL) analyte drops, providing stable SERS signals at sub-millimolar concentration and a detection limit down to the nanogram level in the case of hemoglobin. The presence of a graphene underlayer assures an even surface distribution of SERS hotspots with improved stability of the SERS signal, the collection of well-resolved and intense SERS spectra, and an ultra-flat and photostable SERS background in comparison with other popular disposable supports.
Project description:Assembly of nanowires into ordered macroscopic structures with new functionalities has been a recent focus. In this Letter, we report a new route for ordering hydrophilic Ag nanowires with high aspect ratio by flowing through a glass capillary. The present glass capillary with well-defined silver nanowire films inside can serve as a portable and reusable substrate for surface-enhanced Raman spectroscopy (SERS), which may provide a versatile and promising platform for detecting mixture pollutions. By controlling the flow parameters of nanowire suspensions, initially random Ag nanowires can be aligned to form nanowire arrays with tunable density, forming cambered nanowire films adhered onto the inner wall of the capillary. Compared with the planar ordered Ag nanowire films by the Langmuir-Blodgett (LB) technique, the cambered nanowire films show better SERS performance.
Project description:Limitations of achieving highly sensitive and stable surface-enhanced Raman scattering (SERS) substrate greatly concern the suitable method for fabrication of large-area plasmonic nanostructures. Herein we report a simple approach using template-based synthesis to create a highly ordered two-dimensional array of gold-silver alloy nanowires, followed by the controlled dealloying process. This particular step of mild acid etching (15%v/v nitric acid for 5?min) allowed the formation of Raman hot spots on the nanowire tips while maintaining the integrity of highly active alloy composition and rigid nanowire array structure. Full consideration of SERS substrate performance was accomplished using 4-mercaptobenzoic acid (4-MBA) as a probe molecule. Exceedingly higher SERS signal (150-fold) can be achieved with respect to typical gold film substrate. Moreover, an excellent stability of SERS substrate was also determined for over 3 months storage time. In contrast to the previous studies which stability improvement was accomplished at a cost of sensitivity reduction, the simultaneous improvement of sensitivity and stability makes the controlled dealloying process an excellent choice of SERS substrate fabrication. In addition, uniformity and reproducibility studies indicated satisfactory results with the acceptable values of relative standard deviation.
Project description:Polystyrene (PS) spheres were prepared through an emulsifier-free emulsion polymerization method, in which the reaction time, ionic strength, concentrations of copolymer were studied in detail. The resulting PS microspheres and Ag nanoparticles were used to construct a surface enhanced Raman scattering (SERS) substrate by a layer-by-layer assembly method. A relatively uniform distribution of PS/Ag in the films was obtained, and the multilayer substrate presented excellent SERS reproducibility and a tunable enhancement effect. The SERS substrate was used for detecting harmful pesticides (malachite green and dimetridazole) in food samples, with a limit of detection as low as 3.5 ppb. The obtained plasmonic composite has a promising future in the field of SERS sensing.
Project description:We present a facile and cost-effective manner to fabricate a highly sensitive and stable surface enhanced Raman scattering (SERS) substrate. First, a silicon nanowire array (SiNWA) is tailored by metal-assisted chemical etching (MaCE) method as a scaffold of the desired SERS substrate. Next, with an oblique angle deposition (OAD) method, optimized gold nanoparticles (AuNPs) are successfully decorated on the surface of the SiNWA. These AuNPs enable a strong localized electric field, providing abundant hot spots to intensify the Raman signals from the targeting molecules. By applying a well-established methodology, Taguchi method, which is invented for designing experiments, the optimized combination of parameters is obtained efficiently. The experimental results are also confirmed by finite-difference time-domain (FDTD) simulation calculations. Besides, a gold metal backplate (AuMBP) is applied to further enhancing the Raman signal intensity. Based on this developed SERS substrate, we demonstrated an enhancement factor (EF) of 1.78?×?106 and a coefficient of variation (CV) of 4.2%. Both EF and CV indicate a highly stable property and the optimized SERS substrate substantially outperform the commercial product. In the end, we also demonstrate a quantitative measurement on practical application of detecting malachite green (MG) with concentration from 10?nM to 100??M.
Project description:Noble metal-based surface-enhanced Raman spectroscopy (SERS) has enabled the simple and efficient detection of trace-amount molecules via significant electromagnetic enhancements at hot spots. However, the small Raman cross-section of various analytes forces the use of a Raman reporter for specific surface functionalization, which is time-consuming and limited to low-molecular-weight analytes. To tackle these issues, a hybrid SERS substrate utilizing Ag as plasmonic structures and GaN as charge transfer enhancement centers is presented. By the conformal printing of Ag nanowires onto GaN nanopillars, a highly sensitive SERS substrate with excellent uniformity can be fabricated. As a result, remarkable SERS performance with a substrate enhancement factor of 1.4 × 10<sup>11</sup> at 10 fM for rhodamine 6G molecules with minimal spot variations can be realized. Furthermore, quantification and multiplexing capabilities without surface treatments are demonstrated by detecting harmful antibiotics in aqueous solutions. This work paves the way for the development of a highly sensitive SERS substrate by constructing complex metal-semiconductor architectures.
Project description:Development of multifunctional drug delivery vehicles with therapeutic and imaging capabilities as well as in situ methods of monitoring of intracellular processes will greatly benefit from a simple method of preparation of plasmonic Au structures with nanometer scale gaps between sharp metallic elements where the so-called SERS hot spots can be formed. Here the synthesis of gold lace capsules with average diameters ca. 100 nm made of a network of metallic branches 3-5 nm wide and separated by 1-3 nm gaps is reported. Biocompatible amphiphilic polyurethanes (PUs) were used as template for these particles. The unusual topology of the produced gold lace shells somewhat reminiscent of Fabergé eggs is likely to reflect the network of hydrophobic and hydrophilic domains of PU globules. The gold lace develops from initial open weblike structures by gradual enveloping the PU template. The diameter of gold lace shell is determined by the size of PUs in water and can be adjusted by the molecular mass of PUs. The close proximity between branches makes them excellent supports for surface-enhanced Raman spectroscopy (SERS), which was demonstrated using 1-naphthalenethiol upon excitation with photons with different wavelengths. The loading and releasing of pyrene as a model of hydrophobic drugs and the use of SERS to monitor it were demonstrated.
Project description:Surface-enhanced Raman spectroscopy (SERS) is a powerful tool for vibrational spectroscopy as it provides several orders of magnitude higher sensitivity than inherently weak spontaneous Raman scattering by exciting localized surface plasmon resonance (LSPR) on metal substrates. However, SERS can be unreliable for biomedical use since it sacrifices reproducibility, uniformity, biocompatibility, and durability due to its strong dependence on "hot spots", large photothermal heat generation, and easy oxidization. Here, we demonstrate the design, fabrication, and use of a metal-free (i.e., LSPR-free), topologically tailored nanostructure composed of porous carbon nanowires in an array as a SERS substrate to overcome all these problems. Specifically, it offers not only high signal enhancement (~106) due to its strong broadband charge-transfer resonance, but also extraordinarily high reproducibility due to the absence of hot spots, high durability due to no oxidization, and high compatibility to biomolecules due to its fluorescence quenching capability.
Project description:Ultrasonic morphology modification of silver (Ag) nanowires and their applications in transparent film heaters for defogging in electric vehicles and surface-enhanced Raman scattering (SERS) detectors have been studied. With 10 min ultrasonic treatment of Ag nanowires, the electro-thermal conversion capability of Ag nanowire based transparent film heaters is efficiently improved (about 50% increase in temperature rise), which can be mainly attributed to the cross-section area reduction and the serious agglomerations of the ultrasonic modified Ag nanowire films. Furthermore, the bending or fracture caused by deformation of Ag nanowires after ultrasonic treatment provides more hot spots for SERS, and therefore lead to a significant SERS signal enhancement. This work not only greatly improves the performance of Ag nanowire based transparent film heaters and SERS detectors, but provides a new way for the functional modification of Ag nanowires.