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At least 397 records · Page 22

CVD aluminiding process for producing a modified platinum aluminide bond coat for improved high temperature performance

A method of depositing by chemical vapor deposition a modified platinum aluminide diffusion coating onto a superalloy substrate comprising the steps of applying a layer of a platinum group metal to the superalloy substrate; passing an externally generated aluminum halide gas through an internal gas generator which is integral with a retort, the internal gas generator generating a modified halide gas; and co-depositing aluminum and modifier onto the superalloy substrate. In one form, the modified halide gas is hafnium chloride and the modifier is hafnium with the modified platinum aluminum bond coat comprising a single phase additive layer of platinum aluminide with at least about 0.5 percent hafnium by weight percent and about 1 to about 15 weight percent of hafnium in the boundary between a diffusion layer and the additive layer. The bond coat produced by this method is also claimed.

Nagaraj, Bangalore A.↗

Lunar Sulfur Capture System

The Lunar Sulfur Capture System (LSCS) protects in situ resource utilization (ISRU) hardware from corrosion, and reduces contaminant levels in water condensed for electrolysis. The LSCS uses a lunar soil sorbent to trap over 98 percent of sulfur gases and about two-thirds of halide gases evolved during hydrogen reduction of lunar soils. LSCS soil sorbent is based on lunar minerals containing iron and calcium compounds that trap sulfur and halide gas contaminants in a fixed-bed reactor held at temperatures between 250 and 400 C, allowing moisture produced during reduction to pass through in vapor phase. Small amounts of Earth-based polishing sorbents consisting of zinc oxide and sodium aluminate are used to reduce contaminant concentrations to one ppm or less. The preferred LSCS configuration employs lunar soil beneficiation to boost concentrations of reactive sorbent minerals. Lunar soils contain sulfur in concentrations of about 0.1 percent, and halogen compounds including chlorine and fluorine in concentrations of about 0.01 percent. These contaminants are released as gases such as H2S, COS, CS2,HCl, and HF during thermal ISRU processing with hydrogen or other reducing gases. Removal of contaminant gases is required during ISRU processing to prevent hardware corrosion, electrolyzer damage, and catalyst poisoning. The use of Earth-supplied, single-use consumables to entirely remove contaminants at the levels existing in lunar soils would make many ISRU processes unattractive due to the large mass of consumables relative to the mass of oxygen produced. The LSCS concept of using a primary sorbent prepared from lunar soil was identified as a method by which the majority of contaminants could be removed from process gas streams, thereby substantially reducing the required mass of Earth-supplied consumables. The LSCS takes advantage of minerals containing iron and calcium compounds that are present in lunar soil to trap sulfur and halide gases in a fixedbed reactor downstream of an in-ISRU process such as hydrogen reduction. The lunar-soil-sorbent trap is held at a temperature significantly lower than the operating temperature of the hydrogen reduction or other ISRU process in order to maximize capture of contaminants, but is held at a high enough temperature to allow moisture to pass through without condensing. The lunar soil benefits from physical beneficiation to remove ultrafine particles (to reduce pressure drop through a fixed bed reactor) and to upgrade concentrations of iron and/or calcium compounds (to improve reactivity with gaseous contaminants).

Berggren, Mark↗

Phosphate anion-quaternary ammonium ion pair coordinated polymer membranes

Ion exchange membranes materials according to the present disclosure exhibit improved conductivity at low and intermediate relative humidity without sacrificing mechanical strength. Polymers are provided that include a backbone with one or more aryl groups, a halocarbyl group, and a halocarbyl side chain attached to the backbone, wherein the halocarbyl side chain includes a halide separated from the backbone by a hydrocarbyl chain, a hydrocarbyl ring, or combinations thereof. The halide is substituted with a tertiary amine and halide anions are then exchanged with hydroxide anions. The polymers are then contacted with phosphoric acid, which is deprotonated by the hydroxide ions, forming anions which enhance interactions with adjacent quaternary ammonium groups and induce excess phosphoric acid molecules to cluster around those quaternary ammonium groups. The membranes exhibit negligible dopant leaching even at high relative humidity.

Bae, Chulsung↗

Room-Temperature Ferroelectric Epitaxial Nanowire Arrays with Photoluminescence

The development of large-scale, high-quality ferroelectric semiconductor nanowire arrays with interesting light-emitting properties can address limitations in traditional wide-bandgap ferroelectrics, thus serving as building blocks for innovative device architectures and next-generation high-density optoelectronics. Here, we investigate the optical properties of ferroelectric CsGeX 3 (X = Br, I) halide perovskite nanowires that are epitaxially grown on muscovite mica substrates by vapor phase deposition. Detailed structural characterizations reveal an incommensurate heteroepitaxial relationship with the mica substrate. Furthermore, photoluminescence that can be tuned from yellow-green to red emissions by varying the halide composition demonstrates that these nanowire networks can serve as platforms for future optoelectronic applications. In addition, the room-temperature ferroelectricity and ferroelectric domain structures of these nanowires are characterized using second harmonic generation (SHG) polarimetry. Finally, the combination of room-temperature ferroelectricity with photoluminescence in these nanowire arrays unlocks new avenues for the design of novel multifunctional materials.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Screw-Dislocation-Driven Growth of 2D Perovskite Spiral Microplates

Two-dimensional (2D) organic–inorganic halide perovskites are solution-processable semiconductors that are promising for optoelectronic applications. Understanding crystallization mechanisms to achieve control over nanostructures is important for optimizing desired properties. Here we introduce a versatile strategy to synthesize spiral microplates of diverse 2D perovskites at the air–water interface through screw-dislocation-driven growth. Spirals of 11 2D perovskite compositions (LA) 2 (A) n−1 Pb n X 3n+1 with different spacer (LA) cations, A-cations, halide (X) anions, and n-number can be grown. They typically consist of single- or few-layer perovskite step heights but exhibit stacking complexity when multiple dislocations interact. The spiral microplates exhibit the characteristic optical properties (photoluminescence and second-harmonic generation) of the underlying 2D perovskites. Fluorescence-detected circular dichroism imaging shows that the chirality of the spiral center does not translate to the observed chiroptical properties of the microplate, consistent with the length scale of the chiral distortion. Furthermore, this solution growth of perovskite spirals diversifies the perovskite microstructures for optoelectronics and other applications.

2D halide perovskites↗

Thin Film Synthesis of SrZn2P2 with SrI2 Post-Annealing for Enhanced Crystallinity and Optoelectronic Quality

Ternary Zintl phosphides are promising light-absorbing semiconductors for thin-film optoelectronic applications, but strategies for controlling their microstructure and optoelectronic quality remain underexplored. Here, we report the synthesis of phase-pure SrZn2P2 thin films using radio-frequency co-sputtering in a PH3 + Ar atmosphere and investigate the impact of post-growth processing on their structural and optical properties. Grazing-incidence X-ray scattering and Raman spectroscopy confirm the formation of crystalline SrZn2P2 films over a finite compositional window. Optical measurements reveal clear absorption near the direct-band-gap energy (~1.8 eV) and near-band-edge photoluminescence. Further, we have studied the effects of chemically compatible halide-assisted annealing. It is found that SrI2 treatments lead to pronounced grain growth and reduced diffraction peak broadening while preserving phase purity, in contrast to rapid thermal or forming-gas annealing. Notably, annealing with SrI2 at 450 degrees C significantly enhances both the intensity and spatial uniformity of the photoluminescence, thus connecting the observed microstructural consolidation with improved radiative recombination. Our study demonstrates that halide-assisted annealing provides an effective pathway for microstructural control in SrZn2P2 thin films and highlights a generalizable processing strategy for advancing Zintl phosphide semiconductors toward optoelectronic applications.

14 SOLAR ENERGY↗

Interface Engineering using Vapor Transport Deposited Perovskite Films for Solar Cells

The overarching goal of this project was to demonstrate the viability of vapor transport deposition (VTD) for the fabrication of efficient and stable metal-halide perovskite solar cells. VTD is a solvent-free alternative to conventional solution-processing of the light-absorbing, perovskite active layer. Since solution-processing frequently requires the use of toxic solvents, transition to a dry-processing approach has the potential to remove an obstacle to facile and economically meaningful commercialization. Further, VTD bears similarity to existing industrially-relevant processing approaches used for the production of thin-film CdTe solar modules, suggesting the potential for rapid adoption and transition to industry. The results described within this report offer design rules for the processing of metal-halide perovskites via VTD and new insights into the design of deposition systems to inform future applications.

14 SOLAR ENERGY↗

Förster Resonance Energy Transfer and Enhanced Emission in Cs 4 PbBr 6 Nanocrystals Encapsulated in Silicon Nano-Sheets for Perovskite Light Emitting Diode Applications

Encapsulating Cs 4 PbBr 6 quantum dots in silicon nano-sheets not only stabilizes the halide perovskite, but also takes advantage of the nano-sheet for a compatible integration with the traditional silicon semiconductor. Here, we report the preparation of un-passivated Cs 4 PbBr 6 ellipsoidal nanocrystals and pseudo-spherical quantum dots in silicon nano-sheets and their enhanced photoluminescence (PL). For a sample with low concentrations of quantum dots in silicon nano-sheets, the emission from Cs 4 PbBr 6 pseudo-spherical quantum dots is quenched and is dominated with Pb 2+ ion/silicene emission, which is very stable during the whole measurement period. For a high concentration of Cs 4 PbBr 6 ellipsoidal nanocrystals in silicon nano-sheets, we have observed Förster resonance energy transfer with up to 87% efficiency through the oscillation of two PL peaks when UV excitation switches between on and off, using recorded video and PL lifetime measurements. In an area of a non-uniform sample containing both ellipsoidal nanocrystals and pseudo-spherical quantum dots, where Pb 2+ ion/silicene emissions, broadband emissions from quantum dots, and bandgap edge emissions (515 nm) appear, the 515 nm peak intensity increases five times over 30 min of UV excitation, probably due to a photon recycling effect. This irradiated sample has been stable for one year of ambient storage. Cs 4 PbBr 6 quantum dots encapsulated in silicon nano-sheets can lead to applications of halide perovskite light emitting diodes (PeLEDs) and integration with traditional semiconductor materials.

36 MATERIALS SCIENCE↗

Identification and Suppression of Point Defects in Bromide Perovskite Single Crystals Enabling Gamma‐Ray Spectroscopy

Abstract Methylammonium lead tribromide (MAPbBr 3 ) stands out as the most easily grown wide‐band‐gap metal halide perovskite. It is a promising semiconductor for room‐temperature gamma‐ray ( γ ‐ray) spectroscopic detectors, but no operational devices are realized. This can be largely attributed to a lack of understanding of point defects and their influence on detector performance. Here, through a combination of crystal growth design and defect characterization, including positron annihilation and impedance spectroscopy, the presence of specific point defects are identified and correlated to detector performance. Methylammonium (MA) vacancies, MA interstitials, and Pb vacancies are identified as the dominant charge‐trapping defects in MAPbBr 3 crystals, while Br vacancies caused doping. The addition of excess MABr reduces the MA and Br defects and so enables the detection of energy‐resolved γ ‐ray spectra using a MAPbBr 3 single‐crystal device. Interestingly, the addition of formamidinium (FA) cations, which converted to methylformamidinium (MFA) cations by reaction with MA + during crystal growth further reduced MA defects. This enabled an energy resolution of 3.9% for the 662 keV 137 Cs line using a low bias of 100 V. The work provides direction toward enabling further improvements in wide‐bandgap perovskite‐based device performance by reducing detrimental defects.

Ni, Zhenyi↗

Tailoring Ion Transport in Li 3‐3y Ho 1+y Cl 6‐x Br x via Transition‐Metal Free Structural Planes and Charge Carrier Distribution

Abstract Localized atomistic disorder in halide‐based solid electrolytes (SEs) can be leveraged to boost Li + mobility. In this study, Li + transport in structurally modified Li 3 HoCl 6 , via Br − introduction and Li + deficiency, is explored. The optimized Li 3‐3 y Ho 1+ y Cl 6‐ x Br x achieves an ionic conductivity of 3.8 mS cm −1 at 25 °C, the highest reported for holmium halide materials. 6,7 Li nuclear magnetic resonance and relaxometry investigations unveil enhanced ion dynamics with bromination, attaining a Li + motional rate neighboring 116 MHz. X‐ray diffraction analyses reveal mixed‐anion‐induced phase transitions with disproportionate octahedral expansions and distortions, creating Ho‐free planes with favorable energetics for Li + migration. Bond valence site energy analysis highlights preferred Li + transport pathways, particularly in structural planes devoid of Ho 3+ blocking effects. Molecular dynamics simulations corroborate enhanced Li + diffusion with Br − introduction into Li 3 HoCl 6 . Li‐Ho electrostatic repulsions in the (001) plane presumably drive Li + diffusion into the Ho‐free (002) layer, enabling rapid intraplanar Li + motion and exchange between the 2d and 4h sites. Li 3‐3 y Ho 1+ y Cl 6‐ x Br x also demonstrates good battery cycling stability. These findings offer valuable insights into the intricate correlations between structure and ion transport and will help guide the design of high‐performance fast ion conductors for all‐solid‐state batteries.

Chemistry↗

Crack‐Free Single‐Crystalline LiNiO 2 for High Energy Density All‐Solid‐State Batteries

Abstract Single‐crystalline layered oxide (LiNi 1‐ x ‐ y Mn x Co y O 2 ) cathodes have been found to exhibit exceptional electrochemical properties when coupled with various inorganic solid electrolytes (ISEs) in all‐solid‐state batteries (ASSBs). Their advantages stem from the robust morphological integrity with the absence of grain boundaries and the high electrochemical oxidative stability. Here, ASSBs featuring single‐crystalline LiNiO 2 (LNO) with the highest Ni content are reported, offering a high theoretical specific capacity of 275 mAh g ‐1 alongside a high average discharge voltage (3.7 V vs Li + /Li). Through a careful investigation, it is demonstrated that micron‐sized single‐crystalline LNO (µSC‐LNO) composite cathodes with a halide ISE exhibit a high initial discharge capacity of 205 mAh g ‐1 with an outstanding cycle performance over 200 cycles in room‐temperature ASSBs. The significance of engineering parameters is emphasized, such as particle size and specific density, in promoting a homogeneous and fast Li + transport within the composite cathodes. Furthermore, the formation of undesirable interphase between the halide ISE in the cathode and sulfide ISE separator is elucidated, which may be a critical factor impeding long‐term cyclability of ASSBs. This work provides insights into the design of composite cathodes for high‐energy‐density ASSBs.

Chemistry↗

Evolution of Surface Chemistry in Two‐Dimensional MXenes: From Mixed to Tunable Uniform Terminations

Abstract Surface chemistry of MXenes is of great interest as the terminations can define the intrinsic properties of this family of materials. The diverse and tunable terminations also distinguish MXenes from many other 2D materials. Conventional fluoride‐containing reagents etching approaches resulted in MXenes with mixed fluoro‐, oxo‐, and hydroxyl surface groups. The relatively strong chemical bonding of MXenes’ surface metal atoms with oxygen and fluorine makes post‐synthetic covalent surface modifications of such MXenes unfavorable. In this minireview, we focus on the recent advances in MXenes with uniform surface terminations. Unconventional methods, including Lewis acidic molten salt etching (LAMS) and bottom‐up direct synthesis, have been proven successful in producing halide‐terminated MXenes. These synthetic strategies have opened new possibilities for MXenes because weaker surface chemical bonds in halide‐terminated MXenes facilitate post‐synthetic covalent surface modifications. Both computational and experimental results on surface termination‐dependent properties are summarized and discussed. Finally, we offer our perspective on the opportunities and challenges in this exciting research field.

Jiang, Mengni↗

Evolution of Surface Chemistry in Two‐Dimensional MXenes: From Mixed to Tunable Uniform Terminations

Abstract Surface chemistry of MXenes is of great interest as the terminations can define the intrinsic properties of this family of materials. The diverse and tunable terminations also distinguish MXenes from many other 2D materials. Conventional fluoride‐containing reagents etching approaches resulted in MXenes with mixed fluoro‐, oxo‐, and hydroxyl surface groups. The relatively strong chemical bonding of MXenes’ surface metal atoms with oxygen and fluorine makes post‐synthetic covalent surface modifications of such MXenes unfavorable. In this minireview, we focus on the recent advances in MXenes with uniform surface terminations. Unconventional methods, including Lewis acidic molten salt etching (LAMS) and bottom‐up direct synthesis, have been proven successful in producing halide‐terminated MXenes. These synthetic strategies have opened new possibilities for MXenes because weaker surface chemical bonds in halide‐terminated MXenes facilitate post‐synthetic covalent surface modifications. Both computational and experimental results on surface termination‐dependent properties are summarized and discussed. Finally, we offer our perspective on the opportunities and challenges in this exciting research field.

Jiang, Mengni↗

Iodide Double Perovskites and the Limits of their Structural Stability

AbstractWhile halide double perovskites A2M(I)M(III)X6 have attracted significant attention, examples involving iodides are rare. We examine the limits of the structural stability of iodide double perovskites, presenting the synthesis and single‐crystal structures of Cs2NaScI6 and Cs2NaYI6. Bypassing the common expectation that iodides have small band gaps, these compounds display optical gaps of 3.10 eV [M(III) = Sc] and 3.65 eV [M(III) = Y]. Cs2NaScI6 is the only iodide double perovskite to exhibit a cubic crystal structure at room temperature. Density functional theory‐based electronic structure calculations help understand the role of competing Cs3M(III)2I9 (3 : 2 : 9) phases and provide possible reasons for why iodide double perovskites based around In(III), Sb(III) and Bi(III) cations have proved elusive. We confirm design rules for halide double perovskites based around concepts of the tolerance factor and the radius ratio of the smaller, trivalent ion, but also point to situations such as what is observed for Cs2NaScI6 where a double perovskite can be trapped in a metastable structure.

Mulligan, Anya S.↗

Thermal Elimination of Pyridine from a Uranium Trichloride Precursor

Renewed interest in advanced nuclear reactors, such as Molten Salt Reactors (MSRs), has spurred studies in actinide halide chemistry and property measurements. Several proposed research-scale and commercial MSR designs incorporate uranium trichloride (UCl 3 ) fuel. There are relatively few preparations for isolated actinide halides reported in the literature, therefore novel methods for the isolation of pure material are desired. This communication describes the thermal elimination of pyridine (py) from the coordination complex UCl 3 py 2 to yield gram-scale quantities of UCl 3 . The purity of the UCl 3 product was determined through powder X-ray Diffractometry (pXRD) and Elemental Analysis (EA).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural coherence model for predicting molten salt thermal conductivity informed by the pair distribution function

To enable thermal behavior prediction and design optimization of molten salt reactors, thermal conductivity of molten salts must be characterized in terms of salt composition and temperature. Current theoretical models fail to provide consistent approximations for all halide mixtures, particularly actinide-bearing melts. This study aims to link the short-range order structure of molten salts to the mean free path of energy carriers through a simple structural coherence model informed by the partial pair distribution function. The proposed method is used to predict the thermal conductivity of 33 alkali and alkaline earth halide salts. Predictions approximate experimental measurements with a mean absolute error of 15.7% for dissociating, complexing, and actinide salts, including unary LiCl, NaCl, and MgCl 2 as well as mixtures LiF–NaF–KF (FLiNaK), LiF–BeF 2 (FLiBe), and NaCl–UCl 3 . The work provides evidence for the validity of energy carrier descriptions of molecular-level heat transfer in molten salts, with implications for improved theories of liquid energy transport in general.

Actinide mixtures↗

Interpreting accelerated tests on perovskite modules using photooxidation of MAPbI 3 as an example

Solar panels (modules) based on metal halide perovskites are following a fast track to commercialization. Unlike more established solar cell materials, there are not yet decades-long field observations to increase consumer confidence. The "physics and chemistry of failure" approach is used in other industries and estimates product degradation based on laboratory accelerated tests integrated with an understanding of degradation mechanisms. This work uses that approach to quantify the relationship between accelerated tests and projected product behavior for metal halide perovskite modules. Degradation involving photooxidation of methylammonium lead iodide is used to illustrate the method. Acceleration factors in common accelerated tests are found to be low. Conclusions emphasize that the accelerated tests on photovoltaics should not be interpreted as equivalent across module types or as a green light for commercialization unless supported by the appropriate field data or physics and chemistry of failure analysis.

14 SOLAR ENERGY↗

Smaller Is Better: The Case for Lower-Order Iodoplumbate Species Dominating MAPbI 3 /Dimethylformamide Solutions

Here, using complementary experimental measurements and computational predictions of spectroscopic measurements (EXAFS, XANES, and UV–vis), we have determined the identity of the most stable iodoplumbate species in dilute lead halide perovskite precursor solutions. We have determined which species are most likely to be thermodynamically stable compared to others that are unstable or metastable. Condensed phase ab initio models were constructed, and the resulting ensembles were used to directly compare the computed signals to the experimental results of the EXAFS, XANES, and UV–vis spectra of PbI 2 :MAI in DMF. The results of this study suggest that only Pb 2+ , PbI + , and PbI 2 are dominant in the dilute lead perovskite precursor solutions as thermodynamically stable entities. Our interpretation of the relative stability of iodoplumbate species in solution, based on an analysis of EXAFS and XANES spectra, provides critically important new insight into the species most likely to be responsible for crystal nucleation and growth in these materials. This insight will have a significant consequence on the broad scientific community and will necessitate the reinterpretation of peaks in the UV–vis spectra of lead halide perovskite precursor solutions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗