Physical Deposition Improved SERS Stability of Morphology Controlled Periodic Micro/Nanostructured Arrays Based on Colloidal Templates

An effective and inexpensive method is developed to fabricate periodic arrays by sacrificial colloidal monolayer template route by chemical deposition and further physical deposition. By a colloidal template induced precursor solution dipping strategy, different periodic arrays of semi‐hollow sphere array, inverse opal with monolayer pore arrays and hole arrays are obtained under different conditions. After magnetron sputtering deposition, their morphologies are changed to novel micro/nanostructured arrays of honeycomb‐shaped arrays, hollow cavity arrays, and regular network arrays due to multiple direction deposition of sputtering deposition and shadow effect. After coating a gold thin layer, these periodic micro/nanostructured arrays are used as SERS active substrates and demonstrate a very stable SERS performance compared with periodic arrays achieved by direct colloidal template‐induced chemical deposition. Additionally, a honeycomb‐shaped array displays better SERS enhancement than that of a hollow cavity array or a regular network array. After optimization of honeycomb‐shaped arrays with different periodicities, an array with periodicity of 350 nm demonstrates much stronger SERS enhancement and possesses a low detection limit of 10^?11 M R6G. Such stable SERS performance is useful for practical application in portable Raman detecting devices to detect organic molecules.     

High Surface‐Enhanced Raman Scattering Performance of Individual Gold Nanoflowers and Their Application in Live Cell Imaging

Molecular imaging techniques based on surface‐enhanced Raman scattering (SERS) face a lack of reproducibility and reliability, thus hampering its practical application. Flower‐like gold nanoparticles have strong SERS enhancement performance due to having plenty of hot‐spots on their surfaces, and this enhancement is not dependent on the aggregation of the particles. These features make this kind of particle an ideal SERS substrate to improve the reproducibility in SERS imaging. Here, the SERS properties of individual flower‐like gold nanoparticles are systematically investigated. The measurements reveal that the enhancement of a single gold nanoparticle is independent of the polarization of the excitation laser with an enhancement factor as high as 10⁸. After capping with Raman signal molecules and folic acid, the gold nanoflowers show strong Raman signal in the living cells, excellent targeting properties, and a high signal‐to‐noise ratio for SERS imaging.     

Fabrication and Optical Properties of Periodic Ag Nano‐Pore and Nano‐Particle Arrays with Controlled Shape and Size over Macroscopic Length Scales

A facile and economical route to preparation of highly ordered sliver pore or particle arrays with controlled pore‐shape and size extended over cm² areas is described. The substrates are prepared at planar and curved surfaces via sphere‐imprinted polymer (PDMS) templating using polystyrene spheres with diameters of 820, 600, or 430 nm. Nano‐pore arrays are created by sputtering 80 nm of Ag directly onto the templates and nano‐particle arrays are prepared by electrode‐less deposition of Ag from Tollen's reagent. The shape of the nano‐pore or particles in the array conformed to that of the imprint of the sphere on the template. Stretching the flexible template enable creation of cuboid shaped nano‐voids and nano‐particles following Ag deposition. Diffuse reflectance from the spherical Ag nano‐cavity arrays showed absorbance maxima at wavelengths comparable similar to the diameter of the templating sphere, whereas reflectance from the cuboid arrays, showed little correlation with the sphere diameter. The cuboid nano‐particle arrays showed the most intense visible absorption which is red‐shifted compared to the spherical arrays. White light diffraction from the arrays, observed by rotating 1 cm² substrates relative to a fixed light source, reflected exactly the symmetry axes of the periodic nano‐features in the arrays demonstrating the remarkable macroscopic order of the periodic structures. Raman spectra of 1‐benzenethiol adsorbed at the arrays indicated SERS enhancements from the substrates are attributed mainly to surface nano‐roughness with only moderate contributions from the periodically corrugated structures. Despite excitation at the major resonance dip in the reflectance spectrum, a weak, localized rim dipole mode is found to elicit a small increase in the SERS enhancement factor for the 430 nm diameter spherical arrays. FDTD studies of nano‐void arrays provided insights into v arious factors affecting the SERS experiment and confirmed the array's plasmonic spectra are dominated by propagating plasmon modes under microscope excitation/collection angles.     

Bimetallic Nanostructures as Active Raman Markers: Gold‐Nanoparticle Assembly on 1D and 2D Silver Nanostructure Surfaces

It is demonstrated that bimetallic silver–gold anisotropic nanostructures can be easily assembled from various nanoparticle building blocks with well‐defined geometries by means of electrostatic interactions. One‐dimensional (1D) silver nanowires, two‐dimensional (2D) silver nanoplates, and spherical gold nanoparticles are used as representative building blocks for bottom‐up assembly. The gold nanoparticles are electrostatically bound onto the 1D silver nanowires and the 2D silver nanoplates to give bimetallic nanostructures. The unique feature of the resulting nanostructures is the particle‐to‐particle interaction that subjects absorbed analytes to an enhanced electromagnetic field with strong polarization dependence. The Raman activity of the bimetallic nanostructures is compared with that of the individual nanoparticle blocks by using rhodamine 6G solution as the model analyte. The Raman intensity of the best‐performing silver–gold nanostructure is comparable with the dense array of silver nanowires and silver nanoplates that were prepared by means of the Langmuir–Blodgett technique. An optimized design of a single‐nanostructure substrate for surface‐enhanced Raman spectroscopy (SERS), based on a wet‐assembly technique proposed here, can serve as a compact and low‐cost alternative to fabricated nanoparticle arrays.     

Non-lithographic SERS substrates: tailoring surface chemistry for Au nanoparticle cluster assembly

Near‐field plasmonic coupling and local field enhancement in metal nanoarchitectures, such as arrangements of nanoparticle clusters, have application in many technologies from medical diagnostics, solar cells, to sensors. Although nanoparticle‐based cluster assemblies have exhibited signal enhancements in surface‐enhanced Raman scattering (SERS) sensors, it is challenging to achieve high reproducibility in SERS response using low‐cost fabrication methods. Here an innovative method is developed for fabricating self‐organized clusters of metal nanoparticles on diblock copolymer thin films as SERS‐active structures. Monodisperse, colloidal gold nanoparticles are attached via a crosslinking reaction on self‐organized chemically functionalized poly(methyl methacrylate) domains on polystyrene‐block‐poly(methyl methacrylate) templates. Thereby nanoparticle clusters with sub‐10‐nanometer interparticle spacing are achieved. Varying the molar concentration of functional chemical groups and crosslinking agent during the assembly process is found to affect the agglomeration of Au nanoparticles into clusters. Samples with a high surface coverage of nanoparticle cluster assemblies yield relative enhancement factors on the order of 10⁹ while simultaneously producing uniform signal enhancements in point‐to‐point measurements across each sample. High enhancement factors are associated with the narrow gap between nanoparticles assembled in clusters in full‐wave electromagnetic simulations. Reusability for small‐molecule detection is also demonstrated. Thus it is shown that the combination of high signal enhancement and reproducibility is achievable using a completely non‐lithographic fabrication process, thereby producing SERS substrates having high performance at low cost.     

Controlled Assembly of Highly Raman‐Enhancing Silver Nanocap Arrays Templated by Porous Anodic Alumina Membranes

A convenient nanoscale technique is reported for the fabrication of highly ordered hemispherical silver nanocap arrays templated by porous anodic alumina (PAA) membranes as robust and cost‐efficient surface‐enhanced Raman scattering (SERS) substrates. This geometry produces a high Raman signal due to its periodic hexagonal arrangements and control of the gap between the nanostructures in the sub‐10‐nm regime. The surface structure can be tuned further to optimize the enhancement factor according to optional PAA fabrication and silver deposition parameters. Finite‐difference time‐domain calculations indicate that the structure may possess excellent SERS characteristics due to the high density and abundance of hot spots.     

Self‐Assembled Large Au Nanoparticle Arrays with Regular Hot Spots for SERS

The cost‐effective self‐assembly of 80 nm Au nanoparticles (NPs) into large‐domain, hexagonally close‐packed arrays for high‐sensitivity and high‐fidelity surface‐enhanced Raman spectroscopy (SERS) is demonstrated. These arrays exhibit specific optical resonances due to strong interparticle coupling, which are well reproduced by finite‐difference time‐domain (FDTD) simulations. The gaps between NPs form a regular lattice of hot spots that enable a large amplification of both photoluminescence and Raman signals. At smaller wavelengths the hot spots are extended away from the minimum‐gap positions, which allows SERS of larger analytes that do not fit into small gaps. Using CdSe quantum dots (QDs) a 3–5 times larger photoluminescence enhancement than previously reported is experimentally demonstrated and an unambiguous estimate of the electromagnetic SERS enhancement factor of ≈10⁴ is obtained by direct scanning electron microscopy imaging of QDs responsible for the Raman signal. Much stronger enhancement of ≈10⁸ is obtained at larger wavelengths for benzenethiol molecules penetrating the NP gaps.     

Surface-enhanced Raman scattering of rhodamine 6G on nanowire arrays decorated with gold nanoparticles

We investigate the surface-enhanced Raman scattering (SERS) of rhodamine 6G (R6G) adsorbed on Au nanoparticles attached to InP nanowires. We find that nanowire arrays act as frameworks for effective SERS substrates with a significantly higher Raman signal sensitivity than a planar framework of Au nanoparticles adsorbed two-dimensionally on a flat surface. The SERS signal displays a clear polarization-dependent effect when the nanowires are arranged in a row. We also find that the SERS signal increases with time during continuous laser illumination. The plasmon-enhanced optical forces between Au nanoparticles may either move pairs of nanoparticles closer together or attract adsorbed molecules by moving them to the junctions of Au nanoparticle aggregates. Such effects by plasmon optical forces may cause the observed increase of the SERS signal with continuous laser illumination.     

An effective three-dimensional surface-enhanced Raman scattering substrate based on oblique Si nanowire arrays decorated with Ag nanoparticles

Silicon nanowire arrays (SiNWAs) decorated with metallic nanoparticle heterostructures feature promising applications in surface-enhanced Raman scattering (SERS). However, the densely arranged SiNWAs are usually inconvenient for the following decoration of metallic nanoparticles, and only the top area of silicon nanowires (SiNWs) contributes to the SERS detection. To improve the utilization of the heterostructure, herein, oblique SiNWAs were grown separately, and Ag nanoparticles (AgNPs) were uniformly deposited by magnetron sputtering to get the three-dimensional (3D) SiNWAs decorated with AgNPs (AgNPs-SiNWAs) SERS substrate. The large open surfaces of oblique SiNWs would create more surface area available for the formation of hotspots and improve the adsorption and excitation of analyte molecules on the wire. The optimized AgNPs-SiNWAs substrate exhibits high sensitivity in detecting chemical molecule Rhodamine 6G, and the detection limit can reach 1 × 10^?10 M. More importantly, the substrate also can be used as an effective DNA sensor for label-free DNA detection.     

Carbon nanowalls amplify the surface-enhanced Raman scattering from Ag nanoparticles

We report surface-enhanced Raman scattering (SERS) from Ag nanoparticles decorated on thin carbon nanowalls (CNWs) grown by microwave plasma chemical vapor deposition. The Ag morphology is controlled by exposing the CNWs to oxygen plasma and through the electrodeposition process by varying the number of deposition cycles. The SERS substrates are capable of detecting low concentrations of rhodamine 6G and bovine serum albumin, showing much higher Raman enhancement than ordinary planar HOPG with Ag decoration. The major factors contributing to this behavior include: high density of Ag nanoparticles, large surface area, high surface roughness, and the underlying presence of vertically oriented CNWs. The relatively simple procedure of substrate preparation and nanoparticle decoration suggests that this is a promising approach for fabricating ultrasensitive SERS substrates for biological and chemical detection at the single-molecule level, while also enabling the study of fundamental SERS phenomena.     

Surface-Enhanced Raman Scattering Detection of pH with Silica-Encapsulated 4-Mercaptobenzoic Acid-Functionalized Silver Nanoparticles

Sensors based upon surface-enhanced Raman spectroscopy (SERS) are attractive because they have narrow, vibrationally specific spectral peaks that can be excited using red and near-infrared light which avoids photobleaching, penetrates tissue, and reduces autofluorescence. Several groups have fabricated pH nanosensors by functionalizing silver or gold nanoparticle surfaces with an acidic molecule and measuring the ratio of protonated to deprotonated Raman bands. However, a limitation of these sensors is that macromolecules in biological systems can adsorb onto the nanoparticle surface and interfere with measurements. To overcome this interference, we encapsulated pH SERS sensors in a 30 nm thick silica layer with small pores which prevented bovine serum albumin (BSA) molecules from interacting with the pH-indicating 4-mercaptobenzoic acid (4-MBA) on the silver surfaces but preserved the pH-sensitivity. Encapsulation also improved colloidal stability and sensor reliability. The noise level corresponded to less than 0.1 pH units from pH 3 to 6. The silica-encapsulated functionalized silver nanoparticles (Ag-MBA@SiO(2)) were taken up by J774A.1 macrophage cells and measured a decrease in local pH during endocytosis. This strategy could be extended for detecting other small molecules in situ.     

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.     

Nanofabrication of densely packed metal-polymer arrays for surface-enhanced Raman spectrometry

A key element to improve the analytical capabilities of surface-enhanced Raman spectroscopy (SERS) resides in the performance characteristics of the SERS-active substrate. Variables such as shape, size, and homogeneous distribution of the metal nanoparticles throughout the substrate surface are important in the design of more analytically sensitive and reliable substrates. Electron-beam lithography (EBL) has emerged as a powerful tool for the systematic fabrication of substrates with periodic nanoscale features. EBL also allows the rational design of nanoscale features that are optimized to the frequency of the Raman laser source. In this work, the efficiency of EBL fabricated substrates are studied by measuring the relative SERS signals of Rhodamine 6G and 1,10-phenanthro-line adsorbed on a series of cubic, elliptical, and hexagonal nanopatterned pillars of ma-N 2403 directly coated by physical vapor deposition with 25 nm films of Ag or Au. The raw analyte SERS signals, and signals normalized to metal nanoparticle surface area or numbers of loci, are used to study the effects of nanoparticle morphology on the performance of a rapidly created, diverse collection of substrates. For the excitation wavelength used, the nanoparticle size, geometry, and orientation of the particle primary axis relative to the excitation polarization vector, and particularly the density of nanoparticles, are shown to strongly influence substrate performance. A correlation between the inverse of the magnitude of the laser backscatter passed by the spectrometer and SERS activities of the various substrate patterns is also noted and provides a simple means to evaluate possible efficient coupling of the excitation radiation to localized surface plasmons for Raman enhancement.     

Lithographical gap-size engineered nanoarrays for surface-enhanced Raman probing of biomarkers

Engineered gold nanostructured arrays with feature separation in the sub-10-nm range were fabricated and used for highly sensitive surface enhanced Raman scattering (SERS) detection of biomarkers. Nanostructuring is achieved by combining electron beam lithography with the so-called shadow evaporation technique which involves a two-step Au vapor deposition through a suspended Ge mask while the substrate is tilted in opposite directions. This results in a regular triangular surface pattern with extremely small gap distances that allow positive enhancement of the local electric fields by enabling improvements in the electromagnetic coupling between adjacent nanoparticles. The resulting SERS active surfaces are suitable for the realization of reference procedures for quantifying marker molecules like urea or creatinine at physiologically relevant concentrations.     

Ag Nanoparticle‐Grafted PAN‐Nanohump Array Films with 3D High‐Density Hot Spots as Flexible and Reliable SERS Substrates

A facile fabrication approach of large‐scale flexible films is reported, with one surface side consisting of Ag‐nanoparticle (Ag‐NP) decorated polyacrylonitrile (PAN) nanohump (denoted as Ag‐NPs@PAN‐nanohump) arrays. This is achieved via molding PAN films with ordered nanohump arrays on one side and then sputtering much smaller Ag‐NPs onto each of the PAN‐nanohumps. Surface‐enhanced Raman scattering (SERS) activity of the Ag‐NPs@PAN‐nanohump array films can be improved by curving the flexible PAN film with ordered nanohump arrays during the Ag‐sputtering process to increase the density of the Ag‐NPs on the sidewalls of the PAN‐nanohumps. More 3D hot spots are thus achieved on a large‐scale. The Ag‐NPs@PAN‐nanohump array films show high SERS activity with good Raman signal reproducibility for Rhodamine 6G probe molecules. To trial their practical application, the Ag‐NPs@PAN‐nanohump array films are employed as SERS substrates for trace detection of trinitrotoluene and a congener of polychlorinated biphenyls. A lower detection limit of 10⁻¹²m and 10⁻⁵m can be achieved, respectively. Furthermore, the flexible Ag‐NPs@PAN‐nanohump array films can also be utilized as swabs to probe traces of methyl parathion on the surface of fruits such as apples. The as‐fabricated SERS substrates therefore have promising potential for applications in rapid safety inspection and environmental protection.     

Gold Binary‐Structured Arrays Based on Monolayer Colloidal Crystals and Their Optical Properties

A simple and flexible route is presented to fabricate a gold binary‐structured ordered array by one step based on non‐shadow deposition on a plasma etching‐induced dualistic monolayer colloidal crystal. Such a Au binary‐structure array is built of hexagonally arranged nanoshells and nanorings which stand between two adjacent nanoshells. Six gold nanorings surround each nanoshell. The obtained arrays exhibit both the controllable surface‐plasmon‐resonance (SPR) properties of Au nanoshells and the strong electromagnetic‐field‐enhancement effects of Au nanorings, with the high structural stability of ordered arrays, and show promising potential as the substrate of surface‐enhanced Raman scattering (SERS)‐based devices. The method could also be suitable for fabrication of other material binary‐structured arrays. This study is important in designing and fabricating basal materials for the next generation of multifunctional nanostructured devices.     

Wafer‐Scale Double‐Layer Stacked Au/Al2O3@Au Nanosphere Structure with Tunable Nanospacing for Surface‐Enhanced Raman Scattering

Fabricating perfect plasmonic nanostructures has been a major challenge in surface enhanced Raman scattering (SERS) research. Here, a double‐layer stacked Au/Al₂O₃@Au nanosphere structures is designed on the silicon wafer to bring high density, high intensity “hot spots” effect. A simply reproducible high‐throughput approach is shown to fabricate feasibly this plasmonic nanostructures by rapid thermal annealing (RTA) and atomic layer deposition process (ALD). The double‐layer stacked Au nanospheres construct a three‐dimensional plasmonic nanostructure with tunable nanospacing and high‐density nanojunctions between adjacent Au nanospheres by ultrathin Al₂O₃ isolation layer, producing highly strong plasmonic coupling so that the electromagnetic near‐field is greatly enhanced to obtain a highly uniform increase of SERS with an enhancement factor (EF) of over 10⁷. Both heterogeneous nanosphere group (Au/Al₂O₃@Ag) and pyramid‐shaped arrays structure substrate can help to increase the SERS signals further, with a EF of nearly 10⁹. These wafer‐scale, high density homo/hetero‐metal‐nanosphere arrays with tunable nanojunction between adjacent shell‐isolated nanospheres have significant implications for ultrasensitive Raman detection, molecular electronics, and nanophotonics.     

Development of a surface-enhanced Raman technique for biomarker studies on Mars

Raman spectroscopy has been identified as a potentially useful tool to collect evidence of past or present life on extraterrestrial bodies. However, it is limited by its inherently low signal strength. In this investigation, laboratory tests were conducted using surface-enhanced Raman spectroscopy (SERS) in an "inverted" mode to detect the presence of organic compounds that may be similar to possible biomarkers present on Mars. SERS was used to overcome the inherently low signal intensity of Raman spectroscopy and was an effective method for detecting small concentrations of organic compounds on a number of surfaces. For small organic molecules, dissolution of the molecule to be analyzed in a suitable solvent and depositing it on a prepared SERS substrate for analysis is possible. However, for larger molecules, an "inverted" SERS (iSERS) technique was shown to be effective. In iSERS, nanoparticles of silver or gold were deposited on the mineral substrate/organic compound to be analyzed. Benzotriazole, benzoic acid, and phthalic acid were used as test organic analogs and the iSERS technique was able to detect femtomole levels of the analytes. The interference from various mineral substrates was also examined. Different methods of depositing silver particles were evaluated, including ion beam-assisted vapor deposition and deposition from aqueous colloidal suspensions.     

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.     

In Situ Two‐Step Photoreduced SERS Materials for On‐Chip Single‐Molecule Spectroscopy with High Reproducibility

A method is developed to synthesize surface‐enhanced Raman scattering (SERS) materials capable of single‐molecule detection, integrated with a microfluidic system. Using a focused laser, silver nanoparticle aggregates as SERS monitors are fabricated in a microfluidic channel through photochemical reduction. After washing out the monitor, the aggregates are irradiated again by the same laser. This key step leads to full reduction of the residual reactants, which generates numerous small silver nanoparticles on the former nanoaggregates. Consequently, the enhancement ability of the SERS monitor is greatly boosted due to the emergence of new “hot spots.” At the same time, the influence of the notorious “memory effect” in microfluidics is substantially suppressed due to the depletion of surface residues. Taking these advantages, two‐step photoreduced SERS materials are able to detect different types of molecules with the concentration down to 10^?13m . Based on a well‐accepted bianalyte approach, it is proved that the detection limit reaches the single‐molecule level. From a practical point of view, the detection reproducibility at different probing concentrations is also investigated. It is found that the effective single‐molecule SERS measurements can be raised up to ≈50%. This microfluidic SERS with high reproducibility and ultrasensitivity will find promising applications in on‐chip single‐molecule spectroscopy.