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At least 793 records · Page 44

Reactive flash sintering: MgO and α-Al 2 O 3 transform and sinter into single-phase polycrystals of MgAl 2 O 4

We show that flash experiments with three phase mixed-powders of yttria-stabilized zirconia (8YSZ), MgO, and α-Al 2 O 3 not only produce polycrystals of high density, but also the transformation of magnesia and alumina into single-phase spinel. The presence of zirconia facilitates the onset of the flash. The sintering experiments in the laboratory were extended to live experiments at the National Synchrotron Light Source II at Brookhaven National Laboratory in order to measure the time-dependent evolution of single-phase spinel. The phase transformation occurred in <3 seconds during Stage II. Later, during Stage III the cubic zirconia transformed partly into the monoclinic phase, which reverted back to the cubic phase when the flash was extinguished by turning off the current to the specimen. The results underpin a recent report on the synthesis of single-phase bismuth ferrite from constituent oxides in reactive flash experiments, raising the specter of flash as a method for synthesis as well as sintering of complex oxide ceramics. The role of zirconia in catalyzing the flash in the present study is discussed.

36 MATERIALS SCIENCE↗

Building Low-Cost, High-Efficiency Solar Cells

See how NREL scientists are revitalizing a 50-year-old technique to grow low-cost versions of high-efficiency III-V solar cells. Learn more at https://www.nrel.gov/news/features/2018/improved-way-to-make-iii-v-solar-cells-could-hold-key-to-lower-costs.html

14 SOLAR ENERGY↗

Templated Vapor-Liquid-Solid Epitaxy of III-V Semiconductors on Silicon

Epitaxial growth on silicon remains the most promising method to reduce the cost of optoelectronic-quality III-V semiconductors. Several approaches exist to epitaxially grow III-V material from the vapor phase, but control of 3-D structures remains difficult with these methods. In this work, we present a novel epitaxial growth technique in which photolithography and wet etching are used to establish the geometry of group-III metal, which is then converted to III-V semiconductor by annealing with exposure group-V precursor. The resulting material has been shown to align to the substrate lattice and is optically active, making it a promising approach for III-V PV technologies.

government↗

$\mathrm{ATR}$-$\mathrm{FTIR}$ spectroscopy as a probe for metal ion binding onto immobilized ligands

ATR-FTIR spectroscopy is shown to be useful in probing metal ion binding to ligands immobilized on polymer beads. Lu(III) is the metal ion, phosphinic and sulfonic acids are the immobilized ligands, and polystyrene beads crosslinked at low and high levels are the support. Analysis is based on ligand band positions and intensities before and after complexation as a function of time. ATR spectra of the phosphinic acid show two types of binding sites with different accessibilities: surface ligands that bind Lu(III) from solution and interior ligands that gain ions by diffusion from the surface. Initially bound Lu(III) ions are mobile within the solid phase and their movement is accompanied by the breaking of hydrogen bonds among the phosphinic acid ligands to form Lu(III) phosphinate complexes. Competition between hydrogen bonding and bond-making with Lu(III) contributes to slow sorption rates compared to results from the sulfonic acid ligand whose strong acidity and ionizability allows rapid Lu(III) sorption. Comparing ATR spectra of the phosphinic acid bound to lightly- and highly-crosslinked polystyrene shows how the extent of crosslinking affects the transport mechanism.

36 MATERIALS SCIENCE↗

Predicted Growth of Two-Dimensional Topological Insulator Thin Films of III-V Compounds on Si(111) Substrate

We have carried out systematic first-principles electronic structure computations of growth of ultrathin films of compounds of group III (B, Al, In, Ga, and Tl) with group V (N, P, As, Sb, and Bi) elements on Si(111) substrate, including effects of hydrogenation. Two bilayers (BLs) of AlBi, InBi, GaBi, TlAs, and TlSb are found to support a topological phase over a wide range of strains, in addition to BBi, TlN, and TlBi which can be driven into the nontrivial phase via strain. A large band gap of 134 meV is identified in hydrogenated 2 BL film of InBi. One and two BL films of GaBi and 2 BL films of InBi and TlAs on Si(111) surface possess nontrivial phases with a band gap as large as 121 meV in the case of 2 BL film of GaBi. Persistence of the nontrivial phase upon hydrogenations in the III-V thin films suggests that these films are suitable for growing on various substrates.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

The hydrogen Lyman-alpha emission of Capella

We describe the hydrogen Ly-alpha emission of the spectroscopic binary Capella (G8 III + GO III) recorded at 0.1 A resolution by the International Ultraviolet Explorer. The overt changes in the composite line shape with orbital phase are controlled by the active GO III star and permit a dissection of the stellar components despite the obliteration of the central portion of the profile by atomic hydrogen and deuterium absorption along the 12.5 pc sightline. The Ly-alpha line shape of the active GO III star is surprisingly asymmetric and possibly is variable. Both characteristics suggest a stellar wind of moderate excitation (20,000-100,000 K), a key component of the coronal evolution scenario of Simon and Drake (1989) for the Hertzsprung-gap giants.

Ayres, Thomas R.↗

A study of solar preflare activity using two-dimensional radio and SMM-XRP observations

A study of type III activity at meter-decameter wavelengths in the preflare phase of the February 3, 1986 flare is presented, using data obtained with the Clark Lake Multifrequency Radioheliograph. This activity is compared with similar type III burst activity during the impulsive phase, and it is found that there is a displacement of burst sources between the onset and end times of the activity. A comparison of this displacement at three frequencies suggests that the type III emitting electrons gain access progressively to diverging and different field lines relative to the initial field lines. The energetics of the type III emitting electrons are inferred from observations and compared with those of the associated hard X-ray emitting electrons. The soft X-ray data from SMM-XRP show enhanced emission measure, density, and temperature in the region associated with the preflare type III activity.

Kundu, M. R.↗

Upright and Inverted Single-Junction GaAs Solar Cells Grown by Hydride Vapor Phase Epitaxy

Hydride vapor phase epitaxy (HVPE) is a low-cost alternative to conventional metal-organic vapor phase epitaxy (MOVPE) growth of III-V solar cells. In this work, we show continued improvement of the performance of HVPE-grown single-junction GaAs solar cells. We show over an order of magnitude improvement in the interface recombination velocity between GaAs and GaInP layers through the elimination of growth interrupts, leading to increased short-circuit current density and open-circuit voltage compared with cells with interrupts. One-sun conversion efficiencies as high as 20.6% were achieved with this improved growth process. Solar cells grown in an inverted configuration that were removed from the substrate showed nearly identical performance to on-wafer cells, demonstrating the viability of HVPE to be used together with conventional wafer reuse techniques for further cost reduction. As a result, these devices utilized multiple heterointerfaces, showing the potential of HVPE for the growth of complex and high-quality III-V devices.

14 SOLAR ENERGY↗

Position Assignment and Oxidation State Recognition of Fe and Co Centers in Heterometallic Mixed-Valent Molecular Precursors for the Low-Temperature Preparation of Target Spinel Oxide Materials

A series of mixed-valent, heterometallic (mixed-transition metal) diketonates that can be utilized as prospective volatile single-source precursors for the low-temperature preparation of M x M' 3–x O 4 spinel oxide materials is reported. Three iron–cobalt complexes with Fe/Co ratios of 1:1, 1:2, and 2:1 were synthesized by several methods using both solid-state and solution reactions. On the basis of nearly quantitative reaction yields, elemental analyses, and comparison of metal–oxygen bonds with those in homometallic analogues, heterometallic compounds were formulated as [Fe III (acac) 3 ][Co II (hfac) 2 ] (1), [Co II (hfac) 2 ][Fe III (acac) 3 ][Co II (hfac) 2 ] (2), and [Fe II (hfac) 2 ][Fe III (acac) 3 ][Co II (hfac) 2 ] (3). In the above heteroleptic complexes, the Lewis acidic, coordinatively unsaturated CoII/FeII centers chelated by two hexafluoroacetylacetonate (hfac) ligands maintain bridging interactions with oxygen atoms of acetylacetonate (acac) groups that chelate the neighboring Fe III metal ion. Preliminary assignment of Fe and Co positions/oxidation states in 1–3 drawn from X-ray structural investigation was corroborated by a number of complementary techniques. Single-crystal resonant synchrotron diffraction and neutron diffraction experiments unambiguously confirmed the location of Fe and Co sites in the molecules of dinuclear (1) and trinuclear (2) complexes, respectively. Direct analysis in real time mass spectrometry revealed the presence of Fe III - and Co II -based fragments in the gas phase upon evaporation of precursors 1 and 2 as well as of Fe III , Fe II , and Co II species for complex 3. Theoretical investigation of two possible “valent isomers”, [Fe II I(acac) 3 ][Co II (hfac) 2 ] (1) and [Co III (acac) 3 ][Fe II (hfac) 2 ] (1'), provided an additional support for the metal site/oxidation state assignment giving a preference of 6.48 kcal/mol for the experimentally observed molecule 1. Magnetic susceptibility measurements data are in agreement with the presence of high-spin FeIII and CoII magnetic centers with weak anti-ferromagnetic coupling between those in molecules of 1 and 2. Highly volatile heterometallic complexes 1–3 were found to act as effective single-source precursors for the low-temperature preparation of iron–cobalt spinel oxides Fe x Co 3–x O 4 known as important materials for diverse energy-related applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spectroscopic investigations on structural incorporation pathways of FeIII into zeolite frameworks in cement-relevant environments

Fe{sup III}-containing aluminosilicate zeolites are present in cement-relevant and natural environments. Although Fe{sup III} is known to occur in framework tetrahedral sites where it substitutes isomorphically Al{sup III}O{sub 4} or in extra-framework octahedral sites as free Fe(H{sub 2}O){sub 6}{sup 3+}, the structural incorporation process of Fe{sup III} into different sites is little known. We aim to discern feasible pathways of Fe{sup III} incorporation using hydrothermal synthesis methods and synchrotron-based spectroscopic analyses. Results showed that introducing either Fe{sup 3+} or Fe{sub 2}O{sub 3}·xH{sub 2}O initially during zeolite nucleation did not lead to Fe{sup III} incorporation into the zeolites but only Fe{sub 2}O{sub 3}·xH{sub 2}O prevailed in both cases. However, Fe(NO{sub 3}){sub 3}, FeCl{sub 3}, and Fe{sub 2}O{sub 3}·xH{sub 2}O affected the kind of zeolite formed. A feasible pathway to incorporate tetrahedral Fe{sup III} in the zeolite framework was to introduce firstly Fe{sup III} in the cage of faujasite-Y followed by a phase transformation to chabazite. This study facilitates understanding of Fe{sup III} uptake in zeolites and of Fe{sup III} functional sites that can contribute to immobilization of contaminants.

36 MATERIALS SCIENCE↗

CHAOS. II. Gas-phase abundances in NGC 5194

We have observed NGC 5194 (M51a) as part of the CHemical Abundances of Spirals project. Using the Multi Object Double Spectrographs on the Large Binocular Telescope we are able to measure one or more of the temperature-sensitive auroral lines ([O iii] λ4363, [N ii] λ5755, [S iii] λ6312) and thus measure “direct” gas-phase abundances in 29 individual H ii regions. [O iii] λ4363 is only detected in two H ii regions, both of which show indications of excitation by shocks. We compare our data to previous direct abundances measured in NGC 5194 and find excellent agreement (Δ[log(O/H)]≈0.05) for all but one region. We find no evidence of trends in Ar/O, Ne/O, or S/O within NGC 5194 or compared to other galaxies. We find modest negative gradients in both O/H and N/O with very little scatter (σ ≤ 0.08 dex), most of which can be attributed to random error and not to intrinsic dispersion. The gas-phase abundance gradient is consistent with the gradients observed in other interacting galaxies, which tend to be shallower than gradients measured in isolated galaxies. The N/O ratio (〈log(N/O)〉=−0.62) suggests secondary nitrogen production is responsible for a significantly larger fraction of nitrogen (e.g., factor of 8–10), relative to primary production mechanisms than predicted by theoretical models.

79 ASTRONOMY AND ASTROPHYSICS↗

High-pressure phase transitions of α-quartz under nonhydrostatic dynamic conditions: A reconnaissance study at PETRA III

Hypervelocity collisions of solid bodies occur frequently in the solar system and affect rocks by shock waves and dynamic loading. A range of shock metamorphic effects and high-pressure polymorphs in rock-forming minerals are known from meteorites and terrestrial impact craters. In this paper, we investigate the formation of high-pressure polymorphs of α-quartz under dynamic and nonhydrostatic conditions and compare these disequilibrium states with those predicted by phase diagrams derived from static experiments under equilibrium conditions. We create highly dynamic conditions utilizing a mDAC and study the phase transformations in α-quartz in situ by synchrotron powder X-ray diffraction. Phase transitions of α-quartz are studied at pressures up to 66.1 and different loading rates. At compression rates between 0.14 and 1.96 GPa s -1 , experiments reveal that α-quartz is amorphized and partially converted to stishovite between 20.7 GPa and 28.0 GPa. Therefore, coesite is not formed as would be expected from equilibrium conditions. With the increasing compression rate, a slight increase in the transition pressure occurs. The experiments show that dynamic compression causes an instantaneous formation of structures consisting only of SiO 6 octahedra rather than the rearrangement of the SiO 4 tetrahedra to form a coesite. Although shock compression rates are orders of magnitude faster, a similar mechanism could operate in impact events.

36 MATERIALS SCIENCE↗

The impact of mixed solvents on the complexation thermodynamics of Eu(III) by simple carboxylate and amino carboxylate ligands

To gain insight on the role of mixed solvents on the thermodynamic driving forces for the complexation between trivalent f-elements and organic ligands, solution phase thermodynamic parameters were determined for Eu(III) complexation with 2-hydroxyisobutyric acid (HIBA) and 2-aminoisobutyric acid (AIBA) in mixed methanol (MeOH)-water and N,N-dimethylformamide (DMF)-water solvents. Included in this study were the determination of mixed solvent autoprotolysis constants (pK α ) as well as the thermodynamic formation constants: log β, ΔG, ΔH, and ΔS, for ligand protonation and Eu(III)-ligand complexation utilizing potentiometry and calorimetry techniques. The results presented are conditional thermodynamic values determined at an ionic strength of 1.0 M NaClO 4 and a temperature of 298 K. It was found that moving from an aqueous solution to a binary aqueous-organic solvent affected all solution equilibria to some degree and that the extent of change depended on both the type of mixed solvent and the ligand in each study. Here, the ability to understand and predict these changes in thermodynamic values as a function of solvent composition provides important information about the chemistry of the trivalent f-elements.

2-aminoisobutyric acid↗

Heteroepitaxial growth of Ga2O3 on 4H-SiC by liquid-injection MOCVD for improved thermal management of Ga2O3 power devices

We report on the growth of monoclinic β- and orthorhombic κ-phase Ga2O3 thin films using liquid-injection metal-organic chemical vapor deposition on highly thermally conductive 4H-SiC substrates using gallium (III) acetylacetonate or tris(2,2,6,6-tetramethyl-3,5-heptanedionato) gallium (III). Both gallium precursors produced the β phase, while only the use of the latter led to growth of κ-Ga2O3. Regardless of the used precursor, best results for β-Ga2O3 were achieved at a growth temperature of 700 °C and O2 flows in the range of 600–800 SCCM. A relatively narrow growth window was found for κ-Ga2O3, and best results were achieved for growth temperatures of 600 °C and the O2 flow of 800 SCCM. While phase-pure β-Ga2O3 was prepared, κ-Ga2O3 showed various degrees of parasitic β phase inclusions. X-ray diffraction and transmission electron microscopy confirmed a highly textured structure of β- and κ-Ga2O3 layers resulting from the presence of multiple in-plane domain orientations. Thermal conductivities of 53 nm-thick β-Ga2O3 (2.13 + 0.29/−0.51 W/m K) and 45 nm-thick κ-Ga2O3 (1.23 + 0.22/−0.26 W/m K) were determined by transient thermoreflectance and implications for device applications were assessed. Presented results suggest great potential of heterointegration of Ga2O3 and SiC for improved thermal management and reliability of future Ga2O3-based high power devices.

Materials Science↗

The Mark III VLBI System

Geodetic measurements have errors in centimeter range. Collection of three reports describes both equipment and results of some measurements taken with Mark III very-long-baseline interferometry (VLBI) system. Has demonstrated high accuracy over short baselines, where phase-delay measurements used. Advanced hardware, called Mark III A, developed to improve system performance and efficiency. Original Mark III hardware and III A subsystem upgrades developed as part of NASA Crustal Dynamics Project at Haystack Observatory.

Rogers, A. E. E.↗

Microwave type III pair bursts in solar flares

A solar microwave type III pair burst is composed of normal and reverse-sloped (RS) burst branches with oppositely fast frequency drifts. It is the most sensitive signature of the primary energy release and electron accelerations in flares. This work reports 11 microwave type III pair events in 9 flares observed by radio spectrometers in China and the Czech Republic at a frequency of 0.80–7.60 GHz during 1994–2014. These type III pairs occurred in flare impulsive and postflare phases with separate frequencies in the range of 1.08–3.42 GHz and a frequency gap of 10–1700 MHz. The frequency drift increases with the separate frequency (f{sub x}), the lifetime of each burst is anti-correlated to f{sub x}, while the frequency gap is independent of f{sub x}. In most events, the normal branches are drifting obviously faster than the RS branches. The type III pairs occurring in flare impulsive phase have lower separate frequencies, longer lifetimes, wider frequency gaps, and slower frequency drifts than that occurring in postflare phase. Also, the latter always has strong circular polarization. Further analysis indicates that near the flare energy release sites the plasma density is about 10{sup 10}--10{sup 11} cm{sup −3} and the temperature is higher than 10{sup 7} K. These results provide new constraints to the acceleration mechanism in solar flares.

79 ASTRONOMY AND ASTROPHYSICS↗