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At least 1,621 records · Page 90
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

HEATING MECHANISMS IN THE LOW SOLAR ATMOSPHERE THROUGH MAGNETIC RECONNECTION IN CURRENT SHEETS

We simulate several magnetic reconnection processes in the low solar chromosphere/photosphere; the radiation cooling, heat conduction and ambipolar diffusion are all included. Our numerical results indicate that both the high temperature (≳8 × 10{sup 4} K) and low temperature (∼10{sup 4} K) magnetic reconnection events can happen in the low solar atmosphere (100–600 km above the solar surface). The plasma β controlled by plasma density and magnetic fields is one important factor to decide how much the plasma can be heated up. The low temperature event is formed in a high β magnetic reconnection process, Joule heating is the main mechanism to heat plasma and the maximum temperature increase is only several thousand Kelvin. The high temperature explosions can be generated in a low β magnetic reconnection process, slow and fast-mode shocks attached at the edges of the well developed plasmoids are the main physical mechanisms to heat the plasma from several thousand Kelvin to over 8 × 10{sup 4} K. Gravity in the low chromosphere can strongly hinder the plasmoid instability and the formation of slow-mode shocks in a vertical current sheet. Only small secondary islands are formed; these islands, however, are not as well developed as those in the horizontal current sheets. This work can be applied to understand the heating mechanism in the low solar atmosphere and could possibly be extended to explain the formation of common low temperature Ellerman bombs (∼10{sup 4} K) and the high temperature Interface Region Imaging Spectrograph (IRIS) bombs (≳8 × 10{sup 4}) in the future.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2014

Effects of thermal treatment on the Mg{sub x}Zn{sub 1−x}O films and fabrication of visible-blind and solar-blind ultraviolet photodetectors

Highlights: • Single-phase wurtzite/cubic Mg{sub x}Zn{sub 1−x}O films were grown by RF magnetron sputtering technique. • We focus on the red-shift caused by annealing the Mg{sub x}Zn{sub 1−x}O films. • MSM-structured visible-blind and solar-blind UV photodetectors were fabricated. - Abstract: A series of single-phase Mg{sub x}Zn{sub 1−x}O films with different Mg contents were prepared on quartz substrates by RF magnetron sputtering technique using different MgZnO targets, and annealed under the atmospheric environment. The absorption edges of Mg{sub x}Zn{sub 1−x}O films can cover the whole near ultraviolet and even the whole solar-blind spectra range, and the solar-blind wurtzite/cubic Mg{sub x}Zn{sub 1−x}O films have been realized successfully by the same method. In addition, the absorption edges of annealed films shift to a long wavelength, which is caused by the diffusion of Zn atoms gathering at the surface during the thermal treatment process. Finally, the truly solar-blind metal-semiconductor-metal structured photodetectors based on wurtzite Mg{sub 0.445}Zn{sub 0.555}O and cubic Mg{sub 0.728}Zn{sub 0.272}O films were fabricated. The corresponding peak responsivities are 17 mA/W at 275 nm and 0.53 mA/W at 250 nm under a 120 V bias, respectively.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Electrode and Microstructure Dependence of Oxygen Diffusion in Ferroelectric Hafnium Zirconium Oxide Thin Films

Hafnia-based ferroelectrics hold promise to reduce energy demand for computing by enabling compute-in-memory and as non-volatile memories. The ferroelectric phase in this material system is, in part, stabilized by oxygen vacancies. While oxygen vacancies may be a necessity for phase stability, they limit device endurance through diffusion and accumulation into conducting channels. Herein, it is shown that oxygen diffusion is spatially variable within individual grains of ferroelectric hafnium zirconium oxide (HZO). Using 18 O tracers and finite difference modeling, it is shown that grain boundaries and regions near electrode interfaces allow for relatively rapid oxygen diffusion, with values as much as 10 4 larger than the grain cores. Further, the selection of electrode material affects the diffusion coefficients across all microstructural regions. HZO films in contact with TiN electrodes result in more oxygen-deficient HZO films and higher oxygen diffusion coefficients. Tungsten electrodes result in fewer vacancies and lower diffusion coefficients. Diffusion activation energy differences between the HZO with the two electrodes is reconciled by differing populations of charged and uncharged oxygen vacancies. This insight into the local vacancy populations and diffusion pathways provides a platform for designing hafnia-based films, deposition processes, and integration strategies to reduce vacancy gradients and improve performance.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Diffusion quantum Monte Carlo approach to the polaritonic ground state

Making and using polaritonic states (i.e., hybrid electron-photon states) for chemical applications has recently become one of the most prominent and active fields that connects the communities of chemistry and quantum optics. Modeling of such polaritonic phenomena using ab initio approaches calls for new methodologies, leading to the reinvention of many commonly used electronic structure methods, such as Hartree-Fock, density functional, and coupled cluster theories. Here in this work, we explore the formally exact diffusion quantum Monte Carlo approach to obtain numerical solutions to the polaritonic ground state during the dissociation of the H 2 molecular system. Here, we examine various electron-nuclear-photon properties throughout the dissociation, such as changes to the minimum of the cavity Born-Oppenheimer surface, the localization of the electronic wave function, and the average mode occupation. Finally, we directly compare our results to that obtained with state-of-the-art, yet approximate, polaritonic coupled cluster approaches.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2016

Self-learning kinetic Monte Carlo simulations of Al diffusion in Mg

Atomistic on-lattice self-learning kinetic Monte Carlo (SLKMC) method was used to examine the vacancy-mediated diffusion of an Al atom in pure hcp Mg. Local atomic environment dependent activation barriers for vacancy-atom exchange processes were calculated on-the-fly using climbing image nudged-elastic band method (CI-NEB) and using a Mg-Al binary modified embedded-atom method (MEAM) interatomic potential. Diffusivities of vacancy and Al atom in pure Mg were obtained from SLKMC simulations and are compared with values available in the literature that are obtained from experiments and first-principle calculations. Al Diffusivities obtained from SLKMC simulations are lower, due to larger activation barriers and lower diffusivity prefactors, than those available in the literature but have same order of magnitude. We present all vacancy-Mg and vacancy-Al atom exchange processes and their activation barriers that were identified in SLKMC simulations. We will describe a simple mapping scheme to map a hcp lattice on to a simple cubic lattice that would enable hcp lattices to be simulated in an on-lattice KMC framework. We also present the pattern recognition scheme used in SLKMC simulations.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2015

Combined convective and diffusive simulations: VERB-4D comparison with 17 March 2013 Van Allen Probes observations: VERB-4D

Our study focused on understanding the coupling between different electron populations in the inner magnetosphere and the various physical processes that determine evolution of electron fluxes at different energies. Observations during the 17 March 2013 storm and simulations with a newly developed Versatile Electron Radiation Belt-4D (VERB-4D) are presented. This analysis of the drift trajectories of the energetic and relativistic electrons shows that electron trajectories at transitional energies with a first invariant on the scale of ~100 MeV/G may resemble ring current or relativistic electron trajectories depending on the level of geomagnetic activity. Simulations with the VERB-4D code including convection, radial diffusion, and energy diffusion are presented. Sensitivity simulations including various physical processes show how different acceleration mechanisms contribute to the energization of energetic electrons at transitional energies. In particular, the range of energies where inward transport is strongly influenced by both convection and radial diffusion are studied. Our results of the 4-D simulations are compared to Van Allen Probes observations at a range of energies including source, seed, and core populations of the energetic and relativistic electrons in the inner magnetosphere.

58 GEOSCIENCES↗
DOE OSTI2016

DOUBLE POWER LAWS IN THE EVENT-INTEGRATED SOLAR ENERGETIC PARTICLE SPECTRUM

A double power law or a power law with exponential rollover at a few to tens of MeV nucleon{sup −1} of the event-integrated differential spectra has been reported in many solar energetic particle (SEP) events. The rollover energies per nucleon of different elements correlate with a particle's charge-to-mass ratio (Q/A). The probable causes are suggested as residing in shock finite lifetimes, shock finite sizes, shock geometry, and an adiabatic cooling effect. In this work, we conduct a numerical simulation to investigate a particle's transport process in the inner heliosphere. We solve the focused transport equation using a time-backward Markov stochastic approach. The convection, magnetic focusing, adiabatic cooling effect, and pitch-angle scattering are included. The effects that the interplanetary turbulence imposes on the shape of the resulting SEP spectra are examined. By assuming a pure power-law differential spectrum at the Sun, a perfect double-power-law feature with a break energy ranging from 10 to 120 MeV nucleon{sup −1} is obtained at 1 au. We found that the double power law of the differential energy spectrum is a robust result of SEP interplanetary propagation. It works for many assumptions of interplanetary turbulence spectra that give various forms of momentum dependence of a particle's mean free path. The different spectral shapes in low-energy and high-energy ends are not just a transition from the convection-dominated propagation to diffusion-dominated propagation.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2015

Understanding the Effect of Na in Improving the Performance of CuInSe 2 Based Photovoltaics

Cu(In,Ga)Se 2 (CIGS) thin film photovoltaic technology is in the early stages of commercialization with an annual manufacturing capacity over 1 GW and has demonstrated the highest module efficiency of any of the thin film technologies. However there still is a lack of fundamental understanding of the relationship between the material properties and solar cell device operation. It is well known that the incorporation of a small amount of Na into the CIGS film during processing is essential for high efficiency devices. However, there are conflicting explanations for how Na behaves at the atomic scale. This report investigates how Na is incorporated into the CIGS device structure and evaluates the diffusion of Na into CIGS grain boundaries (GBs) and bulk crystallites. Participants: This project was carried out at the Institute of Energy Conversion at the University of Delaware, collaborating with the Rockett group at the University of Illinois Urbana-Champagne. Significant Findings: The significant outcomes of this project for each task include; Task 1.0: Effect of Na in Devices Fabricated on PVD Deposited CIGS; Na diffusion occurs through the Mo back contact via GBs driven by the presence of oxygen; Na reversibly compensates donor defects in CIGS GBs,Task 2.0: Na Incorporation in Single Crystal CIGS; and bulk Na diffusion proceeds rapidly such that grains are Na-saturated immediately following CIGS thin film manufacture. Industry Guidance: The presented results offer interesting concepts for modification of manufacturing processes of CIGS-based PV modules. Possible approaches to improve control of Na uptake and uniformly increase levels in CIGS films are highlighted for processes that employ either soda-lime glass or NaF as the Na source. Concepts include the potential of O 2 or oxidative based treatments of Mo back contacts to improve Na diffusion through the metal film and increase Na uptake into the growing CIGS. This project has also offered fundamental understanding of the behavior of Na in CIGS grains and GBs, particularly the confirmation that CIGS grains will be saturated with Na immediately following manufacture Summary of Results: Most commercially available CIGS modules are fabricated on soda-lime glass coated with Mo as the back electric contact, and Na in the glass diffuses through the Mo layer into the CIGS during film growth. In Task 1 the transport of Na through Mo was evaluated using x-ray photoelectron surface spectroscopy along with diffusion modeling to obtain diffusion coefficients at several temperatures. It was determined that Na diffusion in Mo only occurs along GBs and that oxygen provides an additional driving force to enhance Na transport. Device data revealed that older Mo substrates with a greater amount of surface oxide resulted in slightly higher efficiencies due to enhanced Na incorporation caused by the oxide. This finding shows that Mo substrates could potentially undergo an oxidation treatment prior to CIGS deposition to further improve and control the incorporation of Na. To determine if in-grain Na affects device performance, in Task 1 Na was selectively removed from GBs using heat/rinse cycles. Due to the low temperature of this treatment, Na at GBS remained mobile while diffusion within the bulk was too slow for Na removal from the grain interiors. Changes in electrical properties were evaluated using conductivity and Seebeck coefficient measurements, with both decreasing as Na was removed to reach values similar to Na-free controls samples. This can be explained by the compensation of donor defects by Na, causing an increase in the free carrier concentration. Devices showed a decrease in open-circuit voltage after Na removal confirming that the beneficial effects of GB Na. The findings of this project will provide guidance for rational optimization of Na incorporation procedures in the manufacturing of CIGS solar cells. While it is known that Na segregates at CIGS GBs, the nature and role of Na diffusion into grain interiors was less clear. In Task 2, single crystal CuInSe 2 was used as a model system to represent the grain interiors of CIGS. Crystals processed by two different methods of different compositions and dislocation densities, were evaluated. Diffusion coefficients were obtained at two temperatures after Na diffusion, giving near identical values, ~2x10 11 cm 2 /s and ~6x10 11 cm2/s at 420°C and 480°C, respectively, for each crystal. Characterization confirmed that dislocation densities were too low to significantly impact the effective diffusion coefficient. The Cu-poor crystal had a higher solubility suggesting that Na diffusion is mediated by Cu-vacancies, but was not accompanied by an expected increase in diffusion coefficient. The activation energy for diffusion was similar to values expected for interstitial diffusion, but the large size of Na + ions should result in a solubility that is much lower than what was experimentally measured. A hybrid interstitial-substitutional mechanism is proposed that combines the fast diffusion of interstitial atoms with the high solubility common for substitutional impurities. Lattice diffusion of Na proceeds fast enough that CIGS grain interiors will have Na concentrations near the solubility limit of 1018 cm -3 when manufactured under standard conditions. Na and K treated epitaxial CIS films showed a significant increase in cathodoluminescence emission intensity, indicating a reduction of non-radiative recombination pathways, which is consistent with improvements in CIGS device performance, though the mechanism is not clear. Pathways forward: Despite the success of this project, there are a number of questions remaining related to further the understanding of the chemistry of Na in CIGS films and devices. These include further elucidation of the mechanisms of Na passivation in CIGS GBs, with identification of which defects are involved and confirmation of the possible effects of in-grain Na on device performance. To complete analysis of the cell structure, conformation of the presence and possible chemistries of Na at the CIGS/CdS junction and/or in the front transparent contacts, and its effects on device performance, is needed.

14 SOLAR ENERGY↗
DOE OSTI2014

Growth kinetics and microstructural evolution during hot isostatic pressing of U-10 wt.% Mo monolithic fuel plate in AA6061 cladding with Zr diffusion barrier

Phase constituents and microstructure changes in RERTR fuel plate assemblies as functions of temperature and duration of hot-isostatic pressing (HIP) during fabrication were examined. The HIP process was carried out as functions of temperature (520, 540, 560 and 580 °C for 90 min) and time (45–345 min at 560 °C) to bond 6061 Al-alloy to the Zr diffusion barrier that had been co-rolled with U-10 wt.% Mo (U10Mo) fuel monolith prior to the HIP process. Scanning and transmission electron microscopies were employed to examine the phase constituents, microstructure and layer thickness of interaction products from interdiffusion. At the interface between the U10Mo and Zr, following the co-rolling, the UZr2 phase was observed to develop adjacent to Zr, and the a-U phase was found between the UZr2 and U10Mo, while the Mo2Zr was found as precipitates mostly within the a-U phase. The phase constituents and thickness of the interaction layer at the U10Mo-Zr interface remained unchanged regardless of HIP processing variation. Observable growth due to HIP was only observed for the (Al,Si)3Zr phase found at the Zr/AA6061 interface, however, with a large activation energy of 457 ± 28 kJ/mole. Thus, HIP can be carried to improve the adhesion quality of fuel plate without concern for the excessive growth of the interaction layer, particularly at the U10Mo-Zr interface with the a-U, Mo2Zr, and UZr2 phases.

99 GENERAL AND MISCELLANEOUS↗
DOE OSTI2013

Hot Isostatic Press Can Optimization for Aluminum Cladding of U-10Mo Reactor Fuel Plates: FY12 Final Report and FY13 Update

Currently, the proposed processing path for low enriched uranium – 10 wt. pct. molybdenum alloy (LEU-10Mo) monolithic fuel plates for high power research and test reactors includes hot isostatic pressing (HIP) to bond the aluminum cladding that encapsulates the fuel foil. Initial HIP experiments were performed at Idaho National Laboratory (INL) on approximately ¼ scale “mini” fuel plate samples using a HIP can design intended for these smaller experimental trials. These experiments showed that, with the addition of a co-rolled zirconium diffusion barrier on the LEU-10Mo alloy fuel foil, the HIP bonding process is a viable method for producing monolithic fuel plates. Further experimental trials at Los Alamos National Laboratory (LANL) effectively scaled-up the “mini” can design to produce full-size fuel prototypic plates. This report summarizes current efforts at LANL to produce a HIP can design that is further optimized for higher volume production runs. The production-optimized HIP can design goals were determined by LANL and Babcock & Wilcox (B&W) to include maintaining or improving the quality of the fuel plates produced with the baseline scaled-up mini can design, while minimizing material usage, improving dimensional stability, easing assembly and disassembly, eliminating machining, and significantly reducing welding. The initial small-scale experiments described in this report show that a formed-can approach can achieve the goals described above. Future work includes scaling the formed-can approach to full-size fuel plates, and current progress toward this goal is also summarized here.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2017

Laser-induced generation of surface periodic structures in media with nonlinear diffusion

A model of fast formation of high-contrast periodic structure appearing on a semiconductor surface under action of laser radiation is proposed. The process of growing a surface structure due to the interaction surface plasmon- polaritons excited on nonequilibrium electrons with incident laser radiation are considered in the framework of a medium with nonlinear diffusion of nonequilibrium carriers (defects). A resonance effect of superfast pico- and subpicosecond amplification of the plasmon-polariton structure generated on the surface, the realization of which can result in a high-contrast defect lattice.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Dynamic Surface Tension and Diffusivity Measurements of NG-CSSX Next Generation Solvent

Since 2008, the Savannah River Site has processed more than four million gallons of radioactive supernatant. To continue compliance with downstream processes, MCU is switching to the improved solvent called Next Generation Solvent (NG-CSSX). The new solvent formulation promises higher cesium removal efficiency and laboratory testing suggests the potential of higher processing rates. Similarly, laboratory testing demonstrated improvements in separation of the solvent from the effluent aqueous streams. To complete implementation at MCU, additional work was needed to develop methods that can measure physical properties relevant to the performance of the new solvent. This work measures two relevant physical properties: static interfacial tension and diffusvity. Both properties play a relevant role in mixing and separating immiscible liquids. This work evaluated the impact of changes in composition or aqueous phase on these physical properties to gauge the sensitivity of the system to the losses of chemical components.

Fondeur, F. F.↗
DOE OSTI2025

Cosmological Neutron Stars Produce Diffuse Axion X-Ray Signatures

Axion-like particles can be abundantly produced through scattering processes in the cores of neutron stars (NSs). If they are ultralight ($m_a \lesssim 10^{-4}$ eV), then they can efficiently convert to detectable photons in the external NS magnetospheres, and if they are heavy ($m_a \gtrsim 1$ eV), then they can decay into photons before reaching Earth. In this work, we search for the resulting X-ray signatures from both of these channels summing over the $\textit{cosmological}$ NS population. We compare the predicted axion-induced X-ray signal to the cosmic X-ray background today as measured by a number of instruments such as NuSTAR, HEAO, Swift, and INTEGRAL. We model the axion-induced signal using NS cooling simulations and magnetic field evolution models. We find no evidence for axions and derive strong constraints for both ultralight and heavy axion scenarios, covering new parameter space for the axion-photon and axion-nucleon couplings. Our results rule out the axion-explanation of the Magnificent Seven X-ray excess from nearby isolated NSs.

Cosmology and Nongalactic Astrophysics (astro-ph.C↗
DOE OSTI2015

Enhancement in Quality Factor of SRF Niobium Cavities by Material Diffusion

An increase in the quality factor of superconducting radiofrequency cavities is achieved by minimizing the surface resistance during processing steps. The surface resistance is the sum of temperature independent residual resistance and temperature/material dependent Bardeen-Cooper-Schrieffer (BCS) resistance. High temperature heat treatment usually reduces the impurities concentration from the bulk niobium, lowering the residual resistance. The BCS part can be reduced by selectively doping non-magnetic impurities. The increase in quality factor, termed as Q-rise, was observed in cavities when titanium or nitrogen thermally diffused in the inner cavity surface.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Electron holography of devices with epitaxial layers

Applicability of electron holography to deep submicron Si devices with epitaxial layers is limited due to lack of the mean inner potential data and effects of the sample tilt. The mean inner potential V{sub 0} = 12.75 V of the intrinsic epitaxial SiGe was measured by electron holography in devices with Ge content C{sub Ge} = 18%. Nanobeam electron diffraction analysis performed on the same device structure showed that SiGe is strain-free in [220] direction. Our results showed good correlation with simulations of the mean inner potential of the strain-free SiGe using density function theory. A new method is proposed in this paper to correct electron holography data for the overlap of potentials of Si and the epitaxial layer, which is caused by the sample tilt. The method was applied to the analysis of the dopant diffusion in p-Field-effect Transistor devices with the identical gate length L = 30 nm, which had alternative SiGe geometry in the source and drain regions and was subjected to different thermal processing. Results have helped to understand electrical data acquired from the same devices in terms of dopant diffusion.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

The grism lens-amplified survey from space (glass). VII. The diversity of the distribution of star formation in cluster and field galaxies at 0.3 ≤ z ≤ 0.7

Exploiting the slitless spectroscopy taken as part of the Grism Lens-Amplified Survey from Space (GLASS), we present an extended analysis of the spatial distribution of star formation in 76 galaxies in 10 clusters at 0.3<z<0.7. We use 85 foreground and background galaxies in the same redshift range as a field sample. The samples are well matched in stellar mass (10{sup 8}−10{sup 11} M{sub ⊙}) and star formation rate (0.5–50 M{sub ⊙} yr{sup −1}). We visually classify galaxies in terms of broad band morphology, Hα morphology, and likely physical process acting on the galaxy. Most Hα emitters have a spiral morphology (41% ± 8% in clusters, 51% ± 8% in the field), followed by mergers/interactions (28% ± 8%, 31% ± 7%, respectively) and early-type galaxies (remarkably as high as 29% ± 8% in clusters and 15% ± 6% in the field). A diversity of Hα morphologies is detected, suggesting a diversity of physical processes. In clusters, 30% ± 8% of the galaxies present a regular morphology, mostly consistent with star formation diffused uniformly across the stellar population (mostly in the disk component, when present). The second most common morphology (28% ± 8%) is asymmetric/jellyfish, consistent with ram-pressure stripping or other non-gravitational processes in 18% ± 8% of the cases. Ram-pressure stripping appears significantly less prominent in the field (2% ± 2%), where the most common morphology/mechanism appears to be consistent with minor gas-rich mergers or clump accretion. This work demonstrates that while environment-specific mechanisms affect galaxy evolution at this redshift, they are diverse and their effects are subtle. A full understanding of this complexity requires larger samples and detailed and spatially resolved physical models.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2022

Current challenges in the physics of white dwarf stars

White dwarfs are a class of stars with unique physical properties. They present many challenging problems whose solution requires advanced theories of dense matter, state-of-the-art experimental techniques, and extensive computing efforts. New ground- and space-based observatories will soon provide an increasingly detailed view of white dwarf stars and reveal new phenomena that will challenge our models. This review is an introduction to the nature of white dwarfs, the physical processes that determine their structure and evolution, and the physical conditions they span. Here we discuss a wide variety of currently unsolved or partially resolved problems in their constitutive physics that are broadly related to equations of state, transport processes and opacities.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

Chemically Driven Multistep Crystallization in the Synthesis of Sodium Yttrium Fluoride Via a Porous, Electrochemically Active Intermediate

Two-step crystallization mechanisms based on liquid–liquid phase separations followed by crystallization are commonly observed both in the laboratory and in nature. While this pathway quite often occurs as a result of a chemical reaction, the subsequent nucleation and growth are often considered as separate, discrete events from the reaction itself. We show this mechanism in the aqueous synthesis sodium yttrium fluoride, but by using a combination of experimental techniques and computational modeling, we show an additional step of solid-state chemical diffusion that is essential to the nucleation mechanism. In this system, we observe at least four distinct steps in the crystallization process, including (1) the segregation of aqueous ions into a dense liquid phase, (2) the formation of a metastable amorphous aggregate, (3) the continuous, gradual solid-state diffusion of sodium and fluoride ions into the amorphous aggregate toward a NaYF4 stoichiometry, and (4) the crystallization of a stable cubic sodium yttrium fluoride phase. Unlike previous descriptions of nucleation and growth, we find that the stoichiometry of the final solid phase evolves throughout the crystallization process rather than being determined at the time of the initial separation from solution. Further, this emphasizes that the chemical reaction cannot be assumed to be a separate event from the phase separation and growth, especially in compounds with variable stoichiometry. We also find that the amorphous aggregate that forms prior to the ion incorporation step adopts a porous, gel-like structure, which we isolated and showed to be electrochemically active, allowing for its potential use as a battery anode in lithium and sodium ion batteries, among other potential applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗