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At least 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Surface plasmon polariton pulse shaping via two-dimensional Bragg grating pairs

Abstract We demonstrate control over the spatial and temporal properties of surface plasmon polaritons (SPPs) launched from nanohole arrays in silver. The arrays provide wave vector matching to allow the conversion of free-space photons into counter-propagating SPPs. SPPs launched from multiple arrays interfere at well-defined spatial positions, and the interference fringes form an all-SPP periodic nano-optical grating which evolves in space and time as the SPPs propagate. The spatio-temporal characteristics of the optical grating can be tuned through various nanohole array parameters such as tilt angle, separation, and array width. In addition, we examine multiperiodic arrays (MPAs) consisting of arrays with different pitches placed adjacent to one another. This platform allows the temporal interference of SPPs with different central wavelengths to be tailored through the MPA geometric and structural parameters. The temporal interference serves as an encoded signal, whereby the frequency components can be controlled by the array properties.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS1975

Electromagnetic wave energy conversion research

Known electromagnetic wave absorbing structures found in nature were first studied for clues of how one might later design large area man-made radiant-electric converters. This led to the study of the electro-optics of insect dielectric antennae. Insights were achieved into how these antennae probably operate in the infrared 7-14um range. EWEC theoretical models and relevant cases were concisely formulated and justified for metal and dielectric absorber materials. Finding the electromagnetic field solutions to these models is a problem not yet solved. A rough estimate of losses in metal, solid dielectric, and hollow dielectric waveguides indicates future radiant-electric EWEC research should aim toward dielectric materials for maximum conversion efficiency. It was also found that the absorber bandwidth is a theoretical limitation on radiant-electric conversion efficiency. Ideally, the absorbers' wavelength would be centered on the irradiating spectrum and have the same bandwith as the irradiating wave. The EWEC concept appears to have a valid scientific basis, but considerable more research is needed before it is thoroughly understood, especially for the complex randomly polarized, wide band, phase incoherent spectrum of the sun. Specific recommended research areas are identified.

Bailey, R. L.↗
DOE OSTI2023

Intensified Tpx3Cam, a fast data-driven optical camera with nanosecond timing resolution for single photon detection in quantum applications

Here we describe a fast data-driven optical camera, Tpx3Cam, with nanosecond scale timing resolution and 80 Mpixel/sec throughput. After the addition of intensifier, the camera is single photon sensitive with quantum efficiency determined primarily by the intensifier photocathode. The single photon performance of the camera was characterized with results on the gain, timing resolution and afterpulsing reported here. The intensified camera was successfully used for measurements in a variety of applications including quantum applications. As an example of such application, which requires simultaneous detection of multiple photons, we describe registration of photon pairs from the spontaneous parametric down-conversion source in a spectrometer. We measured the photon wavelength and timing with respective precisions of 0.15 nm and 3 ns, and also demonstrated that the two photons are anti-correlated in energy.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2023

Laboratory-Scale Coal-Derived Graphene Process (Final Report)

The Energy & Environmental Research Center (EERC) conducted a laboratory-scale coal-derived graphene (CDG) project focused on developing a technological process for making graphene from four U.S. domestic coal or coal wastes, including lignite from North Dakota, subbituminous coal from Wyoming, bituminous coal from Utah, and anthracite from Pennsylvania. The project was divided into two performance or budget periods (BPs), with BP1 comprising the up-front laboratory experiments to make graphene materials from coal beginning on May 1, 2020, to April 30, 2022. BP2 was conducted from May 1, 2022, to April 30, 2023, and was focused on analyzing the CDG process economic feasibility and the technical gaps for technological scale-up and commercialization. During this project, a few different coal-derived high-value products have been demonstrated, including graphite, graphene oxide (GO), reduced graphene oxide (rGO), and graphene quantum dots (GQDs). A new graphite microstructure was discovered and named “croissant graphite” because of the exterior morphological and textural resemblance to croissant food items sold in commercial groceries stores. The new graphite structure and the associated preparation from coal or coal waste feedstocks has been the subject of a U.S. patent application. The systematic experimental processes involving coal cleaning, upgrading, and conversion to high-value carbon products culminated into a developed upgraded coal-to-products (UCP) technology that is being pursued for potential fast-track commercialization, if funding is available. It is envisioned that commercialization of the UCP technology would increase consumption of U.S. domestic coals or coal wastes to make environmentally sustainable high-value products for the electronics industry, high-energy-storage applications, and clean energy technologies such as electric vehicle (EV) lithium-ion batteries (LIBs), for which graphite has become a critical mineral commodity. Croissant graphite microstructures, when observed by field emission scanning electron microscopy (FESEM), display wavy surface morphology and often grow from a base that is made of graphitized particles with honeycomb-like layers, which are believed to be graphene layers. While more studies are needed to fully ascertain the mechanisms of the croissant graphite microstructure formation, it is postulated that their growth may begin from curling of the graphene sheets into ribbon-like structures, and continuous growth and densification of the ribbon-like structures forms croissant microstructures. Additional studies are ongoing to evaluate the electrochemical performance of croissant graphite for LIB applications and to determine the experimental conditions necessary to tune on/off croissant formation so that it can be either optimized or suppressed depending on performance evaluation results. In addition to the discovery of croissant graphite, the graphitization process from the four coal ranks in general was successful. X-ray diffraction (XRD) analysis showed that the degree of graphitization (DoG) ranged from 12% to 80% in an early sample set, and further optimization on lignite coal produces a DoG of about 92%, which was spectacular to see as lignite is the lowest-rank coal. Thus, it is expected that the graphitization performance for higher-rank coals will be similar or better when optimized as well. The coal-derived graphite was used to make GO and rGO. Analytical characterization, e.g., by methods such as Raman spectroscopy, XRD, Fourier transform infrared (FTIR) spectroscopy and FESEM, showed that the sequence of converting the coal to graphite, exfoliating it to GO, and then chemically reducing the GO to rGO was successful. Although coal naturally contains aromatic compounds and some relatively small-sized condensed aromatic units, it does not contain graphene sheets. In the UCP process, the aromatic domains in the coals, particularly low-rank coals, are concentrated and condensed further into graphene sheets, which are ordered into a 3D stack during graphitization. The synthesized graphite is then unpacked by methods such as exfoliation to various graphene products. GQDs were synthesized from all four coal types, and their optical properties were demonstrated to be tunable by the coal precursor preprocessing treatments. In all four coal types, enhanced optical properties were observed for the produced GDQs with incremental improvements made to the coal precursors. GQDs produced from raw coal samples displayed lower ultraviolet–visible (UV–Vis) spectroscopy absorbance intensity compared to those obtained from cleaned and upgraded coal residues. The photoluminescence (PL) intensities also varied with pretreatment conditions and with the concentration of GQDs in aqueous solutions. GQDs obtained from anthracite show longer emission wavelengths and can be excited by visible light as opposed to GQDs derived from the other coal ranks. UV fluorescence 3D maps and spectra revealed that the emission wavelength at which the GQDs solutions display the highest intensity was slightly redshifted based on the coal precursor pretreatments. In low-rank coal (lignite and subbituminous) samples, two clusters were observed in the maps for GQDs, which may suggest that there are potentially two types of fluorophores in solution or two main size populations. The ability to tune the properties of GQDs based on processing methods can be exploited to make GQDs for various optical display or optoelectronics applications. The results also highlight the importance of removing coal-borne impurities to improve the quality of the coal precursor for preparation of graphene products. Coal and/or coal wastes preprocessing methods were developed and applied to clean and upgrade the coal precursors prior to graphitization and subsequent conversion to graphene products. The preprocessing methods involve high specific-gravity separations, mineral acid cleaning (no hydrofluoric acid), and subsequent upgrading by reducing the coal-borne heteroatom (nitrogen, sulfur, and oxygen) content using proprietary chemical agents. Analytical characterization revealed that the preprocessing steps were successful, with ash reductions that range from 38% to 80% and residual ash content that was below the 5 wt% initial target. Based on proximate and ultimate analysis, the heteroatom reduction reactions produced upgraded coal residues with the oxygen content reduced by 8% to 24%, with additional reductions in the nitrogen and sulfur contents. An initial assessment of the waste streams from the UCP process shows very small to negligible environmental impact due to CO 2 , NO x , and SO x because most process steps are performed under inert atmosphere with argon. Consequently, reactive oxygen environments that tend to create these species are avoided. The inorganic and potentially hazardous species are released into aqueous waste streams that are easy to handle for proper disposal. The liquid waste streams were found to contain low-level concentrations of rare-earth elements (REEs), which could be concentrated and recovered as value-added by-products. Additionally, the volatile and gaseous fractions from carbonization and heat treatment contain useful organic compounds that can also be recovered as potential valuable by-products. Thus, the UCP technology is considered an environmentally sustainable and promising emerging technology for making high-value products from coal and coal wastes, with potential additional value-added by-products. Analysis of potential markets for the coal-derived carbon products shows a strong demand in both niche market sectors and across a wide variety of other industrial sectors. Graphite is currently considered a critical mineral commodity that has a large and growing demand in the LIB industry for EV applications. Based on data from Fortune Business Insights (2022) and Marketwatch (2023) reports, the average global graphite market is projected to reach about 33 billion by 2028, growing at a compound annual growth rate (CAGR) of about 7%, with much of this growth expected to be in the LIB industry. GO and rGO have strong market potentials in various application areas, such as coatings for anticorrosion, anti-icing, and antimicrobial protection, thermal barriers, wear resistance, sensors, additive manufacturing such as 3D inks, and others. GQDs are the emerging key player in the bioimaging, photovoltaics, and light-emitting diodes (LEDs) applications, with the potential to replace traditional semiconductor quantum dots (SQDs), which are based on metallic systems that are more toxic and more expensive. Biomedical applications of GQDs are becoming more attractive because of low to no toxicity and extremely low cost compared to SQDs. The major challenges for scale-up and commercialization of coal-derived carbon products such as graphene vary from the inherent attributes of graphene itself to reluctance to accept graphene in new manufacturing processes because of the uncertainty of the unknown. The 2D nature of graphene materials with a thickness of one atom presents significant challenges to proper handling/processing, and process scale-up becomes difficult because it requires high-end, expensive equipment, even for routine handling and analysis for quality assurance and control. Pristine graphene can also be extremely difficult to work into other matrices, thus hindering downstream processibility, especially at large scale. Currently, the cost of graphene and graphene products is still high and presents an economic risk that tends to slow down investment in scaling up emerging technologies. The lack of a standard for graphene materials for quality assurance and quality control poses a great challenge not only for the markets but also for commercialization efforts. A first-look economic feasibility analysis of the UCP technology provided valuable information that suggests the UCP process would be feasible, especially when it is scaled to a pilot scale and could be more competitive at the full scale. Graphitization was found to be the most energy-consuming and most capital-intensive step in the overall process. In small laboratory- and bench-scale experiments, labor is a significant contributor to the total process costs. Although these energy, capital, and labor constraints contribute to a higher selling price for the product, a preliminary economic model suggests that the process would be feasible at large scale when the process is fully integrated, optimized, and automated.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2021

A transmissive concentrator photovoltaic module with cells directly cooled by silicone oil for solar cogeneration systems

Hybrid concentrator photovoltaic-thermal systems can cogenerate electricity and heat by beam-splitting incoming concentrated light onto photovoltaic cells and a thermal receiver to increase total conversion efficiency and potentially reduce system cost. To demonstrate this, we have designed and prototyped a transmissive spectrum-splitting concentrator photovoltaic module that maximizes solar energy conversion by utilizing the entire solar spectrum. Visible light is collected using infrared-transmissive triple-junction photovoltaic cells to achieve an in-band module efficiency of 43.3% for light of wavelength λ < 873 nm, while 44.2% of out-of-band light with λ > 873 nm is transmitted through for collection by a thermal receiver. During testing on a dual-axis tracked parabolic concentrator dish at up to 166 suns, cell temperatures were maintained at 119 °C or below via a novel active cooling method. This cooling system strictly flows silicone oil directly across both sides of the cells, without inhibiting optical transmission, as verified through experimentation and simulation. The module was validated outdoors for 572 sun·hrs, and achieved a maximum thermal receiver temperature of 180 °C. 86.1% of incident solar power is collected at 166 suns average concentration collectively among the electrical, cooling, and thermal receiver subsystems. The remaining 13.9% is lost to mirror reflectivity, dish shadowing, receiver reflection, and thermal losses. The ability to directly cool the cells with an inert silicone oil offers the potential for reduced system cost relative to previous transmissive hybrid concentrator photovoltaic-thermal systems, including microfluidic-cooled designs. This solar cogeneration capability is valuable in a wide range of commercial and industrial applications.

14 SOLAR ENERGY↗
DOE OSTI2020

High-efficiency solar thermophotovoltaic system using a nanostructure-based selective emitter

Herein, we present the design, fabrication, optimization, and experimental results of a high-efficiency planar solar thermophotovoltaic (STPV) system utilizing a micro-textured absorber and a nanostructure multilayer metal-dielectric coated selective emitter fabricated on a tungsten (W) substrate. Light absorptance of more than 90% was achieved at visible and near-infrared wavelengths using the microtextured absorbing surface. The nanostructure selective emitter consists of two thin-film optical coatings of silicon nitride (Si3N4) and a layer of W in between to increase the surface emissivity in spectral regimes matching the quantum efficiency of the thermophotovoltaic (TPV) cells. Gallium antimonide (GaSb)-based TPV cells are used in our STPV design. The experiment was conducted at different operating temperatures using a high-power continuous wave laser diode stack as a simulated source of concentrated incident radiation. Our experimental setup measured a maximum electrical output power density of 1.71 W/cm 2 at 1676 K STPV temperature, and the overall power conversion efficiency of 8.4% after normalizing the output power density to the emitter area. This is the highest STPV system efficiency reported so far for any experimental STPV device. The incident optical laser power on the absorber side was 131 W. This is equivalent to a solar concentration factor of ~2100, which is within the practical limit and readily achievable with Fresnel lens setup.

14 SOLAR ENERGY↗
NASA NTRS1976

Conversion of laser energy to chemical energy by the photoassisted electrolysis of water

Ultraviolet irradiation of the n-type semiconductor TiO2 crystal electrode of an aqueous electrochemical cell evolves O2 at the TiO2 electrode and H2 at the Pt electrode. The gases are typically evolved in a 2:1 (H2:O2) volume ratio. The photoassisted reaction seems to require applied voltages, but values as low as 0.25 V do allow the photoassisted electrolysis to proceed. Prolonged irradiation in either acid or base evolves the gaseous products in amounts which clearly demonstrate that the reaction is catalytic with respect to the TiO2. The wavelength response of the TiO2 and the correlation of product yield and current are reported. The results support the claim that TiO2 is a true photoassistance agent for the electrolysis of water. Minimum optical storage efficiencies of the order of 1 percent can be achieved by the production of H2.

Wrighton, M. S.↗
NASA NTRS2010

Trace Gas Measurements on Mars and Earth Using Optical Parametric Generation

Trace gases and their isotopic ratios in planetary atmospheres offer important but subtle clues as to the origins of a planet's atmosphere, hydrology, geology, and potential for biology. An orbiting laser remote sensing instrument is capable of measuring trace gases on a global scale with unprecedented accuracy, and higher spatial resolution that can be obtained by passive instruments. We have developed an active sensing instrument for the remote measurement of trace gases in planetary atmospheres (including Earth). The technique uses widely tunable, seeded optical parametric generation (OPG) to measure methane, CO2, water vapor, and other trace gases in the near and mid-infrared spectral regions. Methane is a strong greenhouse gas on Earth and it is also a potential biogenic marker on Mars and other planets. Methane in the Earth's atmosphere survives for a shorter time than CO2 but its impact on climate change can be larger than CO2. Methane levels have remained relatively constant over the last decade around 1.78 parts per million (ppm) but recent observations indicate that methane levels may be on the rise. Increasing methane concentrations may trigger a positive feedback loop and a subsequent runaway greenhouse effect, where increasing temperatures result in increasing methane levels. The NRC Decadal Survey recognized the importance of global observations of greenhouse gases and called for simultaneous CH4, CO, and CO2 measurements but also underlined the technological limitations for these observations. For Mars, methane measurements are of great interest because of its potential as a strong biogenic marker. A remote sensing instrument that can measure day and night over all seasons and latitudes can identify and localize sources of biogenic gas plumes produced by subsurface chemistry or biology, and aid in the search for extra-terrestrial life. It can identify the dynamics of methane generation over time and latitude and identify future lander mission sites for more detailed in-situ analysis. In this paper we report on remote sensing measurements of methane using a high peak power, widely tunable optical parametric generator (OPG) operating at 3.3 micron and 1.65 micron. The OPG is pumped by a passively q-switched single frequency laser (3ns, 5KHz, 50uJ) and seeded by a diode laser. The spectral width of both signal and idler of seeded OPG is nearly Fourier transform limited. The output of seeded OPG is single frequency with high spectral purity and is widely tunable. Both 1650 nm and 3300 nm can be generated with a conversion efficiency of more than 30%. We have demonstrated detection of methane at 3274 nm and 1650 nm in a cell and also performed open path atmospheric measurements of methane at the same wavelengths. Finally, we were able to demonstrate simultaneous detection of methane at 3270.4 nm and CO2 at 1578.2 nm. In this paper we will discuss the OPG performance and atmospheric open path measurement results.

Numata, Kenji↗
DOE OSTI2025

Femtosecond wavelength-tunable laser system using gain managed nonlinear amplifier

Optical parametric amplifiers require a seed energy at the spectral range of interest for amplification. In the case of pulsed laser systems, seed pulse characteristics such as spectral energy density and spectral uniformity influence laser system design and performance. In this letter, we present the design and modeling of a few micro-joules, wavelength-tunable, femtosecond parametric amplifier system. We employ a gain-managed nonlinear fiber amplifier output as the seed pulse. This seed pulse is relatively uniform across its bandwidth from 1010 to 1180 nm. Its spectral energy density averages 600 pJ/nm, 30 times higher than conventional counterparts. The overall amplification gain is 175, and the conversion efficiency is 17.5%. The inherent quasi-linear chirp of the seed pulse is utilized to alter the output wavelength. Our tunable femtosecond laser is an enabling technology for high-demand applications such as time-resolved spectroscopy, nonlinear and advanced material research, and biomedical imaging and microscopy modalities.

47 OTHER INSTRUMENTATION↗
NASA NTRSDate not supplied

Lunar Polar Exploration with Beamed Powered Rovers

Use of a laser to transmit power to a photovoltaic array has been proposed many times, including significant work done at NASA Glenn during the 1990s, but until recently the technology has lagged behind the ambitious requirements. The current NASA objective of lunar polar exploration provides the need, and evolution of higher-power and more efficient lasers provides the opportunity. Exploration of the ice-bearing craters near the lunar poles, where complete absence of sunlight precludes solar power, have been identified as a significant technology challenge for NASA’s future exploration. An approach to solve this is to use a laser to send power from the illuminated crater rim to a photovoltaic receiver on a rover inside the permanently dark region. A conceptual design was done of a prototype laser power system to be included on a proposed flight demonstration of the Kilopower space reactor. For the design, the laser transmitter is mounted on a small rover capable of moving to a location in line of sight of the receiving rover, e.g., on a crater rim with a view into the permanently dark region to be explored. A 250-watt laser diode bar transmits power at 808 nm, using a 10.5 cm optical beam director. The beam is received by a GaAs solar array mounted on the exploring rover, where it is converted into electrical power at ~50% optical to electrical efficiency. For the flight demonstration, 50 meters of laser transmission was required. The design showed a total laser mass of 7.8 kg is capable of producing the beam needed, not including the thermal control system. The demonstration design demonstrates 50-m transmission, but it would be valuable to have longer point-to-point beaming on the moon. Long beam paths require higher coherence than the diode laser bars of the demonstration system. The development of high-efficiency diode-pumped fiber lasers meets this technology need: and diode-pumped fiber lasers using the Er/Yb system can be purchased commercially with overall conversion efficiency of greater than 50% at wavelength 1.06 micrometers. Two technologies for a photovoltaic converter for this wavelength are the InGaAs photovoltaic cell, using technology developed for multi-junction space solar cells, or newly-developed high-quantum efficiency silicon cells. The next step to mature the technology would be a lunar flight demonstration. In the future, this has the potential to enhance and enable future human exploration of the moon, harvesting and utilizing the ice resources of these permanently-shadowed craters.

Geoffrey A Landis↗
NASA NTRS2000

Optical Analysis of Transparent Polymeric Material Exposed to Simulated Space Environment

Many innovations in spacecraft power and propulsion have been recently tested at NASA, particularly in non-chemical propulsion. One improvement in solar array technology is solar concentration using thin polymer film Fresnel lenses. Weight and cost savings were proven with the Solar Concentrator Arrays with Refractive Linear Element Technology (SCARLET)-II array on NASA's Deep Space I spacecraft. The Fresnel lens concentrates solar energy onto high-efficiency solar cells, decreasing the area of solar cells needed for power. Continued efficiency of this power system relies on the thin film's durability in the space environment and maintaining transmission in the 300 - 1000 nm bandwidth. Various polymeric materials have been tested for use in solar concentrators, including Lexan(TM), polyethylene terephthalate (PET), several formulations of Tefzel(Tm) and Teflon(TM), and DC 93-500, the material selected for SCARLET-II. Also tested were several innovative materials including Langley Research Center's CPI and CP2 polymers and atomic oxygen- resistant polymers developed by Triton Systems, Inc. The Environmental Effects Group of the Marshall Space Flight Center's Materials, Processes, and Manufacturing Department exposed these materials to simulated space environment and evaluated them for any change in optical transmission. Samples were exposed to a minimum of 1000 equivalent Sun hours of near-UV radiation (250 - 400 nm wavelength). Materials that appeared robust after near-UV exposure were then exposed to charged particle radiation equivalent to a five-year dose in geosynchronous orbit. These exposures were performed in MSFC's Combined Environmental Effects Test Chamber, a unique facility with the capability to expose materials simultaneously or sequentially to protons, low-energy electrons, high-energy electrons, near UV radiation and vacuum UV radiation. Reflectance measurements can be made on the samples in vacuum. Prolonged exposure to the space environment will decrease the polymer film's transmission and thus reduce the conversion efficiency. A method was developed to normalize the transmission loss and thus rank the materials according to their tolerance to space environmental exposure. Spectral results and the material ranking according to transmission loss are presented.

Edwards, David L.↗
NASA NTRS1980

Titanium dioxide antireflection coating for silicon solar cells by spray deposition

A high-speed production process is described for depositing a single-layer, quarter-wavelength thick antireflection coating of titanium dioxide on metal-patterned single-crystal silicon solar cells for terrestrial applications. Controlled atomization spraying of an organotitanium solution was selected as the most cost-effective method of film deposition using commercial automated equipment. The optimal composition consists of titanium isopropoxide as the titanium source, n-butyl acetate as the diluent solvent, sec-butanol as the leveling agent, and 2-ethyl-1-hexanol to render the material uniformly depositable. Application of the process to the coating of circular, large-diameter solar cells with either screen-printed silver metallization or with vacuum-evaporated Ti/Pd/Ag metallization showed increases of over 40% in the electrical conversion efficiency. Optical characteristics, corrosion resistance, and several other important properties of the spray-deposited film are reported. Experimental evidence indicates a wide tolerance in the coating thickness upon the overall efficiency of the cell. Considerations pertaining to the optimization of AR coatings in general are discussed, and a comprehensive critical survey of the literature is presented.

Kern, W.↗
DOE OSTI2021

Performance of Spherical Quantum Well Down Converters in Solid State Lighting

We report the color conversion performance of amber and red emitting quantum dots (QDs) on InGaN solid-state lighting (SSL) light emitting diode (LED) packages. Spherical quantum well (SQW) architectures (CdS/CdSe 1- x S x /CdS) were prepared using a library of thio- and selenourea synthesis reagents and high throughput synthesis robotics. CdS/CdSe 1- x S x QDs with narrow luminescence bands were coated with thick CdS shells (thickness = 1.6-7.5 nm) to achieve photoluminescence quantum yields (PLQY) up to 88% at amber and red emission wavelengths (λ max = 600-642 nm, FWHM < 45 nm). The photoluminescence from SQWs encapsulated in silicone and deposited on LED packages was monitored under accelerated aging conditions (oven temperature = 85 °C, relative humidity = 5-85%, blue optical power density = 3-45 W/cm 2 ) by monitoring the red photon output over several hundred hours of continuous operation. The growth of a ZnS shell on the SQW surface increases the stability under long-term operation but also reduces the PLQY, especially of SQWs with thick CdS shells. The results illustrate that the outer ZnS shell layer is key to optimizing the PLQY and the long-term stability of QDs during operation on SSL packages.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

MgSiP 2 : An Infrared Nonlinear Optical Crystal with a Large Non‐Resonant Phase‐Matchable Second Harmonic Coefficient and High Laser Damage Threshold

Superior infrared nonlinear optical (NLO) crystals are in urgent demand in the development of lasers and optical technologies for communications and computing. The critical challenge is to find a crystal with large non‐resonant phase‐matchable NLO coefficients and high laser damage threshold (LDTs) simultaneously, which however scale inversely. This work reports such a material, MgSiP 2, that exhibits a large second harmonic generation (SHG) coefficient of d 14 ≈ d 36 = 89 ± 5 pm V −1 at 1550 nm fundamental wavelength, surpassing the commercial NLO crystals AgGaS 2 , AgGaSe 2 , and ZnGeP 2 . First principles theory reveals the polarizability and geometric arrangement of the [SiP 4 ] tetrahedral units as the origin of this large nonlinear response. Remarkably, it also exhibits a high LDT value of 684 GW cm −2 , which is six times larger than ZnGeP 2 and three times larger than CdSiP 2 . It has a wide transparency window of 0.53–10.35 µm, allowing broadband tunability. Further, it is Type I and Type II phase‐matchable with large effective SHG coefficients of d eff,I ≈80.2 pm V −1 and d eff,II ≈73.4 pm V −1 . The outstanding properties of MgSiP 2 make it a highly attractive candidate for optical frequency conversion in the infrared.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Highly Nonstoichiometric YAG Ceramics with Modified Luminescence Properties

Abstract Y 3 Al 5 O 12 (YAG) is a widely used phosphor host. Its optical properties are controlled by chemical substitution at its YO 8 or AlO 6 /AlO 4 sublattices, with emission wavelengths defined by rare‐earth and transition‐metal dopants that have been explored extensively. Nonstoichiometric compositions Y 3+x Al 5‐x O 12 ( x ≠ 0) may offer a route to new emission wavelengths by distributing dopants over two or more sublattices simultaneously, producing new local coordination environments for the activator ions. However, YAG typically behaves as a line phase, and such compositions are therefore challenging to synthesize. Here, a series of highly nonstoichiometric Y 3+x Al 5‐x O 12 with 0 ≤ x ≤ 0.40 is reported, corresponding to ≤20% of the AlO 6 sublattice substituted by Y 3+ , synthesized by advanced melt‐quenching techniques. This impacts the up‐conversion luminescence of Yb 3+ /Er 3+ ‐doped systems, whose yellow‐green emission differs from the red‐orange emission of their stoichiometric counterparts. In contrast, the YAG:Ce 3+ system has a different structural response to nonstoichiometry and its down‐conversion emission is only weakly affected. Analogous highly nonstoichiometric systems should be obtainable for a range of garnet materials, demonstrated here by the synthesis of Gd 3.2 Al 4.8 O 12 and Gd 3.2 Ga 4.8 O 12 . This opens pathways to property tuning by control of host stoichiometry, and the prospect of improved performance or new applications for garnet‐type materials.

Chemistry↗
NASA NTRS2003

Refinement of Protocols for Measuring the Apparent Optical Properties of Seawater

Ocean color satellite missions, like the Sea-viewing Wide Field-of-view Sensor (SeaWiFS) or the Moderate Resolution Imaging Spectroradiometer (MODIS) projects, are tasked with acquiring a global ocean color data set, validating and monitoring the accuracy and quality of the data, processing the radiometric data into geophysical units using a set of atmospheric and bio-optical algorithms, and distributing the final products to the scientific community. The long-standing requirement of the SeaWiFS Project, for example, is to produce spectral water-leaving radiances, LW(lambda), to within 5% absolute (lambda denotes wavelength) and chlorophyll a concentrations to within 35% (Hooker and Esaias 1993), and most ocean color sensors have the same or similar requirements. Although a diverse set of activities are required to ensure the accuracy requirements are met (Hooker and McClain 2000), the perspective here is with field observations. The accurate determination of upper ocean apparent optical properties (AOPs) is essential for the vicarious calibration of ocean color data and the validation of the derived data products, because the sea-truth measurements are used to evaluate the satellite observations (Hooker and McClain 2000). The uncertainties with in situ AOP measurements have various sources: a) the sampling procedures used in the field, including the environmental conditions encountered; b) the absolute characterization of the radiometers in the laboratory; c) the conversion of the light signals to geophysical units in a processing scheme, and d) the stability of the radiometers in the harsh environment they are subjected to during transport and use. Assuming ideal environmental conditions, so this aspect can be neglected, the SeaWiFS ground-truth uncertainty budget can only be satisfied if each uncertainty is on the order of 1-2%, or what is generally referred to as 1% radiometry. In recent years, progress has been made in estimating the magnitude of some of these uncertainties and in defining procedures for minimizing them. For the SeaWiFS Project, the first step was to convene a workshop to draft the SeaWiFS Ocean Optics Protocols (hereafter referred to as the Protocols). The Protocols initially adhered to the Joint Global Ocean Flux Study (JGOFS) sampling procedures (JGOFS 1991) and defined the standards for optical measurements to be used in SeaWiFS calibration and validation activities (Mueller and Austin 1992). Over time, the Protocols were revised (Mueller and Austin 1995), and then recurringly updated on essentially an annual basis (Mueller 2000, 2002, and 2003) as part of the Sensor Inter-comparison and Merger for Biological and Interdisciplinary Oceanic Studies (SIMBIOS) project. 98

Hooker, Stanford B.↗
NASA NTRS1980

Radio and white-light observations of coronal transients

Optical, radio and X-ray evidence of violent mass motions in the corona has existed for some years but only recently have the form, nature, frequency and implication of the transients become obvious. In this paper the observed properties of coronal transients are reviewed, with concentration on the white-light and radio manifestations. The classification according to speeds seems to be meaningful, with the slow transients having thermal emissions at radio wavelengths and the fast ones nonthermal. The possible mechanisms involved in the radio bursts are then discussed and estimates of various forms of energy are reviewed. It appears that the magnetic energy transported from the sun by the transient exceeds that of any other form, and that magnetic forces dominate in the dynamics of the motions. The conversion of magnetic energy into mechanical energy, by expansion of the field, provides a possible driving force for the coronal and interplanetary shock waves.

Dulk, G. A.↗
NASA NTRS1993

Pinatubo and pre-Pinatubo optical-depth spectra: Mauna Loa measurements, comparisons, inferred particle size distributions, radiative effects, and relationship to lidar data

The Ames airborne tracking sunphotometer was operated at the National Oceanic and Atmospheric Administration (NOAA) Mauna Loa Observatory (MLO) in 1991 and 1992 along with the NOAA Climate Monitoring and Diagnostics Laboratory (CMDL) automated tracking sunphotometer and lidar. June 1991 measurements provided calibrations, optical-depth spectra, and intercomparisons under relatively clean conditions; later measurements provided spectra and comparisons for the Pinatubo cloud plus calibration checks. June 1991 results are similar to previous MLO springtime measurements, with midvisible particle optical depth at the near-background level of 0.012 +/- 0.006 and no significant wavelength dependence in the measured range (lambda = 0.38 to 1.06 micrometers). The arrival of the Pinatubo cloud in July 1991 increased midvisible particle optical depth by more than an order of magnitude and changed the spectral shape of to an approximate power law with an exponent of about -1.4. By clearly September 1991, the spectrum was broadly peaked near 0.5 micrometers, and by July 1992, it was peaked near 0.8 micrometers. Our optical-depth spectra include corrections for diffuse light. NOAA- and Ames Research Center (ARC)-measured spectra are in good agreement. Columnar size distributions inverted from the spectra show that the initial (July 1991) post-Pinatubo cloud was relatively rich in small particles (r less than 0.25 micrometers), which were progressively depleted in the August-September 1991 and July 1992 periods. Conversely, both of the later periods had more of the optically efficient medium-sized particles (0.25 less than r less than 1 micrometers) than did the fresh July 1991 cloud. These changes are consistent with particle growth by condensation and coagulation. Photometer-inferred column backscatter values agree with those measured by the CMDL lidar on nearby nights. Combining lidar-measured backscatter profiles with photometer-derived backscatter-to-area ratios gives peak particle areas that could cause rapid heterogeneous loss of ozone, given sufficiently low particle acidity and suitable solar zenith angles (achieved at mid- to high latitudes). Top-of-troposphere radiative forcings for the September 1991 and July 1992 optical depths and size distributions over MLO are about -5 and -3 W/sq m, respectively (hence comparable in magnitude but opposite in sign to the radiative forcing caused by the increase in manmade greenhouse gases since the industrial revolution). Heating rates in the Pinatubo layer over MLO are 0.55 +/- 0.13 and 0.41 +/- 0.14 K/d for September 1991 and July 1992, respectively.

Russell, P. B.↗