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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

ALD with Alternative Coreactants: Which Work, Which Do Not, and Why

In this paper, we present a combined experimental and theoretical study that systematically evaluates a series of alcohols (i.e., primary, secondary, and tertiary) as coreactants for trimethylaluminum (TMA)-based atomic layer deposition (ALD) of Al 2 O 3 . We employed in situ quartz crystal microbalance techniques and ex situ X-ray photoelectron spectroscopy to probe growth across a range of temperatures from T = 120 to 285 °C. Dispersion-inclusive hybrid density functional theory was employed to identify potential reaction pathways and compute corresponding Gibbs free-energy barriers and rate coefficients. Experimentally on an Al 2 O 3 surface, sustained thin-film growth, where the rate is constant over many cycles, was only observed with tertiary alcohols (tert-butanol and 2-methyl-2-butanol) at elevated temperatures (e.g., T = 285 °C); for tert-butanol specifically, sustained growth also occurred at T = 240 °C, with no sustained growth at or below T = 210 °C. Growth using primary and secondary alcohols decayed to a negligible value after only 2–3 cycles on an Al 2 O 3 surface at all tested temperatures. Intentional trace additions of H 2 O to anhydrous alcohols restored sustained growth but at reduced deposition rates relative to pure H 2 O. Theoretical analysis supports a bimolecular alkoxy β-H elimination mechanism as the primary reaction pathway: initiated by the formation of a bound alkoxy species, the subsequent β-H elimination step is rate-determining, with a barrier that systematically decreases as the degree of the alcohol coreactant is increased from primary to secondary to tertiary. Computed rate coefficients (k) also indicate a strong temperature dependence (with k increasing by ∼4–5 orders of magnitude from T = 120 to 285 °C) and are consistent with the experimental observation that only tertiary alcohols lead to steady thin-film growth at elevated temperatures. This integrated approach establishes why only certain alcohols can sustain Al 2 O 3 ALD and delivers a predictive framework for identifying effective alcohol coreactants.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Impact of Pendent Ammonium Groups on Solubility and Cycling Charge Carrier Performance in Nonaqueous Redox Flow Batteries

The synthesis, characterization, electrochemical performance, and theoretical modeling of two base-metal charge carrier complexes incorporating a pendent quaternary ammonium group, [Ni(bppn-Me3)][BF4], 3′, and [Fe(PyTRENMe)][OTf]3, 4’, are described. Both complexes were produced in high yield and fully characterized using NMR, IR, and UV–vis spectroscopies as well as elemental analysis and single-crystal X-ray crystallography. The solubility of 3′ in acetonitrile showed a 283% improvement over its neutral precursor, whereas the solubility of complex 4’ was effectively unchanged. Cyclic voltammetry indicates an ∼0.1 V positive shift for all waves, with some changes in reversibility depending on the wave. Bulk electrochemical cycling demonstrates that both 3′ and 4’ can utilize the second more negative wave to a degree, whereas 4’ ceases to have a reversible positive wave. Flow cell testing of 3′ and 4’ with Fc as the posolyte reveals little improvement to the cycling performance of 3′ compared with its parent complex, whereas 4’ exhibits reductions in capacity decay when cycling either negative wave. Postcycling CVs indicate that crossover is the likely source of capacity loss in complexes 3, 3′, and 4’ because there is little change in the CV trace. Density functional theory calculations indicate that the ammonium group lowers the HOMO energy in 3′ and 4’, which may impart stability to cycling negative waves while making positive waves less accessible. The incorporation of a positively charged species can improve solubility, stored electron density, and capacity decay depending on the complex, features critical to high energy density redox flow battery performance.

25 ENERGY STORAGE↗
DOE OSTI2025

Single-shot measurements of shaped XUV FEL pulses with frequency-resolved optical gating

The ability to control the amplitude and phase of extreme ultraviolet (XUV) and X-ray free-electron laser (FEL) pulses can allow for the extension of optical techniques, such as multidimensional spectroscopy or coherent control, to higher photon energies, for probing and controlling core electronic transitions. However, this requires the ability to make single-shot, and complete, electric field measurements of potentially complex FEL pulses, in order to develop, and verify, pulse shaping strategies. Here, we present direct, single-shot measurements of XUV pulses generated under special operating configurations for producing specific pulse shapes from a laser-seeded XUV FEL. To do this, we built upon our past work using transient grating (TG) cross correlation frequency-resolved optical gating (FROG), where an optical reference pulse is diffracted from an XUV TG produced by a pair of interfering FEL pulses. The resulting nonlinear signal versus frequency and delay, i.e., the FROG trace, contains the electric field of the FEL pulse. The FEL pulse electric field is reconstructed from the FROG trace using a phase retrieval algorithm. Here we confirmed three different pulse shaping strategies for generating chirped, double and multiple FEL pulses by tuning the seed laser and FEL parameters and measuring the resulting shaped FEL pulses with TG XFROG. This work paves the way for generating on-demand pulse shapes with a seeded FEL by improving the characterization of FEL pulses, for transform-limited to more complex shapes.

Elverson, Francesca↗
DOE OSTI2020

Effect of Water Concentration in LiPF 6 -Based Electrolytes on the Formation, Evolution, and Properties of the Solid Electrolyte Interphase on Si Anodes

A trace amount of water in an electrolyte is one of the factors detrimental to the electrochemical performance of silicon (Si)-based lithium-ion batteries that adversely affect the formation and evolution of the solid electrolyte interphase (SEI) on Si-based anodes and change its properties. Thus far, a lack of fundamental and mechanistic understanding of SEI formation, evolution, and properties in the presence of water has inhibited efforts to stabilize the SEI for improved electrochemical performance. As such, we investigated the SEI formed in a Gen2 electrolyte (1.2 M LiPF6 in ethylene carbonate/ethyl methyl carbonate, 3:7 wt %, water content: <10 ppm) with and without additional water (50 ppm) at varying potentials (1.0, 0.5, 0.2, and 0.01 V vs Li/Li + ). The impact of additional water on the morphological, (electro)chemical, and structural properties of SEI was studied using microscopic (atomic force microscopy and scanning spreading resistance microscopy) and spectroscopic (X-ray photoelectron spectroscopy, attenuated total reflection Fourier-transform infrared spectroscopy, and time-of-flight secondary ion mass spectrometry) techniques. The SEI exhibits both potential- and water concentration-dependent trends in its morphology and chemical composition. The presence of additional water in the electrolyte causes parasitic reactions, which onset at ~1.0 V, resulting in a reduction of electrolyte components and result in the formation of an insulating, fluorophosphate-rich SEI. In addition, hydrolysis of LiPF 6 creates hydrofluoric acid, which reacts with the surface oxide layer on the Si electrode, leading to a pitted and inhomogeneous SEI structure.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Radio fossils, relics, and haloes in Abell 3266: cluster archaeology with ASKAP-EMU and the ATCA

ABSTRACT Abell 3266 is a massive and complex merging galaxy cluster that exhibits significant substructure. We present new, highly sensitive radio continuum observations of Abell 3266 performed with the Australian Square Kilometre Array Pathfinder (0.8–1.1 GHz) and the Australia Telescope Compact Array (1.1–3.1 GHz). These deep observations provide new insights into recently reported diffuse non-thermal phenomena associated with the intracluster medium, including a ‘wrong-way’ relic, a fossil plasma source, and an as-yet unclassified central diffuse ridge, which we reveal comprises the brightest part of a large-scale radio halo detected here for the first time. The ‘wrong-way’ relic is highly atypical of its kind: it exhibits many classical signatures of a shock-related radio relic, while at the same time exhibiting strong spectral steepening. While radio relics are generally consistent with a quasi-stationary shock scenario, the ‘wrong-way’ relic is not. We study the spectral properties of the fossil plasma source; it exhibits an ultrasteep and highly curved radio spectrum, indicating an extremely aged electron population. The larger scale radio halo fills much of the cluster centre, and presents a strong connection between the thermal and non-thermal components of the intracluster medium, along with evidence of substructure. Whether the central diffuse ridge is simply a brighter component of the halo, or a mini-halo, remains an open question. Finally, we study the morphological and spectral properties of the multiple complex radio galaxies in this cluster in unprecedented detail, tracing their evolutionary history.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2025

Expedition UT-GOM2-2 Site H

Pressure and conventional cores were collected at Site H of the Walker Ridge Protracted Area Block 313 in the Terrebonne Basin, deepwater Gulf of America (Gulf of Mexico) during the University of Texas (UT) Deepwater Hydrate Coring Expedition (UT-GOM2-2). Pressure and conventional cores were collected continuously to a depth of 155.1 meters below the seafloor (mbsf). At deeper depths, cores were taken periodically from hydrate-bearing sands and their bounding muds to a total depth of 861.3 mbsf. 162.6 m of conventional core and 54.8 m of pressure core were recovered. Twelve temperature measurements were made between 27.1 and 144.5 mbsf to determine the geothermal gradient. At the seafloor, more than 4 m of sandy silt of unknown origin was encountered. Beneath this sand, to a depth of about 200 mbsf, the section was composed of interbedded mud and biogenic carbonate ooze. The ooze correlated to low density and high porosity intervals observed in the previously acquired logging while drilling (LWD) data and as measured. These ooze intervals also correspond to lighter sediment color, increased Ca content based on X-ray florescence (XRF) core scanning, and increased calcareous nannofossil abundance. Calcareous nannofossil biostratigraphy constrains the entire record to the Pleistocene (< 0.91 million years), with a pronounced increase in sedimentation rate with depth. Below 200 mbsf, the section was predominantly composed of mud with two thicker, hydrate-bearing coarse-grained intervals, which are commonly known as the Blue and Orange sands. The dissolved gas concentration was quantified from pressure cores. In the shallow section, dissolved methane concentration increased below the sulfate-methane transition zone (SMTZ) and reaches saturation (the limit of solubility for methane) at 147 mbsf. Gas expansion was very common in conventional and depressurized pressure (conventionalized) cores below the SMTZ. At deeper depths, the methane concentration within muds bounding the Blue and Orange reservoirs was generally found to be less than saturation. The dissolved and hydrate gas composition is consistent with a microbial source, containing greater than 99.99% methane and only trace concentrations of ethane, propane, and butane. The methane to ethane ratio (C1 /C2 ) and the methane to ethane plus propane (C1 /(C2 +C3 )) decrease with depth down to at least 678 mbsf, mainly driven by the increase in ethane with depth. It is unclear if this trend continues through the Orange sand interval. The δ13C isotopic signature of methane ranges between -69.9 and -78.5 ‰ relative to the Vienna Pee Dee Belemnite (VPDB) standard. Pressure core recovery in sandy intervals was poor. However, pressure core logs of the Orange sand show intervals of low density and high velocity, which are indicative of high hydrate saturation. One pressure core was degassed and the average hydrate saturation in the core was determined to be 24%. One core from within the Orange sand was composed of interbedded graded sandy silt and mud. The sandy silts from this core are composed of mainly quartz and feldspar with some lithics. Most of the recovered pressure core samples are maintained at near in-situ pressure and temperature (within the hydrate stability field) at the University of Texas Pressure Core Center awaiting analysis. In the shallow section, samples will be used to determine the flux of organic carbon through the basin system, find the rate at which that carbon was consumed, and understand the microbial population responsible for these processes. In the deeper section, samples from in and around the hydrate reservoirs will be used to determine the petrophysical properties of the reservoir and bounding seals in these systems.

03 NATURAL GAS↗
DOE OSTI2026

One Earth Energy FEED Process Design Basis

This report establishes the process design basis for the front-end engineering design (FEED) of a carbon capture and injection facility at One Earth Energy's (OEE) ethanol production plant in Gibson City, Illinois, developed as part of the Illinois Storage Corridor CarbonSAFE Phase III project. The facility is designed to compress and dehydrate up to approximately 458,000 metric tonnes of CO 2 per year, sourced directly from OEE's ethanol fermenters, for permanent injection into a saline aquifer approximately four miles from the plant. At normal operating conditions, the system will process 1,290 metric tonnes of CO 2 per day, assuming 355 operating days per year and an ethanol production rate of 160 million gallons per year. The proposed process trains a multistage centrifugal blower with a five-stage reciprocating compressor, delivering CO 2 to the injection wellhead at up to 1,500 psig. Triethylene glycol (TEG) dehydration, applied after the fourth compression stage, reduces water content to a target of 10 lb/MMscf, well within the 30 lb/MMscf injection limit. Beyond dehydration, no additional treatment is required; trace impurities including oxygen and nitrogen will remain in the injected stream. Key design considerations include the absence of spare cooling tower capacity at the site, necessitating new cooling infrastructure, and the need for a new electrical substation to support large motor loads. The facility is designed for continuous, largely unattended operation, monitored around the clock by existing OEE operations staff. This document serves as the foundational reference for all subsequent detailed engineering activities associated with the OEE CO 2 injection facility.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2023

Significance of pH and iron-sulfur chemistry for molybdenum sequestration under sulfidic conditions

Molybdenum (Mo), a redox-sensitive trace metal, plays an important role in recording ancient oxygenation and deoxygenation events as a paleoredox proxy. The mobility and reactivity of Mo in aqueous conditions are closely tied to the chemistry of reduced sulfur and iron species. However, our current knowledge on the formation, structure, stability, and condensation pathways of FeMoS clusters in aqueous settings remains limited, which has driven the current study. In this study, we conducted systematic experiments investigating the interactions between dissolved Mo (initially introduced as molybdate, MoO 4 2– , or tetrathiomolybdate, MoS 4 2– ), ferrous iron (Fe 2+ ), and sulfide (ΣH 2 S aq ) in variously defined abiotic sulfidic systems to determine the external conditions (i.e., pH, and reactant concentrations and ratios) necessary for the formation of solid-phase Fe-Mo sulfides. Solution samples of each system were monitored using ultraviolet-visible spectroscopy (UV–vis) to track the degree of thiolation of dissolved Mo species. Precipitates were analyzed using X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) to determine their elemental compositions and valences, and structure (i.e., crystalline or amorphous), respectively. All FeMoS precipitates were amorphous and contained 76–90% Mo(IV) and 10–24% Mo(V) with a trend toward lower Mo(IV):Mo(V) ratios with increasing pH. The degree of Mo thiolation, which was strongly dependent on solution pH and Fe 2+ concentrations, greatly affected the amount of Mo sequestered (i.e., an increased degree of Mo thiolation in solution led to an increased amount of Mo in the final FeMoS precipitate). Furthermore, these findings suggest that changes in pH and Fe 2+ concentrations may be responsible for the sulfide-independent variations in Mo behavior observed in euxinic basins.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Comparison of Shadowgraphy and X-Ray Phase Contrast Methods for Characterizing a DT Ice Layer in an Inertial Confinement Fusion Target

Shadowgraphy and x-ray phase contrast (XPC) imaging are two techniques that are used for characterizing the deuterium-tritium ice layer in Inertial Confinement Fusion targets. Each technique has limitations that affect how accurately they can characterize small crystalline defects and measure the ice-thickness non-uniformities that may be only a few micrometers in height. The concern is that shadowgraphy may be overly sensitive to the shape and depth of defects in the surface and insufficiently sensitive to the shape of longer-wavelength roughness, while x-ray phase contrast may be too insensitive to defects in the ice surface. Multiple ice layers with different thicknesses (40 to 63 μm), thickness uniformities (peak-valley variations that range from <2- to 12 μm), and crystal defects were analyzed using shadowgraphy and x-ray phase contrast techniques. The results from each method agree when the ice layer is uniformly thick and the crystal lacks defects. That agreement worsens as the number of defects in the surface of the ice layer increases and the roughness that is determined from a shadowgram image of the target’s limb is greater than can be justified by the number of defects that are seen in the target’s front and rear surfaces. The XPC technique is considerably less sensitive to surface defects, in part due to the poorer dynamic range and image resolution compared to shadowgraphy. Localized regions of the ice layer that are thicker or thinner than the average thickness of the layer are reported by shadowgraphy to be smaller in height and footprint (by up to 30%) than by XPC. As a result, the two techniques report different ice layer thicknesses that can vary by up to 10%. Shadowgraphy results from two caustics that trace different paths through the target, and, in theory, image the same ice-vapor surface (but reflect from either the vapor or ice side of the interface) did not consistently characterize the size or shape of ice features to be the same magnitude. Here, the XPC technique provides the best assessment of low-mode (l < 7) roughness in the ice layer. Shadowgraphy results using the strongest caustic is best for detecting the presence of grooves in the ice, though not for quantifying the size of them. If multiple grooves are present it is best to discard and reform the ice layer.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2025

Surface Phase Stability of Fe 2 O 3 (001) in Hydrogen Reducing Environments: A DFT and XPS Analysis

Here, this study combines density functional theory (DFT) and ab initio thermodynamics calculations with X-ray photoelectron spectroscopy (XPS) investigations to identify the reduction properties of the Fe 2 O 3 (001) surface with implications for corrosion resistance, hydrogen transport, and energy safety. Ab initio thermodynamics modeling predicts fully hydroxylated surface stability across a broad range of pressures (1 × 10 –23 to 1 × 10 5 mbar) and temperatures below 700 K, consistent with previous experimental studies. Above 800 K, exposures to 1 × 10 –4 mbar H 2 , 1 × 10 –4 mbar O 2 , or 1 × 10 –4 mbar H 2 + 1 × 10 –4 mbar O 2 each yield unique XPS signals indicating a loss of −OH coverage, aligning with DFT predictions. Insight into the mechanism of reduction as a function of H 2 exposure is provided, as well as conditions that promote further reduction toward Fe 3 O 4 . Theoretical and experimental investigations indicate the ability to maintain the Fe 2 O 3 protective layer of iron oxides that have been exposed to H 2 environments by including trace amounts of aqueous O2.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2021

Tomographic X-ray particle tracking velocimetry

We investigate the feasibility of in-laboratory tomographic X-ray particle tracking velocimetry (TXPTV) and consider creeping flows with nearly density matched flow tracers. Specifically, in these proof-of-concept experiments we examined a Poiseuille flow, flow through porous media and a multiphase flow with a Taylor bubble. For a full 360° computed tomography (CT) scan we show that the specially selected 60 micron tracer particles could be imaged in less than 3 seconds with a signal-to-noise ratio between the tracers and the fluid of 2.5, sufficient to achieve proper volumetric segmentation at each time step. In the pipe flow, continuous Lagrangian particle trajectories were obtained, after which all the standard techniques used for PTV or PIV (taken at visible wave lengths) could also be employed for TXPTV data. And, with TXPTV we can examine flows inaccessible with visible wave lengths due to opaque media or numerous refractive interfaces. In the case of opaque porous media we were able to observe material accumulation and pore clogging, and for flow with Taylor bubble we can trace the particles and hence obtain velocities in the liquid film between the wall and bubble, with thickness of liquid film itself also simultaneously obtained from the volumetric reconstruction after segmentation. While improvements in scan speed are anticipated due to continuing improvements in CT system components, we show that for the flows examined even the presently available CT systems could yield quantitative flow data with the primary limitation being the quality of available flow tracers.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2021

Using Fission-Track Radiography Coupled with Scanning Electron Microscopy for Efficient Identification of Solid-Phase Uranium Mineralogy at a Former Uranium Pilot Mill (Grand Junction, Colorado)

At a former uranium pilot mill in Grand Junction, Colorado, mine tailings and some subpile sediments were excavated to various depths to meet surface radiological standards, but residual solid-phase uranium below these excavation depths still occurs at concentrations above background. The combination of fission-track radiography and scanning electron microscope energy-dispersive X-ray spectroscopy (SEM-EDS) provides a uniquely efficient and quantitative way of determining mineralogic associations of uranium that can influence uranium mobility. After the creation of sample thin sections, a mica sheet is placed on those thin sections and irradiated in a nuclear research reactor. Decay of the irradiated uranium creates fission tracks that can be viewed with a microscope. The fission-track radiography images indicate thin section sample areas with elevated uranium that are focus areas for SEM-EDS work. EDS spectra provide quantitative elemental data that indicate the mineralogy of individual grains or grain coatings associated with the fission-track identification of elevated uranium. For the site in this study, the results indicated that uranium occurred (1) with coatings of aluminum–silicon (Al/Si) gel and gypsum, (2) dispersed in the unsaturated zone associated with evaporite-type salts, and (3) sorbed onto organic carbon. The Al/Si gel likely formed when low-pH waters were precipitated during calcite buffering, which in turn retained or precipitated trace amounts of Fe, As, U, V, Ca, and S. Understanding these mechanisms can help guide future laboratory and field-scale efforts in determining long-term uranium release rates to groundwater.

58 GEOSCIENCES↗
DOE OSTI2020

Functionalized Polymer Thin Films for Plutonium Capture and Isotopic Screening from Aqueous Sources

The rapid screening of plutonium from aqueous sources remains a critical challenge for nuclear nonproliferation efforts. The determination of trace-level Pu isotopes in water requires offsite sample preparation and analysis; therefore, new methods that combine plutonium purification, concentration, and isotopic screening in a fieldable detection system will provide an invaluable tool for nuclear safeguards. This contribution describes the development and characterization of thin polymer-ligand films for the isolation and concentration of waterborne Pu for direct spectroscopic analyses. Submicron thin films were prepared through spin coating onto Si wafers and consisted of combinations of polystyrene (PS) with dibenzoylmethane, thenoyltrifluoroacetone, and di(2-ethylhexyl)phosphoric acid (HDEHP). Pu uptake studies from solutions at pH from 2.3 to 6.3 indicated that only films containing HDEHP exhibited significant recovery of Pu. High alpha spectroscopy peak energy resolutions were achieved for PS-HDEHP films over a range of film thicknesses from 30 to 250 nm. Furthermore, a separate study was performed to evaluate uptake from a primarily Pu(V) solution where it was observed that doubling the HDEHP loading in the film increased uptake of Pu by an order of magnitude. X-ray photoelectron spectroscopy (XPS) analysis revealed that HDEHP was highly concentrated within the first few nanometers of the film at the higher loading. XPS analysis also revealed that, in the presence of water, HDEHP was stripped from the surface layer of the film at circumneutral pH. While significant losses of ligand were seen in all samples, higher loadings of HDEHP resulted in measurable amounts of ligand retained after a 12-h soak in water. Findings of this study are being used to guide the development of thin-film composite membrane-based detection methods for the rapid, fieldable analysis of Pu in water.

36 MATERIALS SCIENCE↗
DOE OSTI2022

The Solvation of the E. coli CheY Phosphorylation Site Mapped by XFMS

The Escherichia coli CheY protein belongs to a large bacterial response regulator superfamily. X-ray hydroxy radical foot-printing with mass spectroscopy (XFMS) has shown that allosteric activation of CheY by its motor target triggers a concerted internalization of aromatic sidechains. We reanalyzed the XFMS data to compare polar versus non-polar CheY residue positions. The polar residues around and including the 57D phosphorylated site had an elevated hydroxy radical reactivity. Bioinformatic measures revealed that a water-mediated hydrogen bond network connected this ring of residues with the central 57D. These residues solvated 57D to energetically stabilize the apo-CheY fold. The abundance of these reactive residues was reduced upon activation. This result was supported by the bioinformatics and consistent with the previously reported activation-induced increase in core hydrophobicity. It further illustrated XFMS detection of structural waters. Direct contacts between the ring residues and the phosphorylation site would stabilize the aspartyl phosphate. In addition, we report that the ring residue, 18R, is a constant central node in the 57D solvation network and that 18R non-polar substitutions determine CheY diversity as assessed by its evolutionary trace in bacteria with well-studied chemotaxis. These results showcase the importance of structured water dynamics for phosphorylation-mediated signal transduction.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Structural insights into Lewis acid- and F4TCNQ-doped conjugated polymers by solid-state magnetic resonance spectroscopy

Molecular doping strategies facilitate orders of magnitude enhancement in the charge carrier mobility of organic semiconductors (OSCs). Understanding the different doping mechanisms and molecular-level constraints on doping efficiency related to the material energy levels is crucial to develop versatile dopants for OSCs. Given the compositional and structural heterogeneities associated with OSC thin films, insight into dopant–polymer interactions by long-range techniques such as X-ray scattering and electron microscopy is exceedingly challenging to obtain. This study employs short-range probes, solid-state (ss)NMR and EPR spectroscopy, to resolve local structures and intermolecular interactions between dopants such as F4TCNQ (2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane), Lewis acid BCF (tris[pentafluorophenyl] borane) and Lewis base conjugated polymer, PCPDTBT (P4) (poly[2,6-(4,4-bis(2-hexadecyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene)-alt-4,7(2,1,3-benzothiadiazole)]). Analysis of 1 H and 13 C ssNMR spectra of P4, P4 : F4TCNQ and P4 : BCF blends indicates that the addition of dopants induces local structural changes in the P4 polymer, and causes paramagnetism-induced signal broadening and intensity losses. The hyperfine interactions in P4 : BCF and P4 : F4TCNQ are characterized by two-dimensional pulsed EPR spectroscopy. For P4 : F4TCNQ, 19 F ssNMR analysis indicates that the F4TCNQ molecules are distributed and aggregated into different local chemical environments. By comparison, BCF molecules are intermixed with the P4 polymer and interact with traces of water molecules to form BCF–water complexes that serve as Brønsted acid sites, as revealed by 11 B ssNMR spectroscopy. These results indicate that the P4–dopant blends exhibit complex morphology with different distributions of dopants, whereby the combined use of ssNMR and EPR provides essential insights into how higher doping efficiency is observed with BCF and a mediocre efficiency is associated with F4TCNQ molecules.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Unlocking the Origins of Ultracool Dwarf Radio Emission

Empirical trends in stellar X-ray and radio luminosities suggest that low-mass ultracool dwarfs (UCDs) should not produce significant radio emission. Defying these expectations, strong nonthermal emission has been observed in a few UCDs in the 1–10 GHz range, with a variable component often attributed to global aurorae and a steady component attributed to other processes, such as gyrosynchrotron emission. While both auroral and gyrosynchrotron emission peak near the critical frequency, only the latter radiation is expected to extend into millimeter wavelengths. We present Atacama Large Millimetre/Submillimeter Array (ALMA) 97.5 GHz and Very Large Array 33 GHz observations of a small survey of 5 UCDs. LP 349-25, LSR J1835+3259, and NLTT 33370 were detected at 97.5 GHz, while LP 423-31 and LP 415-20 resulted in nondetections at 33 GHz. A significant flare was observed in NLTT 33370, which reached a peak flux of 4880 ± 360 μJy, exceeding the quiescent flux by nearly an order of magnitude and lasting 20 s. These ALMA observations show bright 97.5 GHz emission with spectral indices ranging from α = 0.76 to α = −0.29, suggestive of optically thin gyrosynchrotron emission. If such emission traces magnetic reconnection events, then this could have consequences for both UCD magnetic models and the atmospheric stability of planets in orbit around them. Overall, our results provide confirmation that gyrosynchrotron radiation in radio-loud UCDs can remain detectable into the millimeter regime.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2025

LABQ3: Bayesian method for quantification of mineral compositions and nano-scale elemental mapping of 3D synchrotron XCT data

Quantitative analysis of mineral compositions is essential in understanding geochemical, mineralogical and environmental processes. Fine-resolution 3D imaging is widely done using synchrotron X-ray computed tomography (XCT), but existing analyses are limited to visualization and segmentation. This paper presents a new method, Linear Attenuation Bayesian Quantitative 3D-mapper (LABQ3), based on the linearity of X-ray attenuation with respect to elemental concentrations. To address the random variability in attenuation measurements, LABQ3 employs Bayesian decision theory to minimize classification error, using reference attenuation distributions from scans of pure mineral standards. To demonstrate LABQ3 and test its performance, we studied precipitated carbonate samples. XCT scans were done at multiple energies using the transmission X-ray microscope (TXM) at beamline 32-ID-C of the Advanced Photon Source at Argonne National Laboratory. The reconstructed 3D images have a voxel size of 20 nm. Analyses revealed rich nano-scale compositional heterogeneity within individual particles. A mixture of calcium and cadmium produced an overall stoichiometric composition of (Ca 0.78 ,Cd 0.22 )CO 3 , with some voxels containing nearly pure CdCO 3 . The addition of zinc led to an overall stoichiometric composition of 33% Ca, 28% Cd, 39% Zn, with a nearly pure CaCO 3 core and compositional zonation through the rim. These compositional gradients are related to temporal sequences of carbonate mineral formation where Cd precipitated at the beginning in (Ca,Cd)CO 3 , while Cd and Zn precipitated at the end in (Ca, Cd,Zn)CO 3 . Results differ from bulk analyses using Inductively Coupled Plasma-Mass Spectrometry (ICP-MS), showing that LABQ3 provides particle-specific insights. LABQ3 distinguishes itself by quantifying chemical compositions along a continuum, making it different from XCT analyses based on segmentation. LABQ3 allows simultaneous acquisition of morphology and chemical composition in 3D, facilitating the interpretation of chemical gradients of trace elements, quantification of solid solution compositions, inferences about temporal sequences of mineral precipitation, and addressing other concerns about solid-phase chemistry.

58 GEOSCIENCES↗
DOE OSTI2020

Ultrasonication-assisted trace amount solvent synthesis of Cs 4 PbBr 6 crystal with ultra-bright green light emission

Cs 4 PbBr 6 crystals have been synthesized by an ultrasonication-assisted trace amount polar solvent method. The prepared green Cs 4 PbBr 6 material was found to have high photoluminescence (PL) brightness and 10 ns PL lifetime. The prepared green light emitting device can achieve the maximum brightness of 3.8 × 10 9 cd/m 2 , which is nearly 100 times higher than a wick. The white light emitting device based on Cs 4 PbBr 6 crystals has better performance than commercial products, which can cover 32.3% of the color gamut and achieves 107.3% coverage for International Commission on Illumination (CIE)1931 and 84.8% coverage for CIE1976.

36 MATERIALS SCIENCE↗