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At least 91 records · Page 5

Advances in Colloidal InP-Based Quantum Dots for Photocatalytic Hydrogen Evolution

Photocatalytic materials for hydrogen generation are typically categorized into UV-absorbing metal oxides and visible-range semiconductors such as chalcogenides or perovskites, which often incorporate toxic elements. To address environmental concerns of the latter group, indium phosphide (InP)-based quantum dots (QDs) have recently emerged as a less toxic alternative. These nanocrystals (NCs) benefit from a broadband and tunable absorption spectrum, which is well matched for solar photochemistry, and offer suitable electronic characteristics to drive photoinduced charge separation. This perspective provides a comprehensive summary of the recent advancements in developing InP-based NCs with a focus on photocatalytic hydrogen production. We discuss synthetic strategies that enhance the catalytic activity of these materials and highlight key challenges that must be addressed to enhance their performance. Finally, we explore future research directions aimed at improving photocatalytic efficiency and integrating InP-based QDs into practical solar-to-fuel conversion systems.

Hydrogen↗

Frenkel excitons in heat-stressed supramolecular nanocomposites enabled by tunable cage-like scaffolding

Delocalized Frenkel excitons—coherently shared excitations among chromophores—are responsible for the remarkable efficiency of supramolecular light-harvesting assemblies within photosynthetic organisms. The translation of nature’s design principles to applications in optoelectronic devices has been limited by the fragility of the supramolecular structures used and the delicate nature of Frenkel excitons, particularly under mildly changing solvent conditions and elevated temperatures and upon deposition onto solid substrates. Here, we overcome those functionalization barriers through composition of stable supramolecular light-harvesting nanotubes enabled by tunable (~4.3–4.9 nm), uniform (±0.3 nm) cage-like scaffolds. High-resolution cryogenic electron microscopy, combined with scanning electron microscopy, broadband femtosecond transient absorption spectroscopy and near-field scanning optical microscopy revealed that excitons within the cage-like scaffolds are robust, even under extreme heat stress, and control over nanocomposite dimensions is maintained on solid substrates. Our bio-inspired nanocomposites provide a general framework for the development of next-generation organic devices made from stable supramolecular materials.

14 SOLAR ENERGY↗

Diagnostic for Plasma Enhanced Chemical Vapor Deposition and Etch Systems

In order to meet NASA's requirements for the rapid development and validation of future generation electronic devices as well as associated materials and processes, enabling technologies ion the processing of semiconductor materials arising from understanding etch chemistries are being developed through a research collaboration between Stanford University and NASA-Ames Research Center, Although a great deal of laboratory-scale research has been performed on many of materials processing plasmas, little is known about the gas-phase and surface chemical reactions that are critical in many etch and deposition processes, and how these reactions are influenced by the variation in operating conditions. In addition, many plasma-based processes suffer from stability and reliability problems leading to a compromise in performance and a potentially increased cost for the semiconductor manufacturing industry. Such a lack of understanding has hindered the development of process models that can aid in the scaling and improvement of plasma etch and deposition systems. The research described involves the study of plasmas used in semiconductor processes. An inductively coupled plasma (ICP) source in place of the standard upper electrode assembly of the Gaseous Electronics Conference (GEC) radio-frequency (RF) Reference Cell is used to investigate the discharge characteristics and chemistries. This ICP source generates plasmas with higher electron densities (approximately 10(exp 12)/cu cm) and lower operating pressures (approximately 7 mTorr) than obtainable with the original parallel-plate version of the GEC Cell. This expanded operating regime is more relevant to new generations of industrial plasma systems being used by the microelectronics industry. The motivation for this study is to develop an understanding of the physical phenomena involved in plasma processing and to measure much needed fundamental parameters, such as gas-phase and surface reaction rates. species concentration, temperature, ion energy distribution, and electron number density. A wide variety of diagnostic techniques are under development through this consortium grant to measure these parameters. including molecular beam mass spectrometry (MBMS). Fourier transform infrared (FTIR) spectroscopy, broadband ultraviolet (UV) absorption spectroscopy, a compensated Langmuir probe. Additional diagnostics. Such as microwave interferometry and microwave absorption for measurements of plasma density and radical concentrations are also planned.

Cappelli, Mark A.↗

Evaluation of a Variable-Impedance Ceramic Matrix Composite Acoustic Liner

As a result of significant progress in the reduction of fan and jet noise, there is growing concern regarding core noise. One method for achieving core noise reduction is via the use of acoustic liners. However, these liners must be constructed with materials suitable for high temperature environments and should be designed for optimum absorption of the broadband core noise spectrum. This paper presents results of tests conducted in the NASA Langley Liner Technology Facility to evaluate a variable-impedance ceramic matrix composite acoustic liner that offers the potential to achieve each of these goals. One concern is the porosity of the ceramic matrix composite material, and whether this might affect the predictability of liners constructed with this material. Comparisons between two variable-depth liners, one constructed with ceramic matrix composite material and the other constructed via stereolithography, are used to demonstrate this material porosity is not a concern. Also, some interesting observations are noted regarding the orientation of variable-depth liners. Finally, two propagation codes are validated via comparisons of predicted and measured acoustic pressure profiles for a variable-depth liner.

Jones, M. G.↗

Evaluation of SWIR Crop Residue Bands for the Landsat Next Mission

This research reports the findings of a Landsat Next expert review panel that evaluated the use of narrow shortwave infrared (SWIR) reflectance bands to measure ligno-cellulose absorption features centered near 2100 and 2300 nm, with the objective of measuring and mapping non-photosynthetic vegetation (NPV), crop residue cover, and the adoption of conservation tillage practices within agricultural landscapes. Results could also apply to detection of NPV in pasture, grazing lands, and non-agricultural settings. Currently, there are no satellite data sources that provide narrowband or hyperspectral SWIR imagery at sufficient volume to map NPV at a regional scale. The Landsat Next mission, currently under design and expected to launch in the late 2020’s, provides the opportunity for achieving increased SWIR sampling and spectral resolution with the adoption of new sensor technology. This study employed hyperspectral data collected from 916 agricultural field locations with varying fractional NPV, fractional green vegetation, and surface moisture contents. These spectra were processed to generate narrow bands with centers at 2040, 2100, 2210, 2260, and 2230 nm, at various bandwidths, that were subsequently used to derive 13 NPV spectral indices from each spectrum. For crop residues with minimal green vegetation cover, two-band indices derived from 2210 and 2260 nm bands were top performers for measuring NPV (R^(2) = 0.81, RMSE = 0.13) using bandwidths of 30 to 50 nm, and the addition of a third band at 2100 nm increased resistance to atmospheric correction residuals and improved mission continuity with Landsat 8 Operational Land Imager Band 7. For prediction of NPV over a full range of green vegetation cover, the Cellulose Absorption Index, derived from 2040, 2100, and 2210 nm bands, was top performer (R^(2) = 0.77, RMSE = 0.17), but required a narrow (≤20 nm) bandwidth at 2040 nm to avoid interference from atmospheric carbon dioxide absorption. In comparison, broadband NPV indices utilizing Landsat 8 bands centered at 1610 and 2200 nm performed poorly in measuring fractional NPV (R^(2) = 0.44), with significantly increased interference from green vegetation

Wells Dean Hively↗

A Portable Nitrogen Dioxide Instrument Using Cavity-Enhanced Absorption Spectroscopy

The Portable (2.7 kg) Cavity-enhanced Absorption of Nitrogen Dioxide (PCAND) instrument for measuring in situ nitrogen dioxide (NO2) was developed using incoherent, broadband cavity-enhanced absorption spectroscopy (IBBCEAS). An LED light source centered at 408 nm was coupled to a cavity 15 cm in length, achieving an effective optical pathlength of ~520 m. Our precision was measured as 94 pptv (1 s). To date, we have flown this instrument on 3 balloon and 1 UAV test flights. This instrument records data to an SD card and outputs data (via an RS232 port) to external devices including a commercial radiosonde (iMet) for real-time data downlink.

TROPOMI↗

Broadband titanium nitride disordered metasurface absorbers

We experimentally demonstrate titanium nitride (TiN) broadband metasurface perfect absorbers by conformally coating plasmonic TiN films onto disordered anodic aluminum oxide (AAO) nanotemplates. The disordered metasurface absorbers exhibit polarization-insensitive and weak angle-dependent perfect absorption over the entire visible and near-infrared spectral regions (300 < λ < 2500 nm). We show from experimental results and numerical simulations that the light scattering induced by the strong disorder of the AAO nanopores and the strong absorption of the TiN deposited on their sidewall are of critical importance for achieving broadband perfect absorption. The TiN disordered metasurface perfect absorbers are superior to many other types of broadband perfect absorbers previously reported and are more suitable for practical applications especially in harsh environments. The device concept for broadband perfect absorption based on plasmonic metal-nitride film coated disordered dielectric media could potentially be extended to significantly enhance the efficiency of solar energy harvesting and the performance of hot-carrier based optoelectronics.

Chang, Chun-Chieh (ORCID:0000000337282454)↗

Watching Excited State Dynamics with Optical and X-ray Probes: The Excited State Dynamics of Aquocobalamin and Hydroxocobalamin

Femtosecond time-resolved X-ray absorption (XANES) at the Co K-edge, X-ray emission (XES) in the Co Kβ and valence-to-core regions, and broadband UV–vis transient absorption are combined to probe the femtosecond to picosecond sequential atomic and electronic dynamics following photoexcitation of two vitamin B12 compounds, hydroxocobalamin and aquocobalamin. Polarized XANES difference spectra allow identification of sequential structural evolution involving first the equatorial and then the axial ligands, with the latter showing rapid coherent bond elongation to the outer turning point of the excited state potential followed by recoil to a relaxed excited state structure. Time-resolved XES, especially in the valence-to-core region, along with polarized optical transient absorption suggests that the recoil results in the formation of a metal-centered excited state with a lifetime of 2–5 ps. In conclusion, this combination of methods provides a uniquely powerful tool to probe the electronic and structural dynamics of photoactive transition-metal complexes and will be applicable to a wide variety of systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microwave Kinetic Inductance Detector with Selective Polarization Coupling

A conventional low-noise detector requires a technique to both absorb incident power and convert it to an electrical signal at cryogenic temperatures. This innovation combines low-noise detector and readout functionality into one device while maintaining high absorption, controlled polarization sensitivity, and broadband detection capability. The resulting far-infrared detectors can be read out with a simple approach, which is compact and minimizes thermal loading. The proposed microwave kinetic inductance detector (MKID) consists of three basic elements. The first is the absorptive section in which the incident power is coupled to a superconducting resonator at far-infrared frequency above its superconducting critical frequency (where superconductor becomes normal conductor). This absorber's shape effectively absorbs signals in the desired polarization state and is resonant at the radio frequency (RF) used for readout of the device. Control over the metal film used in the absorber allows realization of structures with either a 50% broadband or 100% resonance absorptance over a 30% fractional bandwidth. The second element is a microwave resonator - which is realized from the thin metal films used to make the absorber as transmission lines - whose resonance frequency changes due to a variation in its kinetic inductance. The resonator's kinetic inductance is a function of the power absorbed by the device. A low-loss dielectric (mono-crystalline silicon) is used in a parallel-plate transmission line structure to realize the desired superconducting resonators. There is negligible coupling among the adjacent elements used to define the polarization sensitivity of each detector. The final component of the device is a microwave transmission line, which is coupled to the resonator, and allows detection of changes in resonance frequency for each detector in the focal plane array. The spiral shape of the detector's absorber allows incident power with two polarizations to couple to the detector equally. A stepped impedance resonator was used that allows the incident power absorbed in the detecting membrane area to be uniformly distributed in the detector's transmission line at the RF readout frequency. This maximizes the sensitivity of the detector. The signal is read out via a frequency multiplexing technique that requires a minimum number of interface transmission lines for readout. This reduces the packaging complexity and coupling to the device's thermal environment.

Wollack, Edward↗

Dynamically tunable multicolor emissions from zero-dimensional Cs 3 LnCl 6 (Ln: europium and terbium) nanocrystals with wide color gamut

This study demonstrates dynamically tunable multicolor emissions from a single component, zero-dimensional (0-D) cesium europium chloride (Cs 3 EuCl 6 ) and cesium terbium chloride (Cs 3 TbCl 6 ) nanocrystals (NCs). Highly uniform colloidal Cs 3 EuCl 6 and Cs 3 TbCl 6 NCs are synthesized via the heating-up method. Excitation-wavelength-dependent multicolor emissions from Cs 3 EuCl 6 and Cs 3 TbCl 6 NCs are observed. Under excitation of 330–400 nm, both NCs exhibit blue photoluminescence (PL). Under wavelengths shorter than 330 nm, characteristic red and green emissions are observed from Cs 3 EuCl 6 and Cs 3 TbCl 6 , respectively, owing to the atomic emissions from the f-orbitals in trivalent europium (Eu 3+ ) and terbium (Tb 3+ ) ions. Cs 3 EuCl 6 and Cs 3 TbCl 6 NCs exhibit broadband excitation spectra and enhanced absorption properties. Particularly, Cs 3 EuCl 6 NCs exhibit a very narrow full-width at half-maximum in both blue and red PL and no overlap between the two spectra. Further, the photophysical properties of these NCs are further investigated to understand the multicolor PL origins by time-resolved and temperature-dependent PL measurements. Finally, the potential applications of Cs 3 EuCl 6 and Cs 3 TbCl 6 NCs as anti-counterfeiting inks for high-level security are demonstrated. Given their broadband excitation with enhanced absorption properties and dynamically tunable colors with a wide color gamut, Cs 3 EuCl 6 and Cs 3 TbCl 6 NCs have great potential as novel multicolor NC emitters for many emerging applications.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Radiative transfer in a clumpy universe: The colors of high-redshift galaxies

We assess the effects of the stochastic attenuation produced by intervening QSO absorption systems on the broadband colors of galaxies at cosmological distances. We compute the H I opacity of a clumpy universe as a function of redshift, including scattering in resonant lines, such as Lyman alpha, Lyman beta, Lyman gamma, and higher order members, and Lyman-continuum absorption. Both the numerous, optically thin Lyman-alpha forest clouds and the rarer, optically thick Lyman limit systems are found to contribute to the obscuration of background sources. We study the mean properties of primeval galaxies at high redshift in four broad optical passbands, U(sub n), B, G, and R. Even if young galaxies radiated a significant amount of ionizing photons, the attenuation due to the accumulated photoelectric opacity along the path is so severe that sources beyond z approximately 3 will drop out of the U(sub n) image together. We also show that the observed B-R color of distant galaxies can be much redder than expected from a stellar population. At z approximately 3.5, the blanketing by discrete absorption lines in the Lyman series is so effective that background galaxies appear, on average, 1 mag fainter in B. By z approximately 4, the observed B magnitude increment due to intergalactic absorption exceeds 2 mag. By modeling the intrinsic UV spectral energy distribution of star-forming galaxies with a stellar population synthesis code, we show that the (B-R)(sub AB) approximately 0 criterion for identifying 'flat-spectrum,' metal-producing galaxies is biased against objects at z greater than 3. The continuum blanketing from the Lyman series produces a characteristic staircase profile in the transmitted power. We suggest that this cosmic Lyman decrement might be used as a tool to identify high-z galaxies.

Madau, Piero↗

Structural and Spectroscopic Analysis of Ln(II) 18-crown-6 and Benzo-18-crown-6 Complexes (Ln = Sm, Eu, Yb)

Three Ln 2+ 18-crown-6 complexes of the formula Ln(18-crown-6)I 2 (Ln = Sm, Eu, Yb) were isolated from the explicit synthesis of the corresponding LnI 2 salts with 18-crown-6 and tetrabutylammonium tetraphenylborate in organic media under air-free conditions. Each metal complex forms a distorted hexagonal bipyramidal geometry and crystallizes in the monoclinic space group P2 1 /n. Comparatively, crystallization of Ln(benzo-18-crown-6)I 2 (Ln = Sm, Eu, Yb) from the reaction of LnI2 with tetrabutylammonium tetraphenylborate and benzo-18-crown-6 in THF/ethanol under similarly air-free conditions yields two polymorphs. The first form, α, crystallizes in the monoclinic space group P2 1 /c (or the nonstandard setting P2 1 /n for α-Yb); whereas the second polymorph, β, crystallizes in P$\bar{1}$. While the geometries of the molecules only vary slightly, the molecular packing and intramolecular contacts are quite different. In the structure of β, π–π interactions between the benzo- moieties of adjacent molecules are observed, whereas these interactions are absent in α. Despite the similarities in these classically 4f n+1 lanthanide systems, the complexes display distinct spectroscopic features in their respective absorption and photoluminescence spectra. Broadband 5d → 4f photoluminescence was observed for the Sm and Eu compounds in the NIR region and UV–visible region, respectively. None of the three Yb compounds exhibit photoluminescence UV–visible-NIR region; however, a unique photooxidation event was observed resulting in characteristic Yb(III) 4f → 4f transitions in the NIR region of the absorption spectra of these compounds. Finally, these findings are discussed along with structural comparisons of the 18-crown-6 and benzo-18-crown-6 compounds as well as other reported Ln(II) crown complexes in the literature.

crystals↗

Radiative properties of Cirrus clouds: FIRE IFO case October 28, 1986

A description of the radiative properties of two cirrus clouds sampled on 10/28/88 in the FIRE cirrus IFO is presented. The clouds are characterized in terms of the broadband infrared effective emittance, cloud fractional absorptance, shortwave heating rate, cloud albedo and vertical velocity. The broadband fluxes used in these calculations were obtained from measurements made by pyranometers and pyrgeometers. The shortwave irradiances were corrected to a horizontal plane and normalized to the same time by taking into account Sabreliner flight information (i.e., pitch, roll, heading and angle of attack), as well as sun-earth geometry considerations. Since only one aircraft was used, broadband fluxes at different levels in the cloud were not measured simultaneously. As a result, sampling errors may occur due to the nonsteady state of the cloud field or due to the possibility that the flight legs were not flown directly above or below each other. To minimize these errors and to simplify the analysis, the necessary variables were averaged and the averages used in the calculations. The downwelling shortwave and longwave irradiances were used as selection criteria to remove cloud free data encountered along the data sampling leg.

Hein, Paul F.↗

Chandra Grating Spectroscopy of Embedded Wind Shock X-ray Emission from O Stars Shows Low Plasma Temperatures and Significant Wind Absorption

We present a uniform analysis of six examples of embedded wind shock (EWS) O star X-ray sources observed at high resolution with the Chandra grating spectrometers. By modeling both the hot plasma emission and the continuum absorption of the soft X-rays by the cool, partially ionized bulk of the wind we derive the temperature distribution of the shock-heated plasma and the wind mass-loss rate of each star. We find a similar temperature distribution for each star’s hot wind plasma, consistent with a power-law differential emission measure, dlogEMdlogT, with a slope a little steeper than -2, up to temperatures of only about107K. The wind mass-loss rates, which are derived from the broadband X-ray absorption signatures in the spectra, are consistent with those found from other diagnostics. The most notable conclusion of this study is that wind absorption is a very important effect, especially at longer wavelengths. More than 90 per cent of the X-rays between 18 and 25 ̊A produced by shocks in the wind of ζPup are absorbed, for example. It appears that the empirical trend of X-ray hardness with spectral subtype among O stars is primarily an absorption effect.

David H Cohen↗

Dispersion-Engineered Deep Sub-Wavelength Plasmonic Metasurfaces for Broadband Seira Applications

Surface enhanced infrared absorption (SEIRA) spectroscopy is a powerful tool in which plasmonically enhanced electromagnetic fields provide high-sensitivity molecular detection. Most SEIRA platforms operate at a single resonant frequency, which must be tuned to match that of the target molecule, and commonly rely on time-consuming lithographic techniques. This study presents a high-throughput and cost-effective plasmonic metasurface for broadband, tunable, and strong infrared signal enhancement. The platform is built upon the principle of dispersion-engineered plasmonic Fabry–Pérot (FP) nanocavity arrays. It offers 1) tight squeezing of infrared (IR) photons into deep sub-wavelength nano-volumes and 2) spectrally tunable near-field enhancements of up to ≈10 6 , two to three orders of magnitude higher than most optical metasurface systems. By coupling multilayer nano-thin film deposition and nanoskiving fabrication techniques, the dispersive FP metasurfaces can be rapidly and reproducibly constructed in a scalable and lithography-free manner. Using IR spectroscopy, the selective and sensitive label-free detection of a molecular monolayer is achieved at a range of frequencies. An enhancement factor of nearly 10 5 is measured at the carbonyl (C = O) vibrational marker band of the molecule. The confluence of high field enhancement, broadband plasmonic response, and facile fabrication makes this metasurface a promising platform for SEIRA spectroscopy.

36 MATERIALS SCIENCE↗

New Broadband LIDAR for Greenhouse Carbon Dioxide Gas Sensing in the Earth's Atmosphere

We present demonstration of a novel broadband lidar technique capable of dealing with the atmospherically induced variations in CO2 absorption using a Fabry-Perot based detector and a broadband laser. The Fabry-Perot solid etalon in the receiver part is tuned to match the wavelength of several CO2 absorption lines simultaneously. The broadband technique tremendously reduces the requirement for source wavelength stability, instead putting this responsibility on the Fabry- Perot based receiver. The instrument technology we are developing has a clear pathway to space and realistic potential to become a robust, low risk space measurement system.

Georgieva, Elena↗

Mode-Selective Vibrational Energy Transfer Dynamics in 1,3,5-Trinitroperhydro-1,3,5-triazine (RDX) Thin Films

The coupling of inter- and intramolecular vibrations plays a critical role in initiating chemistry during the shock-to-detonation transition in energetic materials. In this work, we report on the subpicosecond to subnanosecond vibrational energy transfer (VET) dynamics of the solid energetic material 1,3,5-trinitroperhydro-1,3,5-triazine (RDX) by using broadband, ultrafast infrared transient absorption spectroscopy. Experiments reveal VET occurring on three distinct time scales: subpicosecond, 5 ps, and 200 ps. The ultrafast appearance of signal at all probed modes in the mid-infrared suggests strong anharmonic coupling of all vibrations in the solid, whereas the long-lived evolution demonstrates that VET is incomplete, and thus thermal equilibrium is not attained, even on the 100 ps time scale. Density functional theory and classical molecular dynamics simulations provide valuable insights into the experimental observations, revealing compression-insensitive time scales for the initial VET dynamics of high-frequency vibrations and drastically extended relaxation times for low-frequency phonon modes under lattice compression. Mode selectivity of the longest dynamics suggests coupling of the N–N and axial NO2 stretching modes with the long-lived, excited phonon bath.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

SDSS-IV MaStar: Stellar parameter determination with continuum-supplemented full-spectrum fitting

We present a stellar parameter catalog built to accompany the MaStar Stellar Library, which is a comprehensive collection of empirical, medium-resolution stellar spectra. We constructed this parameter catalog by using a multicomponent χ 2 fitting approach to match MaStar spectra to models generated by interpolating the ATLAS9-based BOSZ model spectra. The total χ 2 for a given model is defined as the sum of components constructed to characterize narrow-band features of observed spectra (e.g., absorption lines) and the broadband continuum shape separately. Extinction and systematics due to flux calibration were taken into account in the fitting. The χ 2 distribution for a given region of model space was sampled using a Markov chain Monte Carlo (MCMC) algorithm, the data from which were then used to extract atmospheric parameter estimates (T eff , log g, [Fe/H], and [α/Fe]), their corresponding uncertainties, and direct extinction measurements. Two methods were used to extract parameters and uncertainties: one that accepts the MCMC’s prescribed minimum-χ 2 result, and one that uses Bayesian inference to compute a likelihood-weighted mean from the χ 2 distribution sampled by the MCMC. Results were evaluated for internal consistency using repeat observations where available and by comparing them with external data sets (e.g., APOGEE-2 and Gaia DR2). Our spectral-fitting exercise reveals possible deficiencies in current theoretical model spectra, illustrating the potential power of MaStar spectra for helping to improve the models. This paper represents an update to the parameters that were originally presented with SDSS-IV DR17. The MaStar parameter catalog containing our BestFit results is available on the SDSS-IV DR17 website as part of version 2 of the MaStar stellar parameter value-added catalog.

79 ASTRONOMY AND ASTROPHYSICS↗