Ultrasensitive enhanced Raman spectroscopy by hybrid surface-enhanced and interference-enhanced Raman scattering with metal-insulator-metal structures.

High-sensitivity, reproducible, and low-cost substrate has been a major obstacle for practical sensing application of surface-enhancement Raman scattering (SERS). In this work, we report a type of simple SERS substrate which is composed of metal-insulator-metal (MIM) structure of Ag nanoisland (AgNI)-SiO2-Ag film (AgF). The substrates are fabricated by only evaporation and sputtering processes, which are simple, fast and low-cost. By combining the hotspots and interference-enhanced effects in AgNIs and the plasmonic cavity (SiO2) between AgNIs and AgF, the proposed SERS substrate shows an enhancement factor (EF) of 1.83 × 108 with limit of detection (LOD) down to 10-17 mol/L for rhodamine 6 G (R6G) molecules. The EFs are ∼18 times higher than that of conventional AgNIs without MIM structure. In addition, the MIM structure shows excellent reproducibility with relative standard deviation (RSD) less than 9%. The proposed SERS substrate is fabricated only with evaporation and sputtering technique and the conventionally used lithographic methods or chemical synthesis are not required. This work provides a simple way to fabricate ultrasensitive and reproducible SERS substrates which show great promise for developing various biochemical sensors with SERS.

Surface-enhanced Raman Scattering of Au-Ag bimetallic nanopillars fabricated using surface-plasmon lithography.

Arrays of gold-silver (Au-Ag) bimetallic nanopillars were fabricated by a newly developed surface-plasmon lithography (SPL) and their enhancement properties as surface-enhanced Raman scattering (SERS) substrates have been studied. We demonstrated that the SPL is a low-cost and high efficiency method for the fabrication of SERS substrates with both high sensitivity and reproducibility. The nanopillars showed a good response in the detection of methylene blue molecules at a low concentration of 1.0 × 10-11mol· l-1. The SERS enhancement factors (EFs) are on the orders of 107and the relative standard deviation of SERS intensity is <8% over an area of 50µm × 50µm. The EFs increase fast with the height increasing from 200 to 530 nm, then increase slowly when further increase the height of the nanopillars to 1100 nm. In addition, the Au-Ag bimetallic coating has shown much higher SERS enhancement than the coatings of either the pure Au or Ag. The excellent SERS enhancement and reproducibility of the Au-Ag coated nanopillars indicated that the fabricated SERS substrates can be used for the detection of biochemical molecules at trace level and the SPL is a promising method for fabrication of SERS substrates.

Multiple-resonant pad-rod nanoantennas for surface-enhanced infrared absorption spectroscopy.

Due to the ability to tightly confine electromagnetic energy, plasmonic nanoantennas have been widely studied for surface-enhanced infrared absorption (SEIRA) spectroscopy, surface-enhanced Raman spectroscopy as well as refractive index sensing. However, most of the nanoantennas are limited by narrow resonant band and it is rather challenging to detect multiple molecular fingerprints. In this work, we report dual and triple- resonant pad-rod plasmonic nanoantennas which are nanorods with large pads at their ends placed above gold (Au) mirror separated by a spacer layer. By adjusting the geometries, the nanoantennas have demonstrated dual and triple resonant bands enabling detection of molecular fingerprints at different wavelength. The calculated maximum SEIRA enhancement factor is around 1.8 × 106, which is among the highest reported so far. The pad-rod plasmonic nanoantennas have been used for the detection of molecules of polymethyl methacrylate (PMMA) by SEIRA and fingerprints of C=O and C-H bands are clearly identified. This work has shown that the multiple-resonant pad-rod plasmonic nanoantennas are promising for chemical and biomolecular sensing by the detection of vibrational fingerprints with SEIRA.

High optical transmittance of aluminum ultrathin film with hexagonal nanohole arrays as transparent electrode.

We fabricate samples of aluminum ultrathin films with hexagonal nanohole arrays and characterize the transmission performance. High optical transmittance larger than 60% over a broad wavelength range from 430 nm to 750 nm is attained experimentally. The Fano-type resonance of the excited surface plasmon plaritons and the directly transmitted light attribute to both of the broadband transmission enhancement and the transmission suppression dips.

Resonance control of mid-infrared metamaterials using arrays of split-ring resonator pairs.

We present our design, fabrication and characterization of resonance-controllable metamaterials operating at mid-infrared wavelengths. The metamaterials are composed of pairs of back-to-back or face-to-face U-shape split-ring resonators (SRRs). Transmission spectra of the metamaterials are measured using Fourier-transform infrared spectroscopy. The results show that the transmission resonance is dependent on the distance between the two SRRs in each SRR pair. The dips in the transmission spectrum shift to shorter wavelengths with increasing distance between the two SRRs for both the back-to-back and face-to-face SRR pairs. The position of the resonance dips in the spectrum can hence be controlled by the relative position of the SRRs. This mechanism of resonance control offers a promising way of developing metamaterials with tunability for optical filters and bio/chemical sensing devices in integrated nano-optics.

Real time hybridization studies by resonant waveguide gratings using nanopattern imaging for Single Nucleotide Polymorphism detection.

2D imaging of biochips is particularly interesting for multiplex biosensing. Resonant properties allow label-free detection using the change of refractive index at the chip surface. We demonstrate a new principle of Scanning Of Resonance on Chip by Imaging (SORCI) based on spatial profiles of nanopatterns of resonant waveguide gratings (RWGs) and its embodiment in a fluidic chip for real-time biological studies. This scheme allows multiplexing of the resonance itself by providing nanopattern sensing areas in a bioarray format. Through several chip designs we discuss resonance spatial profiles, dispersion and electric field distribution for optimal light-matter interaction with biological species of different sizes. Fluidic integration is carried out with a black anodized aluminum chamber, advantageous in term of mechanical stability, multiple uses of the chip, temperature control and low optical background. Real-time hybridization experiments are illustrated by SNP (Single Nucleotide Polymorphism) detection in gyrase A of E. coli K12, observed in evolution studies of resistance to the antibiotic ciprofloxacin. We choose a 100 base pairs (bp) DNA target (~30 kDa) including the codon of interest and demonstrate the high specificity of our technique for probes and targets with close affinity constants. This work validates the safe applicability of our unique combination of RWGs and simple instrumentation for real-time biosensing with sensitivity in buffer solution of ~10 pg/mm². Paralleling the success of RWGs sensing for cells sensing, our work opens new avenues for a large number of biological studies.

Extraordinary mid-infrared transmission of subwavelength holes in gold films.

Gold (Au) nanoholes are fabricated with electron-beam lithography and used for the investigation of extraordinary transmission in mid-infrared regime. Transmission properties of the nanoholes are studied as the dependence on hole-size. Transmittance spectra are characterized by Fourier transform infrared spectroscopy (FTIR) and enhanced transmittance through the subwavelength holes is observed. The transmission spectra exhibit well-defined maximum and minimum of which the position are determined by the lattice of the hole array. The hole-size primarily influence the transmission intensity and bandwidth of the resonance peak. With an increase of hole-size, while keep lattice constant fixed, the intensity of the resonance peak and the bandwidth increases, which are due to the localized surface plasmons. Numerical simulation for the transmission through the subwavelength holes is performed and the simulated results agree with the experimental observations.

Single-molecule detection of SARS-CoV-2 N protein on multilayered plasmonic nanotraps with surface-enhanced Raman spectroscopy.

The spread of the SARS-CoV-2 virus has had an unprecedented impact, both by posing a serious risk to human health and by amplifying the burden on the global economy. The rapid identification of the SARS-CoV-2 virus has been crucial to preventing and controlling the spread of SARS-CoV-2 infections. In this study, we propose a multilayered plasmonic nanotrap (MPNT) device for the rapid identification of single particles of SARS-CoV-2 virus in ultra-high sensitivity by surface-enhanced Raman scattering (SERS). The MPNT device is composed of arrays of concentric cylindrical cavities with Ag/SiO2/Ag multilayers deposited on the top and at the bottom. By varying the diameter of the cylinders and the thickness of the multilayers, the resonant optical absorption and local electric field were optimized. The SERS enhancement factors of the proposed device are of the order of 108, which enable the rapid identification of SARS-CoV-2 N protein in concentrations as low as 1.25 × 10-15－12.5 × 10-15 g mL-1 within 1 min. The developed MPNT SERS device provides a label-free and rapid detection platform for SARS-CoV-2 virus. The general nature of the device makes it equally suitable to detect other infectious viruses.

Broadband plasmon induced transparency in terahertz metamaterials.

Plasmon induced transparency (PIT) could be realized in metamaterials via interference between different resonance modes. Within the sharp transparency window, the high dispersion of the medium may lead to remarkable slow light phenomena and an enhanced nonlinear effect. However, the transparency mode is normally localized in a narrow frequency band, which thus restricts many of its applications. Here we present the simulation, implementation, and measurement of a broadband PIT metamaterial functioning in the terahertz regime. By integrating four U-shape resonators around a central bar resonator, a broad transparency window across a frequency range greater than 0.40 THz is obtained, with a central resonance frequency located at 1.01 THz. Such PIT metamaterials are promising candidates for designing slow light devices, highly sensitive sensors, and nonlinear elements operating over a broad frequency range.

A comprehensive SERS, SEM and EDX study of individual atmospheric PM2.5 particles in Chengdu, China.

Characterization of atmospheric fine particulate matter (PM2.5) in large cities has important implications for the study of their sources and formation mechanisms, as well as in developing effective measures to control air pollution. Herein, we report a holistic physical and chemical characterization of PM2.5 by combining surface-enhanced Raman scattering (SERS) with scanning electron microscopy (SEM) and electron-induced X-ray spectroscopy (EDX). PM2.5 particles were collected in a suburban area of Chengdu, a large city in China with a population over 21 million. A special SERS chip composed of inverted hollow Au cone (IHAC) arrays was designed and fabricated to allow direct loading of PM2.5 particles. SERS and EDX were used to reveal the chemical composition, and particle morphologies were analyzed from SEM images. SERS data of atmospheric PM2.5 indicated qualitatively the presence of carbonaceous particulate matter, sulfate, nitrate, metal oxides and bioparticles. The EDX showed the presence of the elements C, N, O, Fe, Na, Mg, Al, Si, S, K, and Ca in the collected PM2.5. Morphology analysis showed that the particulates were mainly in the form of flocculent clusters, spherical, regular crystal shaped or irregularly shaped particles. Our chemical and physical analyses also revealed that the main sources of PM2.5 are automobile exhaust, secondary pollution caused by photochemical reactions in the air, dust, emission from nearby industrial exhaust, biological particles, other aggregated particles, and hygroscopic particles. SERS and SEM data collected during three different seasons showed that carbon-containing particles are the principal sources of PM2.5. Our study demonstrates that the SERS based technique, when combined with standard physicochemical characterization methods, is a powerful analytical tool to determine the sources of ambient PM2.5 pollution. Results obtained in this work may be valuable to the prevention and control of PM2.5 pollution in air.

Surface-enhanced Raman scattering on gold nanotrenches and nanoholes.

Dependent effects on edge-to-edge distance and incidence polarization in surface-enhanced Raman Scattering (SERS) were studied in detection of 4-mercaptopyridine (4-MPy) molecules absorbed on gold nanotrenches and nanoholes. The gold nanostructures with controllable size and period were fabricated using electron-beam lithography. Large SERS enhancement in detection of 4-MPy molecules on both nanostructred substrates was observed. The SERS enhancement increased exponentially with decrease of edge-to-edge distance for both the nanotrenches and nanoholes while keeping the sizes of the nanotrenches and nanoholes unchanged. Investigation of polarization dependence showed that the SERS enhancement of nanotrenches was much more sensitive to the incidence polarizations than that of nanoholes.

Fabrication of metallic nanostructures of sub-20 nm with an optimized process of E-beam lithography and lift-off.

A process consisting of e-beam lithography and lift-off was optimized to fabricate metallic nanostructures. This optimized process successfully produced gold and aluminum nanostructures with features size less than 20 nm. These structures range from simple parallel lines to complex photonic structures. Optical properties of gold split ring resonators (SRRs) were characterized with Raman spectroscopy. Surface-Enhanced Raman Scattering (SERS) on SRRs was observed with 4-mercaptopyridine (4-MPy) as molecular probe and greatly enhanced Raman scattering was observed.

Identification and classification of particle contaminants on photomasks based on individual-particle Raman scattering spectra and SEM images.

Particle contamination of photo masks is a significant issue facing the micro-nanofabrication process. It is necessary to analyze the particulate matter so that the contamination can be effectively controlled and eliminated. In this study, Raman spectroscopy was used in combination with scanning electron microscopy with energy analysis (SEM-EDX) techniques to study the contamination of individual particles on the photomask. From Raman spectroscopic analysis, the Raman bands of particles mainly contributed to the vibrational modes of the elements C, H, O, and N. Their morphology and elemental composition were determined by SEM-EDX. The sizes of the particles are mostly less than 0.8 µm according to the SEM image analysis. Hierarchical clustering analysis (HCA) of the Raman spectra of particles have shown that the particles can be classified into six clusters which are assigned to CaCO3, hydrocarbon and hydrocarbon polymers, mixture of NH4NO3 and few (NH4)2SO4, mixtures metal oxides, D and G peaks of carbon, fluorescent and (NH4)2SO4 clusters. Finally, principal component analysis (PCA) was used to verify the correctness of the classification results. The identification and classification analysis of individual particles of photomask contamination illustrate the chemical components of the particles and provide insights into mask cleaning and how to effectively avoid particle contamination.

Surface-enhanced Raman scattering with gold-coated silicon nanopillars arrays: The influence of size and spatial order.

Nanopillars have been extensively explored as promising substrates for surface-enhanced Raman scattering (SERS) owing to their high sensitivity and excellent reproducibility. Most of the researches have been focused on the fabrication methods of nanopillars, and the dependences of SERS effects on geometrical size and spatial order are rarely investigated. In this work, SERS properties of nanopillars with different sizes (115-185 nm) and spatial orders (square and rhombus orders) have been studied. The work has shown that the nanopillars not only have high enhancement capability and high signal reproducibility, but also the enhancement is insensitive to the size and spatial orders. The measured enhancement factors (EFs) are 2.3-4.0 × 106 and signal reproducibility (relative standard deviation, RSD) are âˆ¼ 5.2%-6.9%, which are among the best of the similar SERS substrates reported. The variation of SERS intensity was as low as approximately 4.8% with the variation of pillar size from 115, 135, 145, to 160 nm. The insensitiveness and high reproducibility have been ascribed to the combined excitation of localized surface plasmon resonance (LSPR) and propagating surface plasmons (SPPs) of the nanopillars. Optical properties of the nanopillars are studied both experimentally and numerically to understand the physics behind the SERS performance.

Detecting small lung tumors in mouse models by refractive-index microradiology.

Refractive-index (phase-contrast) radiology was able to detect lung tumors less than 1 mm in live mice. Significant micromorphology differences were observed in the microradiographs between normal, inflamed, and lung cancer tissues. This was made possible by the high phase contrast and by the fast image taking that reduces the motion blur. The detection of cancer and inflammation areas by phase contrast microradiology and microtomography was validated by bioluminescence and histopathological analysis. The smallest tumor detected is less than 1 mm(3) with accuracy better than 1 × 10(-3) mm(3). This level of performance is currently suitable for animal studies, while further developments are required for clinical application.

Large-Scale, Bandwidth-Adjustable, Visible Absorbers by Evaporation and Annealing Process.

Optical absorbers have received a significant amount of attention due to their wide range of applications in biomedical sensing, solar cell, photon detection, and surface-enhanced Raman spectroscopy. However, most of the optical absorbers are fabricated with high-cost sophisticated nanofabrication techniques, which limit their practical applications. Here, we introduce a cost-effective method to fabricate an optical absorber by using a simple evaporation technique. The absorbers are composed of evaporated nanoparticles above a silver (Ag) mirror separated by a silicon oxide layer. Experimental results show over 77% absorption in the wavelength range from 470 to 1000 nm for the absorber with isolated Ag nanoparticles on the top. The performance of the absorber is adjustable with the morphology and composition of the top-layer nanoparticles. When the top layer was hybrid silver-copper (Ag-Cu) nanoparticles (NPs), the absorption exceeding 90% of the range of 495-562 nm (bandwidth of 67 nm) was obtained. In addition, the bandwidth for over 90% absorption of the Ag-Cu NP absorber was broadened to about 500 nm (506-1000 nm) when it annealed at certain temperatures. Our work provides a simple way to make a highly efficient absorber of a large area for the visible light, and to transit absorption from a narrow band to broadband only by temperature treatment.

Origins of PM10 determined by the micro-proton induced X-ray emission spectra of single aerosol particles.

The micro-proton induced X-ray emission (micro-PIXE) spectrum of a single aerosol particle (SAP) was considered as its fingerprint for tracing its origin. A proton microprobe was used to extract fingerprints of SAPs. Environmental monitoring samples of PM(10) were collected from a heavy industrial area of Shanghai and were analyzed by proton microprobe for finding their pollution sources. In order to find the sources of SAPs collected from environmental monitoring sites, a fingerprint database of SAPs collected from various pollution sources was established. The origins of samples collected through environmental monitoring were identified by comparison of the micro-PIXE spectra of SAPs with those of SAPs in the fingerprint database using a pattern recognition technique. The results of this study show that most of the measured PM(10) is derived from metallurgic industry, soil dust, coal combustion, automobile exhaust, and motorcycle exhaust. The study also shows that the proton microprobe is an ideal tool for the analysis of SAPs. The unidentified particles of PM(10) are classified into seven classes by hierarchical cluster analysis based on the element peak intensity in the spectra.

Characterization of PM(2.5) in the ambient air of Shanghai City by analyzing individual particles.

PM(2.5) samples were collected simultaneously at three representative areas (central city, industrial area and clean air suburban) of Shanghai City. Their morphologies and elemental compositions were determined by scanning electron microscopy coupled with energy analysis (SEM-EDX). The particles were classified into four groups based on morphology and elemental composition. Soot aggregates and spherical fly ash particles were the two dominant types and they were identified as originating from automobile exhaust, metallurgical industry and coal combustion. The size distribution of the particles showed that most had diameters in the range of 0.2-1.4 microm. Individual particles were measured by synchrotron radiation micro-beam X-ray fluorescence (micro-SXRF) and the micro-SXRF spectra were obtained. Pattern recognition techniques, which took the micro-SXRF spectrum of a single aerosol particle as its fingerprint, were used to identify the origins of the particles. Seven source types were identified. They were: metallurgical industry, vehicle exhaust, soil dust, coal combustion, diesel exhaust, oil combustion and motorcycle exhaust. Metallurgical industry, automobile exhaust, and coal combustion were recognized to be the main pollution sources of PM(2.5) in the air of Shanghai City.

Anomalous Surface Wave Launching by Handedness Phase Control.

Anomalous launch of a surface wave with different handedness phase control is achieved in a terahertz metasurface based on phase discontinuities. The polarity of the phase profile of the surface waves is found to be strongly correlated to the polarization handedness, promising polarization-controllable wavefront shaping, polarization sensing, and environmental refractive-index sensing.

Enhanced extraordinary optical transmission (EOT) through arrays of bridged nanohole pairs and their sensing applications.

Extraordinary optical transmission (EOT) through arrays of gold nanoholes was studied with light across the visible to the near-infrared spectrum. The EOT effect was found to be improved by bridging pairs of nanoholes due to the concentration of the electromagnetic field in the slit between the holes. The geometrical shape and separation of the holes in these pairs of nanoholes affected the intensity of the transmission and the wavelength of resonance. Changing the geometrical shapes of these nanohole pairs from triangles to circles to squares leads to increased transmission intensity as well as red-shifting resonance wavelengths. The performance of bridged nanohole pairs as a plasmonic sensor was investigated. The bridged nanohole pairs were able to distinguish methanol, olive oil and microscope immersion oil for the different surface plasmon resonance in transmission spectra. Numerical simulation results were in agreement with experimental observations.