Wafer-scale surface-enhanced Raman scattering (SERS) substrates fabricated using maskless lithography are important for scalable production targets. Large-area, leaning silver-capped silicon nanopillar (Ag NP) structures suitable for SERS molecular detection at extremely low analyte concentrations are investigated. Theoretical results show that isolated Ag NPs essentially support two localized surface plasmon (LSP) modes. The most prominent LSP resonance is observed in the near-infrared region (~800 nm) and can be tuned by changing the diameter of the silicon nanopillars (Si NPs). The corresponding electric field distribution maps indicate that the maximum E-field enhancement is found at the Ag cavity, i.e. the bottom part of the Ag cap. We argue that the plasmon coupling between the resonant Ag cap cavities contributes most to the enhancement of the Raman signal. We experimentally evaluate these findings and show that by exposing Si NPs to an O 2 -plasma the average Ag NP cluster size, and thus the overall inter-pillar coupling, can be systematically reduced. We show that deposition of Cr adhesion layers on Si NPs (>3 nm) introduce plasmon coupling loss to the Ag NP LSP cavity mode that significantly reduces the SERS intensity. Results also show that short exposures to the O 2 -plasma and the use of 1-3 nm Cr adhesion layers are advantageous for reducing the signal background noise from Ag NPs. In addition, influence of the Ag NP height and Ag metal thickness on SERS intensities is investigated and optimal fabrication process parameters are evaluated. Finally, the SERS spectrum from 100 pM of trans-1,2-bis (4-pyridyl) ethylene (BPE) is recorded showing distinct characteristic Raman vibrational modes. The calculated enhancement factor is of the order of 10 8 , and the SERS signal intensity exhibits a standard deviation of around 14% (660 data points) across a 5x5 mm 2 surface area.

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There is an increasing demand for rapid, sensitive, and low cost analytical methods to routinely screen antibiotic residues in food products. Conventional detection of antibiotics involves sample preparation by liquid-liquid or solid-phase extraction, followed by analysis using liquid chromatography-mass spectrometry (LC-MS), capillary electrophoresis (CE), or gas chromatography (GC). The process is labor-intensive, time-consuming, and expensive. In this study, we developed a new analytical method that combines magnetic molecularly imprinted polymer (MMIP)-based sample preparation with surface-enhanced Raman spectroscopy (SERS)-based detection for quantitative analysis of cloxacillin in pig serum. MMIP microspheres were synthesized using a core-shell technique. The large loading capacity and high selectivity of the MMIP microspheres enabled efficient extraction of cloxacillin, while the magnetically susceptible characteristics greatly simplified sample handling procedures. Low cost and robust SERS substrates consisting of vertical gold capped silicon nanopillars were fabricated and employed for the detection of cloxacillin. Quantitative SERS was achieved by normalizing signal intensities using an internal standard. By coherently combining MMIP extraction and silicon nanopillar-based SERS biosensor, good sensitivity toward cloxacillin was achieved. The detection limit was 7.8 pmol. Cloxacillin recoveries from spiked pig plasma samples were found to be more than 80%.

Abstract:Localized surface plasmon resonances (LSPR) and plasmon couplings in Ag capped Si Nanopillar (Ag NP) structures are studied using 3D FEM simulations and dark-field scattering microscopy. Simulations show that a standalone Ag NP supports two LSPR modes, i.e. the particle mode and the cavity mode. The LSPR peak position of the particle mode can be tuned by changing the size of the Ag cap, and can be hybridized by leaning of pillars. The resonance position of the cavity resonance mode can be tuned primarily via the diameter of the Si pillar, and cannot be tuned via leaning of Ag NPs. The presence of a substrate dramatically changes the intensity of these two LSPR modes by introducing constructive and destructive interference patterns with incident and reflected fields. Experimental scattering spectra can be interpreted using theoretical simulations. The Ag NP substrate displays a broad plasmonic resonance band due to the contribution from both the hybridized particle LSPR and the cavity LSPR modes.

We demonstrate the direct photothermal probing and mapping of single plasmonic nanostructures via the temperature-induced detuning of nanomechanical string resonators. Single Au nanoslits and nanorods are illuminated with a partially polarized focused laser beam (λ = 633 nm) with irradiances in the range of 0.26-38 μW/μm(2). Photothermal heating maps with a resolution of ∼375 nm are obtained by scanning the laser over the nanostructures. Based on the string sensitivities, absorption efficiencies of 2.3 ± 0.3 and 1.1 ± 0.7 are extracted for a single nanoslit (53 nm × 1 μm) and nanorod (75 nm × 185 nm). Our results show that nanomechanical resonators are a unique and robust analysis tool for the low-power investigation of thermoplasmonic effects in plasmonic hot spots.

Practical implementation of surfaced enhanced Raman spectroscopy (SERS) sensing is hindered by complexity of real-life samples, which often requires long and costly pretreatment and purification. Here, we present a novel nanopillar-assisted SERS chromatography (NPC-SERS) method for simultaneous quantitation of target molecules and analysis of complex, multicomponent fluids, e.g., human urine spiked with a model drug paracetamol (PAR). Gold-coated silicon nanopillar (AuNP) SERS substrates and a centrifugal microfluidic platform are tactfully combined, which allows (i) a precise and fully automated sample manipulation and (ii) spatial separation of different molecular species on the AuNP substrate. The NPC-SERS technique provides a novel approach for wetting the stationary phase (AuNP) using the “wicking effect”, and thus minimizes dilution of analytes. Separation of PAR and the main human urine components (urea, uric acid, and creatinine) has been demonstrated. Quantitative detection of PAR with ultrawide linear dynamic range (0–500 ppm) is achieved by analyzing the spreading profiles of PAR on the AuNP surface. NPC-SERS transforms SERS into a sensing technique with general applicability, facilitating rapid and quantitative detection of analytes in complex biofluids, such as saliva, blood, and urine.

We report a novel nanofabrication process via block copolymer lithography using solvent vapor annealing. The nanolithography process is facile and scalable, enabling fabrication of highly ordered periodic patterns over entire wafers as substrates for surface-enhanced Raman spectroscopy (SERS). Direct silicon etching with high aspect ratio templated by the block copolymer mask is realized without any intermediate layer or external precursors. Uniquely, an atomic layer deposition (ALD)-assisted method is introduced to allow reversing of the morphology relative to the initial pattern. As a result, highly ordered silicon nanopillar arrays are fabricated with controlled aspect ratios. After metallization, the resulting nanopillar arrays are suitable for SERS applications. These structures readily exhibit an average SERS enhancement factor of above 10(8), SERS uniformities of 8.5% relative standard deviation across 4 cm, and 6.5% relative standard deviation over 5 × 5 mm(2) surface area, as well as a very low SERS background. The as-prepared SERS substrate, with a good enhancement and large-area uniformity, is promising for practical SERS sensing applications.

To enable affordable detection and diagnostic, there is a need for low-cost and mass producible miniaturized sensing platforms. We present a fully polymeric microfluidic lab-on-a-chip device with integrated gold (Au)-capped nanocones for sensing applications based on surface-enhanced Raman spectroscopy (SERS). All base components of the device were fabricated via injection molding (IM) and can be easily integrated using ultrasonic welding. The SERS sensor array, embedded in the bottom of a fluidic channel, was created by evaporating Au onto IM nanocone structures, resulting in densely packed Au-capped SERS active nanostructures. Using a Raman active model analyte, trans-1,2-bis-(4pyridyl)-ethylene, we found a surface-averaged SERS enhancement factor of ∼5 × 10 6 with a relative standard deviation of 14% over the sensor area (2 × 2 mm 2 ), and a 18% signal variation among substrates. This reproducible fabrication method is costeffective, less time consuming, and allows mass production of fully integrated polymeric, microfluidic systems with embedded high-density and high-aspect ratio SERS sensor.