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Surface-Enhanced X-Ray Fluorescence

Surface-enhanced x-ray fluorescence (SEn-XRF) spectroscopy is a form of surface- enhanced spectroscopy that was conceived as a means of obtaining greater sensitivity in x-ray fluorescence (XRF) spectroscopy. As such, SEn-XRF spectroscopy joins the ranks of such other, longer-wavelength surface-enhanced spectroscopies as those based on surface-enhanced Raman scattering (SERS), surface-enhanced resonance Raman scattering (SERRS), and surfaceenhanced infrared Raman absorption (SEIRA), which have been described in previous NASA Tech Briefs articles. XRF spectroscopy has been used in analytical chemistry for determining the elemental compositions of small samples. XRF spectroscopy is rapid and quantitative and has been applied to a variety of metal and mineralogical samples. The main drawback of XRF spectroscopy as practiced heretofore is that sensitivity has not been as high as required for some applications. In SEn-XRF as in the other surface-enhanced spectroscopies, one exploits several interacting near-field phenomena, occurring on nanotextured surfaces, that give rise to local concentrations of incident far-field illumination. In this case, the far-field illumination comes from an x-ray source. Depending on the chemical composition and the geometry of a given nanotextured surface, these phenomena could include the lightning-rod effect (concentration of electric fields at the sharpest points on needlelike surface features), surface plasmon resonances, and grazing incidence geometric effects. In the far field, the observable effect of these phenomena is an increase in the intensity of the spectrum of interest - in this case, the x-ray fluorescence spectrum of chemical elements of interest that may be present within a surface layer at distances no more than a few nanometers from the surface.

Anderson, Mark↗

NASA Tech Briefs, January 2005

Topics covered include: Fiber-Optic Sensor Would Monitor Growth of Polymer Film; Sensors for Pointing Moving Instruments Toward Each Other; Pd/CeO2/SiC Chemical Sensors; Microparticle Flow Sensor; Scattering-Type Surface-Plasmon-Resonance Biosensors; Diode-Laser-Based Spectrometer for Sensing Gases; Improved Cathode Structure for a Direct Methanol Fuel Cell; X-Band, 17-Watt Solid-State Power Amplifier; Improved Anode for a Direct Methanol Fuel Cell; Tools for Designing and Analyzing Structures; Interactive Display of Scenes with Annotations; Solving Common Mathematical Problems; Tools for Basic Statistical Analysis; Program Calculates Forces in Bolted Structural Joints; Integrated Structural Analysis and Test Program; Molybdate Coatings for Protecting Aluminum Against Corrosion; Synthesizing Diamond from Liquid Feedstock; Modifying Silicates for Better Dispersion in Nanocomposites; Powder-Collection System for Ultrasonic/Sonic Drill/Corer; Semiautomated, Reproducible Batch Processing of Soy; Hydrogen Peroxide Enhances Removal of NOx from Flue Gases; Subsurface Ice Probe; Real-Time Simulation of Aeroheating of the Hyper-X Airplane; Using Laser-Induced Incandescence To Measure Soot in Exhaust; Method of Real-Time Principal-Component Analysis; Insect-Inspired Flight Control for Unmanned Aerial Vehicles; Domain Compilation for Embedded Real-Time Planning; Semantic Metrics for Analysis of Software; Simulation of Laser Cooling and Trapping in Engineering Applications; Large Fluvial Fans and Exploration for Hydrocarbons; Doping-Induced Interband Gain in InAs/AlSb Quantum Wells; Development of Software for a Lidar-Altimeter Processor; Upgrading the Space Shuttle Caution and Warning System; and Fractal Reference Signals in Pulse-Width Modulation.

Source record↗

NASA Tech Briefs, April 2013

Topics covered include: Fully Integrated, Miniature, High-Frequency Flow Probe Utilizing MEMS Leadless SOI Technology; Nanoscale Surface Plasmonics Sensor With Nanofluidic Control; Advanced Dispersed Fringe Sensing Algorithm for Coarse Phasing Segmented Mirror Telescopes; Neural Network Back-Propagation Algorithm for Sensing Hypergols; Bulk Moisture and Salinity Sensor; Change-Based Satellite Monitoring Using Broad Coverage and Targetable Sensing; Circularly Polarized Microwave Antenna Element with Very Low Off-Axis Cross-Polarization; Ultra-Low Heat-Leak, High-Temperature Superconducting Current Leads for Space Applications; Flash Cracking Reactor for Waste Plastic Processing; An Automated Safe-to-Mate (ASTM) Tester; Wireless Chalcogenide Nanoionic-Based Radio-Frequency Switch; Compute Element and Interface Box for the Hazard Detection System; DOT Transmit Module; Composite Aerogel Multifoil Protective Shielding; Li-Ion Electrolytes with Improved Safety and Tolerance to High-Voltage Systems; Polymer-Reinforced, Non-Brittle, Lightweight Cryogenic Insulation; Controlled, Site-Specific Functionalization of Carbon Nanotubes with Diazonium Salts; Regenerable Sorbent for CO2 Removal; Sprayable Aerogel Bead Compositions With High Shear Flow Resistance and High Thermal Insulation Value; Lexan Linear Shaped Charge Holder with Magnets and Backing Plate; Robotic Ankle for Omnidirectional Rock Anchors; Wind, Wave, and Tidal Energy Without Power Conditioning; An Active Heater Control Concept to Meet IXO Type Mirror Module Thermal-Structural Distortion Requirement; Waterless Clothes-Cleaning Machine; Integrated Electrical Wire Insulation Repair System; LVGEMS Time-of-Flight Mass Spectrometry on Satellites; Surface Inspection Tool for Optical Detection of Surface Defects; Per-Pixel, Dual-Counter Scheme for Optical Communications; Certification-Based Process Analysis; Surface Navigation Using Optimized Waypoints and Particle Swarm Optimization; Smart-Divert Powered Descent Guidance to Avoid the Backshell Landing Dispersion Ellipse; Estimating Foreign-Object-Debris Density from Photogrammetry Data; Adaptive Sampling of Spatiotemporal Phenomena with Optimization Criteria; Building a 2.5D Digital Elevation Model From 2D Imagery; Eyes on the Earth 3D; Target Trailing With Safe Navigation for Maritime Autonomous Surface Vehicles; Adams-Based Rover Terramechanics and Mobility Simulator - ARTEMIS; ISTP CDF Skeleton Editor; Uplink Summary Generator (ULSGEN) Version 1.0; Robotics On-Board Trainer (ROBoT); Software Engineering Tools for Scientific Models; Automatic Data Filter Customization Using a Genetic Algorithm; Tracker Toolkit; Towards Efficient Scientific Data Management Using Cloud Storage; On a Formal Tool for Reasoning About Flight Software Cost Analysis; A Nanostructured Composites Thermal Switch Controls Internal and External Short Circuit in Lithium Ion Batteries; Spacecraft Crew Cabin Condensation Control; and Functional Near-Infrared Spectroscopy Signals Measure Neuronal Activity in the Cortex.

Source record↗

Electride Mediated Surface Enhanced Raman Scattering (SERS)

An electride may provide surface enhanced Raman scattering (SERS). The electride, a compound where the electrons serve as anions, may be a ceramic electride, such as a conductive ceramic derived from mayenite, or an organic electride, for example. The textured electride surface or electride particles may strongly enhance the Raman scattering of organic or other Raman active analytes. This may also provide a sensitive method for monitoring the chemistry and electronic environment at the electride surface. The results are evidence of a new class of polariton (i.e., a surface electride-polariton resonance mechanism) that is analogous to the surface plasmon-polariton resonance that mediates conventional SERS.

Anderson, Mark S.↗

Method of Stamping Surface-Enhance Raman Spectroscopy for Label-Free, Multiplexed, Molecular Sensing and Imaging

The present disclosure relates the use of a stamping surface enhanced Raman scattering (S-SERS) technique with nanoporous gold disk (NPGD) plasmonic substrates to produce a label-free, multiplexed molecular sensing and imaging technique. A NPGD SERS substrate is stamped onto a surface containing one or more target molecules, followed by SERS measurement of the target molecules located between the surface and SERS substrate. The target molecules may be deposited on the surface, which may be a carrier substrate such as polydimethylsiloxane (PDMS).

Shih, Wei-Chuan↗

Single-dish and VLBI Observations of Cygnus X-3 During the 2016 Giant Flare Episode

In 2016 September, the microquasar Cygnus X-3 underwent a giant radio flare, which was monitored for 6 d with the Medicina Radio Astronomical Station and the Sardinia Radio Telescope. Long observations were performed in order to follow the evolution of the flare on an hourly scale, covering six frequency ranges from 1.5 to 25.6 GHz. The radio emission reached a maximum of 13.2 +/- 0.7 Jy at 7.2 GHz and 10 +/- 1 Jy at 18.6 GHz. Rapid flux variations were observed at high radio frequencies at the peak of the flare, together with rapid evolution of the spectral index: α steepened from 0.3 to 0.6 (with Sν ∝ ν −α) within 5 h. This is the first time that such fast variations are observed, giving support to the evolution from optically thick to optically thin plasmons in expansion moving outward from the core. Based on the Italian network (Noto, Medicina and SRT) and extended to the European antennas (Torun, Yebes, Onsala), very long baseline interferometry (VLBI) observations were triggered at 22 GHz on five different occasions, four times prior to the giant flare, and once during its decay phase. Flux variations of 2 h duration were recorded during the first session. They correspond to a mini-flare that occurred close to the core 10 d before the onset of the giant flare. From the latest VLBI observation we infer that 4 d after the flare peak the jet emission was extended over 30 mas.

Egron, E.↗

Tunable mid-wave infrared spectral filters based on GexSbyTez for multispectral imaging

The mid-wave infrared (MWIR) spectrum contains a wealth of invaluable information including the spectral ‘fingerprint’ of many chemical species and has applications in remote sensing and astronomical imaging. Traditionally, filtering for the MWIR is achieved by means of passive multilayer interference (dichroic) filters, Fabry-Perot-based micro-electro-mechanical system (MEMS) filters, liquid crystal tunable filters, and focal plane array (FPA) filters. For accurate multispectral imaging applications, these approaches suffer from various limitations such as: having moving parts; exhibiting slow response times, and; having limited spectral bandwidth / resolution. Recently, there has been significant interest toward ‘active’ spectral imaging technologies, whereby the ability to provide electrically tunable narrowband filtering—spanning the entire MWIR—is highly desirable. In this work we introduce a new spectral imaging technology, namely actively tunable optical transmission filters using the phase-change material (PCM) GexSbyTez (GST). The GST exhibits a large, reversible change in its refractive index across the MWIR upon a phase transition (from amorphous to crystalline). This refractive index modulation governs the filter’s optical characteristics. Through an optical stimulus or applied voltage—which changes the GST state from amorphous to crystalline—one can actively tune the filter with MHz speed. We incorporate GST into optimized guided mode resonance (GMR) and plasmonic nanohole array (PNA) device architectures, enabling <10nm spectral resolution and tunable operation across 3~5µm. Our proposed PCM-MWIR filter will be able to extract the maximum amount of ‘useful’ information within the atmosphere for remote Earth sensing measurements at operational speeds orders of magnitude faster than current airborne-based sensors. Moreover, it may enable affordable SmallSat-based MWIR instrumentation which is complimentary to other observation systems. The MISSE (Materials International Space Station Experiment-Flight Facility) experiment has been proposed as a testbed for a PCM-based tunable MWIR filter module to allow exposure of the module to the low Earth orbit space environment. This will provide valuable data regarding the robustness of the filter to withstand the radiation and atomic oxygen environment and allow assessment of the technology for use in space applications.

Kim, Hyun Jung↗

Crowd-Sourced Technology Challenge for Improving Visual Color Detection of Hydrazine and Monomethylhydrazine Vapors in Spacecraft Environments

NASA currently uses a visual colorimetric detection method for potential hydrazine, monomethylhydrazine (MMH), or unsymmetrical dimethylhydrazine (UDMH) contamination in the International Space Station. Astronauts exposed to propellants or their residues during extravehicular activities may transfer contaminants into the airlock. The colorimetric detection method employs the Contamination Detection Kit (CDK), which uses a potassium tetrachloroaurate redox reaction with the propellant hydrazine vapors and a color comparison card to determine airborne concentrations. Seeking ideas for improvement, the NASA Tournament Lab (NTL) crowdsourced a way to tackle the challenge of detecting hydrazine and MMH vapors using colorimetric detection methods. This Rid the Rocket competition drew over 200 participants and 20 submissions from around the world proposing innovative ways to develop a new chemical colorimetric detection method for hydrazine and MMH vapors on spacecraft. Using a phased approach to evaluate contestants, NASA eventually narrowed the field to five finalists from the United States, Romania, Taiwan, and India. Concept papers and hardware submissions were judged on feasibility, creativity, and ability to detect hydrazine and MMH vapors before being sent to the NASA White Sands Test Facility for laboratory evaluation. Finalists employed variations of sampling methods and color-detection chemistry using a variety of sampling pumps and indicator pads or solutions—including those employing potassium or hydrogen tetrachloroaurate, para -dimethylaminobenzaldehyde (PDAB), and modifiers including sodium metasilicate and cetyltrimethylammonium bromide—to enhance gold nanoparticle formation and surface plasmon resonance (SPR) resulting in visual blue to purple color development. This paper presents a summary of the crowdsourced submissions and results of laboratory testing.

Crowd-Sourced↗

The Trajectory of Recent Solid State Fusion Results

Both NASA and Google have explored and funded Low Energy Nuclear Reaction (LENR) aka Solid-State Fusion or Lattice Confinement Fusion (LCF) research. NASA has funded efforts since 1989, and Google Research began in 2014. Google, and researchers initially-funded by Google, published significant scientific papers in Nature, Nature Communications and the Journal of Applied Physics. NASA began a significant set of LENR-triggering programs in 2012 resulting in papers in Physical Review C, the Journal of Electroanalytical Chemistry and the Journal of Condensed Matter Nuclear Science. Both NASA and Google engaged researchers across fields of nuclear physics, chemistry, electrochemistry, material science and more. NASA built upon early novel gas pumping experiments then followed the patented work of the US Navy SPAWAR (US8,419,919, “System and Method to Generate Particles”) and experiments with the Naval Surface Warfare Centers. Google supported researchers at Lawrence Berkeley National Laboratory (LBNL), the University of British Columbia (UBC), MIT and others. This resulted in patent applications and two granted patents (US10264661B2, “Target structure for enhanced electron screening” and US10566094B2 “Enhanced electron screening through plasmon oscillations”). These separate efforts, unknown to the researchers at the time, provided the impetus for the DoE ARPA-E LENR program followed by the DARPA DSO “Mechanisms for Amplification of Fusion Reaction Rates in Solids” (MARRS) program. This document briefly describes the overlapping NASA and Google Research efforts in plasma loading and electron screening emphasizing the results of the latest paper in Nature Communications. The papers and patents cited are listed.

electron screening↗

Impact of Surface Enhanced Raman Spectroscopy in Catalysis

Catalysis stands as an indispensable cornerstone of modern society, underpinning the production of over 80% of manufactured goods and driving over 90% of industrial chemical processes. As the demand for more efficient and sustainable processes grows, better catalysts are needed. Understanding the working principles of catalysts is key, and over the last 50 years, surface-enhanced Raman Spectroscopy (SERS) has become essential. Discovered in 1974, SERS has evolved into a mature and powerful analytical tool, transforming the way in which we detect molecules across disciplines. In catalysis, SERS has enabled insights into dynamic surface phenomena, facilitating the monitoring of the catalyst structure, adsorbate interactions, and reaction kinetics at very high spatial and temporal resolutions. This review explores the achievements as well as the future potential of SERS in the field of catalysis and energy conversion, thereby highlighting its role in advancing these critical areas of research.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

De Nive Quinquangula: Pentagonal Snowflake Metal Nanocrystals as an Example of Emergence Phenomenon in Nanotechnology Complex Systems

The formation of snowflakes (SFL) is one of the most captivating phenomena in nature. The fabrication of multimetallic gold (Au) nanoparticles containing copper (Cu) and iron (Fe) is reported, which adopt snowflake-like morphology after nanoparticle aggregation. The synthesis of these snowflake-like Au microcrystals occurs mainly by kinetic control. In this process, a surfactant-assisted salt reduction method is employed on a heated substrate. Here, the metal salts react within seconds to form nanoparticles. This process results in a hierarchical structure with pseudo-pentagonal symmetry and chiroptical activity. We discuss how large superstructures emerge from nanoparticle aggregation, resembling natural snowflakes. However, unlike ice snowflakes, which exhibit hexagonal symmetry, the Au snowflakes display pentagonal symmetry. It is proposed that the formation of these snowflake-like microcrystals is the result of the complexity involved in the crystal growth process and represents an example of the phenomenon of emergence, which has become very significant in several fields of modern science, including physics, biology, chemistry, economics, philosophy, and poetry. The term emergent is used to evoke the collective behavior of a large number of microscopic constituents that is qualitatively different than the behaviors of the individual constituents.

36 MATERIALS SCIENCE↗

Solution-Processed Temperature-Adaptive Radiative Paint as a Thermal Imaging Sensitizer

Thermography detects mid-infrared radiation from surfaces based on the Stefan-Boltzmann law, mapping surface temperatures and potentially revealing subsurface thermal activity. Recent developments offer an alternative strategy to traditional camera-based improvements: a thermal imaging sensitizer (TIS) coating whose emissivity increases sharply with local temperature, amplifying small thermal variations into high-contrast signals. Existing TIS structures are nanofabricated solid membranes and face significant challenges in fabrication complexity. Here, in this study, we present a solution-processed, liquid form of TIS, termed temperature-adaptive radiative paint (TARP), to address these limitations. TARP offers drastically reduced fabrication costs, scalability to large areas, applicability to curved surfaces, and an extended operating temperature range, while maintaining the function of temperature amplification. Application of TARP enhances small temperature contrast by more than 3 times, substantially improving ambient thermography and enabling broader applications such as detection of structural defects and hot spots in electronic components.

paint↗

Crystallization of the Transdimensional Electron Liquid

Wigner crystallization of free electrons at room temperature has been explored theoretically for a new class of metallic ultrathin (transdimensional) materials whose properties can be controlled by their thickness. Our calculations of the melting surface, critical electron density and temperature explain consistently the experimental data reported previously. We show that by reducing the material thickness one can Wigner-crystallize free electrons at room temperature to get them pinned onto a two-dimensional triangular lattice of a supersolid inside of the crystalline material. Such a solid melts and freezes reversibly with increase and decrease of electron doping or temperature, whereby its resistivity behaves opposite to the free electron gas model predictions.

Wigner crystal↗

Solution-Processed Ultrafast, Room-Temperature Single-Photon Source at 1550 nm

Single photons are cornerstones of quantum technologies. The need for an ultrafast, bright, and stable photon source emitting in the telecom-band at ∼1550 nm, ideally operating at room temperature, has resulted in a decades-long quest. However, to date, telecom sources are hampered by inherently long radiative lifetimes that severely limit brightness and speed, material instability, or the need for cryogenic operation. Here, in this study, stable colloidal PbS/CdS quantum dots emitting at 1550 nm (C-band) or 1350 nm (O-band) are embedded in a solution-synthesized nanoparticle-on-mirror cavity. Single cavity-coupled quantum dots experience extreme Purcell factors up to 10,700, resulting in ultrafast emission lifetimes of 65 ps, along with near-complete blinking suppression. As a result, 12 million single photons are emitted per second affording a single photon source at 1550 nm that is more than two orders of magnitude brighter than previously possible at room-temperature. These telecom-band single photon sources are solution-processable and lithography-free and may leverage mature colloidal fabrication technologies for future quantum applications.

36 MATERIALS SCIENCE↗

Ultrafast and Highly Collimated Radially Polarized Photons at Room Temperature from a Colloidal Quantum Dot Coupled to a Hybrid Nanoantenna

To harness the potential of radially polarized photons for classical and quantum communication applications, we demonstrate an on-chip, room-temperature device, which generates highly directional radially polarized photons at very high rates. The photons are emitted from a giant CdSe/CdS colloidal quantum dot (gQD) accurately positioned at the tip of a metal nanocone centered inside a hybrid metal-dielectric bullseye antenna. We show that due to the large and selective Purcell enhancement specifically for the out-of-plane optical dipole of the gQD, the emitted photons can have a very high degree of radial polarization (>93%), based on a quantitative metric. Our study emphasizes the importance of accurate gQD positioning for optimal radial polarization purity through extensive experiments and simulations, which contribute to the fundamental understanding of radial polarization in nanostructured devices and pave the way for implementation of such systems in practical applications using structured quantum light.

36 MATERIALS SCIENCE↗

Roadmap for Photonics with 2D Materials

Triggered by advances in atomic-layer exfoliation and growth techniques, along with the identification of a wide range of extraordinary physical properties in self-standing films consisting of one or a few atomic layers, two-dimensional (2D) materials such as graphene, transition metal dichalcogenides (TMDs), and other van der Waals (vdW) crystals now constitute a broad research field expanding in multiple directions through the combination of layer stacking and twisting, nanofabrication, surface-science methods, and integration into nanostructured environments. Photonics encompasses a multidisciplinary subset of those directions, where 2D materials contribute remarkable nonlinearities, long-lived and ultraconfined polaritons, strong excitons, topological and chiral effects, susceptibility to external stimuli, accessibility, robustness, and a completely new range of photonic materials based on layer stacking, gating, and the formation of moiré patterns. These properties are being leveraged to develop applications in electro-optical modulation, light emission and detection, imaging and metasurfaces, integrated optics, sensing, and quantum physics across a broad spectral range extending from the far-infrared to the ultraviolet, as well as enabling hybridization with spin and momentum textures of electronic band structures and magnetic degrees of freedom. The rapid expansion of photonics with 2D materials as a dynamic research arena is yielding breakthroughs, which this Roadmap summarizes while identifying challenges and opportunities for future goals and how to meet them through a wide collection of topical sections prepared by leading practitioners.

2D materials↗

Broadband nonreciprocal thermal emissivity and absorptivity

A body that violates Kirchhoff’s law of thermal radiation exhibits an inequality in its spectral directional absorptivity and emissivity. Achieving such an inequality is of fundamental interest as well as a prerequisite for achieving thermodynamic limits in photonic energy conversion and radiative cooling. Thus far, inequalities in the spectral directional emissivity and absorptivity have been limited to narrow spectral resonances, or wavelengths well beyond the infrared regime4. Bridging the gap from basic demonstrations to practical applications requires control over a broad spectral range of the unequal spectral directional absorptivity and emissivity. In this work, we demonstrate broadband nonreciprocal thermal emissivity and absorptivity by measuring the thermal emissivity and absorptivity of gradient epsilon-near-zero InAs layers of subwavelength thicknesses (50 nm and 150 nm) with an external magnetic field. The effect occurs in a spectral range (12.5–16 μm) that overlaps with the infrared transparency window and is observed at moderate (1 T) magnetic fields.

42 ENGINEERING↗