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We present a freeform-segmented reflector-based microfluidic system for conventional Raman and Surface-Enhanced Raman Scattering (SERS) analysis. The segmented reflector is directly designed by a numerical approach. The polymer-based Raman system strongly suppresses the undesirable background because it enables confocal detection of Raman scattering through the combination of a freeform reflector and a microfluidic chip. We perform systematic simulations using non-sequential ray tracing with the Henyey-Greenstein model to assess the Raman scattering behavior of the substance under test. We fabricate the freeform reflector and the microfluidic chip by means of ultra-precision diamond turning and laser cutting respectively. We demonstrate the confocal behavior by measuring the Raman spectrum of ethanol. Besides, we calibrate the setup by performing Raman measurements on urea and potassium nitrate solutions with different concentrations. The detection limit of our microfluidic system is approximately 20 mM according to the experiment. Finally, we implement a SERS microfluidic chip and discriminate 100 μM urea and potassium nitrate solutions.

Surface-enhanced Raman spectroscopy (SERS)-based molecular detection at extremely low concentrations often relies on mapping of a SERS substrate. This yields a large number (>1000) of SERS spectra that can improve the limit of detection; however, the signal collection time is a major constraint. In this work, a wide line (WL) laser focusing technique aimed at fast mapping of SERS substrates is presented. The WL technique enables acquisition of thousands of SERS spectra in a few seconds without missing any of the electromagnetic “hot spots” in the illuminated area. In addition, the SERS signal averaging across the line in the WL mode displays extremely high signal-to-noise ratios. The advantages of the WL technique for SERS-based sensing are verified using different analyte molecules, that is, p-coumaric acid and melamine. Results show that the limit of detection can be improved by one order of magnitude compared to results obtained using a commercial Raman microscope.

Ultra-sensitive in-field measurements of most forensic substances still today remain a challenge for first responders and forensic investigators. Handheld Raman spectroscopy equipment is getting more and more routinely used in the field for evidence collection, however, restricted to measurements of pure or high concentration samples. Here, surface-enhanced Raman scattering (SERS) sensing of common forensic substances with commercially available SERS substrates and handheld spectrometers, have been investigated. 3D Finite Element Method (FEM) and Density Functional Theory (DFT) simulations were used to interpret the high SERS enhancement of the Ag nanopillar substrate and the detection of the substances, respectively. The forensic generality and high performance of the analytical method were demonstrated by explicit detection of close to unprecedented amounts, down to femtograms, of Cyclosarin, RDX, Amphetamine and Picric acid. Implications are ultra-sensitive in-field SERS detection of these substances with commercial equipment.

Robust, macroscopically uniform, and highly sensitive substrates for surface-enhanced Raman spectroscopy (SERS) are fabricated using wafer-scale block copolymer lithography. The substrate consists of gold nanoparticles that can slide and aggregate on dense and recyclable alumina/silicon nanohoodoos. Hot-spot engineering is conducted to maximize the SERS performance of the substrate. The substrate demonstrates remarkably large surface-averaged SERS enhancements, greater than 107 (>108 in hot spots), with unrivalled macroscopic signal uniformity as characterized by a coefficient of variation of only 6% across 4 cm. After SERS analyses, the nanohoodoos can be recycled by complete removal of gold via a one-step, simple, and robust wet etching process without compromising performance. After eight times of recycling, the substrate still exhibits identical SERS performance in comparison to a new substrate. The macroscopic uniformity combined with recyclability at conserved high performance is expected to contribute significantly on the overall competitivity of the substrates. These findings show that the gold nanoparticles sliding on recyclable nanohoodoo substrate is a very strong candidate for obtaining cost-effective, high-quality, and reliable SERS spectra, facilitating a wide and simple use of SERS for both laboratorial and commercial applications

Carbon nanotubes (CNTs) and graphene are at the center of a significant research effort due to their unique physical and chemical properties, which promise high technological impact. For the future development of all the foreseen applications, it is of particular interest the study of binding interactions between carbon nanostructures and functional groups. An appropriate method is the surface-enhanced Raman spectroscopy (SERS), which provides a large amplification of Raman signals when the probed molecule is adsorbed on a nanosized metallic surface. In this chapter, we present a review of principal results obtained applying SERS for the characterization of pristine and functionalized CNTs and graphene. The obtained results encourage us to consider SERS as a powerful method to obtain a rapid monitor of the procedures used to interface graphene and nanotubes.

The number of newly developed genetic variants of microbial cell factories for production of biochemicals has been rapidly growing in recent years, leading to an increased need for new screening techniques. We developed a method based on surface-enhanced Raman scattering (SERS) coupled with liquid-liquid extraction (LLE) for quantification of p-coumaric acid (pHCA) in the supernatant of genetically engineered Escherichia coli (E. coli) cultures. pHCA was measured in a dynamic range from 1 μM up to 50 μM on highly uniform SERS substrates based on leaning gold-capped nanopillars, which showed an in-wafer signal variation of only 11.7%. LLE using dichloromethane as organic phase was combined with the detection in order to increase selectivity and sensitivity by decreasing the effect of interfering compounds from the analytes of interest. The difference in pHCA production yield between three genetically engineered E. coli strains was successfully evaluated using SERS and confirmed with high-performance liquid chromatography. As this novel approach has potential to be automated and parallelized, it can be considered for high-throughput screening in metabolic engineering.

Picric acid (PA) is a severe environmental and security risk due to its unstab e, toxic, and explosive properties. It is also challenging to detect in trace amounts and in situ because of its highly acidic and anionic character. Here, we assess sensing of PA under nonlaboratory conditions using surface-enhanced Raman scattering (SERS) silver nanopillar substrates and handheld Raman spectroscopy equipment. The advancing elasto-capillarity effects are explained by molecular dynamics simulations. We obtain a SERS PA detection limit on the order of 20 ppt, corresponding attomole amounts, which together with the simple analysis methodology demonstrates that the presented approach is highly competitive for ultrasensitive analysis in the field.

In this work, we present a dual-functional sensor that can perform surface-enhanced Raman spectroscopy (SERS) based identification and electrochemical (EC) quantification of analytes in liquid samples. A lithography-free reactive ion etching process was utilized to obtain nanostructures of high aspect ratios distributed homogeneously on a 4-inch fused silica wafer. The sensor was made up of three-electrode array, obtained by subsequent e-beam evaporation of Au on nanostructures in selected areas through a shadow mask. The SERS performance was evaluated through surface-averaged enhancement factor (EF), which was ~6.2 x 105, and spatial uniformity of EF, which was ~13% in terms of relative standard deviation. Excellent electrochemical performance and reproducibility were revealed by recording cyclic voltammograms. On nanostructured electrodes, paracetamol (PAR) showed an improved quasi-reversible behavior with decrease in peak potential separation (∆Ep ~90mV) and higher peak currents (Ipa/Ipc ~1), comparing to planar electrodes (∆Ep ~560mV). The oxidation potential of PAR was also lowered by ~80 mV on nanostructured electrodes. To illustrate dual-functional sensing, quantitative evaluation of PAR ranging from 30 µM to 3 mM was realized through EC detection, and presence of PAR was verified by its SERS fingerprint.

The ideal surface-enhanced Raman spectroscopy (SERS) substrate should fulfil the following: (a) predictable SERS enhancement, (b) macroscale SERS signal uniformity, and (c) suitability for mass production at low costs. Macroscale SERS uniformity and reproducibility at practical levels are big obstacles, which have been preventing most SERS substrates from reliable sensing applications. We have previously shown that SERS-active nanopillar structures, fabricated by lithography-free processes, exhibit high average SERS enhancements and are mass producible. Here, we report an optimized process and show that the improved structures exhibit unrivalled macroscale SERS uniformities (RSD: ∼2.5% in millimeter scale, ∼7% in wafer scale) and reproducibility (RSD: ∼1.5% across 3 wafers), while at the same time exhibiting a very large average SERS enhancement factor of >108. The obtained SERS uniformity (~2.5% RSD in millimeter scale) is the best to date measured on large-area solid SERS substrates. Fast and reproducible SERS analysis of trans-1,2-bis (4-pyridyl) ethylene down to 4x10-13 mol is demonstrated using the optimized structures. We emphasize that achieving simultaneously macroscopic, practical-level SERS signal reproducibility and high enhancement via a lithography-free process is a notable advance towards industrialization of substrate-based SERS sensors.

We present an improved procedure for analytical detection of toxic polychlorinated biphenyls (PCB) using surface-enhanced Raman scattering (SERS) spectroscopy. A gold-capped silicon nanopillar substrate was utilized to concentrate PCB molecules within an area of high electromagnetic fields through formation of microsized nanopillar clusters, and consequently, so-called “hot spots” can be formed. In order to improve PCB detection limit, 3,3',4,4'-tetrachlorobiphenyl (PCB77) compounds were chemically modified with a – SCH3 (PCB77-SCH3) group. Experimental and numerical analysis of vibrational modes showed only minor differences between standard PCB77 and PCB77-SCH3. Consequently, we observe significantly increased SERS signals for –SCH3 modified PCB77 while retaining most vibrational modes that characterize standard PCB77. Results point towards more efficient path for detecting different PCB congeners from real-life samples. We interpret the result as PCB77-SCH3 link to gold surface via sulfur atoms that facilitates accumulation of the modified PCB molecules on the metal surface. For similar SERS experimental conditions most spectral characteristics of PCB77 are identifiable down to concentrations of ~10-5 M while PCB77-SCH3 spectral fingerprint is retained in ~10-8 M range.

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%.

Metal-coated nanostructured surfaces have shown promise as substrates for surface-enhanced Raman spectroscopy (SERS) as they allow chemical trace detection with high sensitivity and rapid response. This sensitivity and specificity makes SERS especially interesting for environmental and biological analysis. Metal-capped silicon nanopillars, fabricated through a maskless ion etch, are state-of-the-art for on-chip SERS substrates. A dense cluster of high aspect ratio polymer nanocones was achieved by using high-throughput polymer injection moulding over a large area replicating a silicon nanopillar structure. Gold-capped polymer nanocones display similar SERS sensitivity as silicon nanopillars, while being easily integrable into a microfluidic chips.

The invention relates to a method for preparing a substrate (105a) comprising a sample reception area (110) and a sensing area (111). The method comprises the steps of: 1) applying a sample on the sample reception area; 2) rotating the substrate around a predetermined axis; 3) during rotation, at least part of the liquid travels from the sample reception area to the sensing area due to capillary forces acting between the liquid and the substrate; and 4) removing the wave of particles and liquid formed at one end of the substrate. The sensing area is closer to the predetermined axis than the sample reception area. The sample comprises a liquid part and particles suspended therein.

A standard protocol for analysis of microbial factories requires the screening of several populations in order to find the bestperforming ones. Standard analytical methods usually include high performance liquid chromatography (HPLC), thin layerchromatography (TLC) or spectrophotometry, which are expensive and time-consuming processes. Surface Enhanced Raman Spectroscopy (SERS), instead, is a highly sensitive spectroscopic technique for specific, fast and real-time sensing of biologicalsamples. Here we demonstrate the use of SERS to discriminate between two different bacterial populations based on detection ofp-coumaric acid (pHCA) in cell supernatant.SERS active substrates, based on leaning gold-capped silicon nanopillars, were used for detection. They were successfullyused to detect culture medium spiked with pHCA, and the effect of medium dilution was studied. For analysis of biologicalproduction of pHCA, triplicate cultures of E. coli strains expressing a pHCA-forming enzyme (P) as well as of a non-producingstrain (C) were grown. Then, supernatant samples were collected and their pHCA content was measured using SERS and HPLCfor comparison. The intensity of the pHCA Raman mode at 1169 cm-1 (CH-rocking motion) showed different trends for P and Cstrains, similar to the results obtained using the HPLC method. Results illustrate that SERS can be used for quick and semiquantitativediscrimination of pHCA concentrations in cell supernatant medium.

Threats from chemical warfare agents, commonly known as nerve gases, constitute a serious security issue of increasing global concern because of surging terrorist activity worldwide. However, nerve gases are difficult to detect using current analytical tools and outside dedicated laboratories. Here we demonstrate that surface-enhanced Raman scattering (SERS) can be used for sensitive detection of femtomol quantities of two nerve gases, VX and Tabun, using a handheld Raman device and SERS substrates consisting of flexible gold-covered Si nanopillars. The substrate surface exhibits high droplet adhesion and nanopillar clustering due to elasto-capillary forces, resulting in enrichment of target molecules in plasmonic hot-spots with high Raman enhancement. The results may pave the way for strategic life-saving SERS detection of chemical warfare agents in the field., QC 20171214

The invention relates to a method and system of detecting the presence of one or more specific target analytes in a sample. The method comprises the steps of exposing a SERS-active surface to the sample so as to capture analytes from the sample by adherence to the SERS-active surface; acquiring an ensemble X of Raman/SERS-spectra measured at different locations on the SERS-active surface; for each target analyte, determining a target spectrum representative of that target analyte; modelling the ensemble X of measured Raman/SERS-spectra using a factorization-model, wherein the factorization-model includes a loadings matrix A times a spectral component matrix S, wherein matrix elements of A and S are all real and non-negative; jointly estimating parameters in the factorization-model, the estimated parameters including at least A and S; for each target analyte, selecting amongst the spectral components of S a target component corresponding to the target spectrum of that target analyte; and determining presence of the one or more target analytes at least on the basis of the estimated loadings for the selected target components. During estimation at least one of the one or more target components is populated according to a p re-determined function.

In this work, we present recent results of lifetime optimization for nano-structured black silicon and its photovoltaic applications. Black silicon nano-structures provide significant reduction of silicon surface reflection due to highly corrugated nanostructures with excellent light trapping properties. We applied reactive ion etching technology at -20ºC to create nano-structures on silicon samples and obtained an average reflectance below 0.5%. For passivation purposes, we used 37 nm ALD Al2O3 films. Lifetime measurements resulted in 1220 µs and to 4170 µs for p- and ntype CZ silicon wafers, respectively. This is promising for use of black silicon RIE nano-structuring in a solar cell process flow

Tunable plasmonic platforms are important for a variety of applications such as photovoltaics, LED's, optoelectronics, medical research, and biosensors. In particular, development of label-free plasmonic biosensors is one of the key research areas that utilizes plasmonic nanostructures for detection of biologically relevant molecules at low concentrations. The authors have developed a cost-effective, fast, and lithography-free method to fabricate transparent fused silica nanocylinders. The technique allows tuning of nanocylinder height, diameter, and density and can be scaled to large surface areas, such as 8 in. wafers. The authors demonstrate that gold coated nanocylinders support localized surface plasmon resonances (LSPR) from visible to near infrared wavelengths. The plasmonic platform can be characterized as suspended gold nanorings and exhibits a sensitivity of 658 nm RIU-1 with a figure-of-merit of 10, comparable to other state-of-the-art LSPR sensing platforms that utilize more complex nanofabrication pathways. It was observed that the LSPR peak positions can be controlled by varying the geometry of the nanocylinders. The authors illustrate surface functionalization, biosensing, and surface regeneration properties of the platform using thiols and detection of bovine serum albumin (BSA). The observed LSPR shifts for 11-mercaptoundecanoic acid and BSA was 12 and 26 nm, respectively.

A substrate for a plurality of different measurement set-ups such as SERS, SPR and LSPR which substrate has a base and a plurality of elongate elements with metallic tips. A metallic layer is present on the base surface between the elongate elements and gaps or cavities exist between the layer and the tips or elongate elements. When the elongate elements and the base are transparent, transmission measurement set-ups are also possible.