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Solving the “Coloring Problem” in InPd 3– x Ag x ( x = 0–0.7) by Phase Diagrams Modeling and Diffraction Experiments

Here, a series of InPd 3–x Ag x (x = 0–1) compositions were synthesized by conventional high-temperature synthesis, and as-synthesized samples were characterized by powder X-ray diffraction experiments. Up to x = 0.7, InPd 3–x Ag x adopts the ternary substitutional variant of the InPd 3 structure (TiAl 3 -type), when x > 0.7, elemental Ag starts to segregate along with the main phase. Accurate structural characterization in InPd 3–x Ag x faces a critical challenge due to the narrow X-ray scattering contrast among constituents In, Pd, and Ag and nearly identical neutron scattering lengths of Pd and Ag. To overcome this “coloring problem”, a combination of calculation of phase diagrams modeling (CALPHAD) and diffraction techniques (X-ray and neutron) was employed. In the compositional range 0 ≤ x ≤ 0.7, InPd 3–x Ag x presents a ternary variant of the TiAl 3 -type structure, where Ag atoms selectively substitute one (the 2b Wyckoff site) of the two Pd sites in InPd 3 . Notably, in contrast to the isologous InPd 3–x Cu x (x = 0–1) system, Ag substitution does not form an ordered VRh 2 Sn-type structure at the limiting composition. The distinct site preference in InPd 3–x Ag x is elucidated by charge population analysis, electronic structure calculations, and orbital-resolved chemical bonding investigations, and the extent of substitution is supported by formation free energy calculations.

36 MATERIALS SCIENCE↗

Defect-Limited Mobility and Defect Thermochemistry in Mixed A-Cation Tin Perovskites: (CH3NH3)1-xCsxSnBr3

Hybrid organic-inorganic semiconductors crystallizing in the perovskite structure present a significant opportunity for realizing defect-tolerant semiconductors. In this work, we examine the solid solution, (CH3NH3)1-xCsxSnBr3, and identify the thermochemistry dictating the intrinsic carrier concentrations and how local structural distortions influences this electronic behavior. This family of compounds exhibits the expected systematic trend in decreasing optical gap with the cesium to methylammonium A-site mixing ratio, x, in the visible region. However, the carrier mobility, as determined from time-resolved microwave conductivity measurements, trends opposite to that expected from first-principles calculations combined with Boltzmann scattering theory calculations of the carrier mobility. We propose that this is a result of increasing carrier scattering with x in (CH3NH3)1-xCsxSnBr3 due to a significant increase in the carrier density with x. By examining the dependence of the carrier density as a function of x, we infer the compositional-dependence of the average enthalpy and nonconfigurational entropy per defect. While diffraction reveals a cubic aristotypic perovskite structure as a function of x at room temperature, the pair distribution functions obtained from synchrotron X-ray total scattering from these materials are better described by symmetry-adapted displacement modes of the Pm3m crystal structure, which we attribute to a large degree of anharmonic dynamics of the atom positions. This analysis shows that CH3NH3+-rich compositions retain mostly linear Sn-Br-Sn bonding environments through the displacements, while Cs+-rich compositions lead to more significantly bent Sn-Br-Sn environments. We propose that these bent bonding arrangements in Cs-rich compositions yield a higher propensity for defect formation. This also provides a rationale for carrier trapping that gives rise to anomalous microwave transients. Together, these results provide insight into the structure-dynamics-properties relationships in this highly anharmonic system with high amplitude atomic motions and low defect formation energies.

defect thermochemistry↗

Chemical Compensation Challenges in Processing Antiferroelectric PbZrO 3 Thin Films

The electric field-induced antipolar-to-polar phase transition in antiferroelectric materials is accompanied by large changes in the structural and functional response, making them attractive for many applications ranging from pulsed energy capacitors to high-strain-high (blocking-)force actuators, solid-state heating and cooling systems, and optoelectronic devices. PbZrO 3 , as an end member of the PZT, (x)PbZr 1–x Ti x O 3 , solid solution, has been the subject of many studies. However, processing of perovskite PbZrO 3 is extremely challenging due to phase instabilities induced by Pb loss at the temperatures necessary for perovskite crystallization. Here, we discuss the challenges associated with Pb loss, as well as its compensation through bulk Pb overstoichiometry and interfacial PbO additions, in chemical solution processed, highly oriented PbZrO 3 thin films. For both 042 o - and 001 o -oriented (o-orthorhombic distortion) PbZrO 3 thin films, the crystallization interfaces are the most important contributors to Pb loss and off-stoichiometric outcomes, and no single approach was sufficient to address these challenges. Pb-rich and Pb-deficient nonperovskite phases including ZrO x were only observable through microscopic characterization, and X-ray diffraction alone could not rule out the presence of such secondary phases. “Ideal” macroscopic antiferroelectric polarization-electric field double hysteresis curves were observed despite (at times) the large presence of secondary phases. However, reduced saturation polarization and increased phase transition electric fields were observed concomitantly with the presence of secondary phase(s) and tentatively assigned to the voltage drop across the ZrO x nanocrystals. Based on these results, it is imperative that the presence of secondary phases always be addressed (beyond X-ray diffraction spectra) in order to correctly evaluate the properties of antiferroelectric films.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Large Hyperfine Coupling Arising from Pseudo- 2 S Ground States in a Series of Lutetium(II) Metallocene Complexes

The synthesis of molecules with strong coupling between electronic and nuclear spins represents an important challenge in molecular quantum information science. Here, we report the synthesis and characterization of the divalent lutetium metallocene complexes Lu(Cp Me 5 )(Cp iPr 5 ) (Cp Me 5 = pentamethylcyclopentadienyl; Cp iPr 5 = pentaisopropylcyclopentadienyl), Lu(Cp iPr 4 Et ) 2 (Cp iPr 4 Et = ethyltetraisopropylcyclopentadienyl), and Lu(Cp iPr 4 ) 2 (Cp iPr 4 = tetraisopropylcyclopentadienyl). The molecular structures of these complexes, as determined through singlecrystal X-ray diffraction, feature a common bent sandwich geometry, with average Cp–Lu–Cp angles ranging from 159.9° to 152.6°. Analysis of continuous-wave electron paramagnetic resonance (EPR) spectra for the complexes reveals nearly isotropic g tensors with only a slight deviation from that of a free electron. Moreover, an extremely large splitting of the eight-line spectra indicates the presence of strong hyperfine coupling, and simulations provide isotropic hyperfine coupling constants of A iso = 4.38, 4.30, and 4.17 GHz across the series, where the value of A iso is found to decrease as the Cp–Lu–Cp angle becomes more acute. Notably, these values are the largest yet observed for any lanthanide complex. Moreover, EPR and computational analysis show that the large values of A iso stem from large s-orbital character up to 41.2% in the corresponding singly occupied molecular orbitals. To our knowledge, this degree of s-character in a molecular orbital is the largest yet reported for an open-shell isolable complex. These results outline a general strategy toward the isolation of paramagnetic molecules with strong hyperfine coupling and highly isotropic doublet electronic ground states.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Alkali cation stabilization of defects in 2D MXenes at ambient and elevated temperatures

Transition metal carbides have been adopted in energy storage, conversion, and extreme environment applications. Advancements in their 2D counterparts, known as MXenes, enable the design of unique structures at the ~1 nm thickness scale. Alkali cations have been essential in MXenes manufacturing processing, storage, and applications, however, exact interactions of these cations with MXenes are not fully understood. In this study, using Ti 3 C 2 T x , Mo 2 TiC 2 T x , and Mo 2 Ti 2 C 3 T x MXenes, we present how transition metal vacancy sites are occupied by alkali cations, and their effect on MXene structure stabilization to control MXene’s phase transition. We examine this behavior using in situ high-temperature x-ray diffraction and scanning transmission electron microscopy, ex situ techniques such as atomic-layer resolution secondary ion mass spectrometry, and density functional theory simulations. In MXenes, this represents an advance in fundamentals of cation interactions on their 2D basal planes for MXenes stabilization and applications. Broadly, this study demonstrates a potential new tool for ideal phase-property relationships of ceramics at the atomic scale.

42 ENGINEERING↗

Interplay between element-specific distortions and electrocatalytic oxygen evolution for cobalt–iron hydroxides

A microscopic understanding of how Fe-doping of Co(OH) 2 improves electrocatalytic oxygen evolution remains elusive. We study two Co 1–x Fex(OH) 2 series that differ in fabrication protocol and find composition alone poorly correlates to catalyst performance. Structural descriptors extracted using X-ray diffraction, X-ray absorption spectroscopy, and Raman spectroscopy reveal element-specific distortions in Co 1–x Fe x (OH) 2 . These structural descriptors are composition-dependent within individual sample series but inconsistent across fabrication protocols, revealing fabrication-dependence in catalyst microstructure. Correlations between structural parameters from different techniques show that Fe–O resists bond length changes, forcing distortion of Co environments. We find the difference in O–M–O bond angles between Co and Fe sites to correlate with electrocatalytic behavior across both sample series, which we attribute to asymmetric distortion of potential energy surfaces for the Co(III) to Co(IV) oxidation. A Tafel slope consistent with a rate-limiting step without electron transfer emerges as the O–Co–O angle decreases, implying a distortion-induced transition in the rate-limiting step. The fabrication dependence of electronic and bonding structure in the catalysts should be considered in theoretical and high-throughput analyses of electrocatalyst materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atomic layer deposition of nickel sulfide thin films and their thermal and electrochemical stability

Nickel sulfides (NiS x ) show promise for a range of energy and other applications, but their (in)stability under processing and operating conditions is scarcely studied. Herein, we have developed a new NiS x atomic layer deposition process using an easily synthesized NiCl 2 (TMPDA) precursor (TMPDA = N,N,N′,N′-tetramethyl-1,3-propanediamine) with H 2 S. Thin films deposited at 165–225 °C consist mostly of the β-NiS phase and display low resistivity (∼40–120 μΩ cm), high purity (<3 at% impurities), and a rough morphology. The thermal stability of the NiS x thin films is studied using high-temperature X-ray diffraction, revealing that structural and compositional changes occur in reducing, inert, and oxidizing atmospheres at approximately 300–400 °C. Under electrochemical water splitting conditions, the films are unstable in acid due to dissolution, especially at oxidizing potentials. In an alkaline electrolyte, we do not observe Ni dissolution, but β-NiS transforms to Ni 3 S 2 under HER conditions, possibly supplemented with Ni and/or Ni(OH) 2 species. Under alkaline OER, all sulfur is lost and NiOOH is formed. In addition to offering an attractive, scalable route to the synthesis of NiS x thin films, our work highlights the importance of thermal and electrochemical (in)stability of sulfides as a crucial step for understanding and engineering materials for energy and other applications.

Mattinen, Miika [Univ. of Helsinki (Finland); Stan↗

GdWN 3 is a nitride perovskite

Nitride perovskites ABN3 are an emerging and highly underexplored class of materials that are of interest due to their intriguing calculated ferroelectric, optoelectronic, and other functional properties. Incorporating novel A-site cations is one strategy to tune and expand such properties; for example, Gd 3+ is compelling due to its large magnetic moment, potentially leading to multiferroic behavior. However, the theoretically predicted ground state of GdWN 3 was a non-perovskite monoclinic structure. Here, we experimentally show that GdWN 3-y crystallizes in a perovskite structure. High-throughput combinatorial sputtering with activated nitrogen is employed to synthesize thin films of Gd 2-x W x N 3-y O y with oxygen content y < 0.05. Ex situ annealing crystallizes a polycrystalline perovskite phase in a narrow composition window near x = 1. LeBail fits of synchrotron grazing incidence wide angle x-ray scattering data are consistent with a perovskite ground-state structure. Refined density functional theory calculations that included antiferromagnetic configurations confirm that the ground-state structure of GdWN 3 is a distorted Pnma perovskite with antiferromagnetic ordering, in contrast to prior predictions. Initial property measurements find that GdWN 3-y is paramagnetic down to T = 2 K with antiferromagnetic correlations and that the absorption onset depends on cation stoichiometry. This work provides an important path toward both the rapid expansion of the emerging family of nitride perovskites and understanding their potential multiferroic properties.

14 SOLAR ENERGY↗

Designing Ta C Virtual Substrates for Vertical Al x Ga 1 − x N Power Electronics Devices

Power electronics are critical for a sustainable energy future, playing a key role in electrification and integration of renewable energy sources into the grid. Advances in ultrawide band gap materials are needed to handle higher powers in smaller form factors while reducing electrical and thermal losses. High Al content Al x Ga 1 − x N is theoretically capable of meeting these demands, but its impact in power electronics has been severely restricted by a lack of substrates that can satisfy conductivity, lattice matching, and/or thermal expansion requirements. We demonstrate that electrically conductive Ta C can be used as a virtual substrate for Al x Ga 1 − x N heteroepitaxy. Scaleably sputtered Ta C grown on Al 2 O 3 , followed by high-temperature face-to-face annealing, produces a thin film Ta C template with an effective hexagonal lattice constant matched to Al 0.70 Ga 0.30 N . Annealing of the Ta C promotes recrystallization, significantly improving crystallinity and reducing crystalline defects from as-deposited columnar grains to a step-and-terrace surface morphology, enabling the subsequent growth of high-quality Al 0.70 Ga 0.30 N by molecular beam epitaxy. X-ray diffraction and scanning transmission electron microscopy confirm that the Al x Ga 1 − x N layer is heteroepitaxially aligned, strain-free, and lattice-matched, transitioning abruptly from Ta C to Al x Ga 1 − x N without intermediate phases. These results demonstrate Ta C virtual substrates as electrically conductive, lattice-matched, and thermally compatible templates for vertical Al x Ga 1 − x N devices that can meet the growing power needs of a sustainable energy future. Published by the American Physical Society 2024

36 MATERIALS SCIENCE↗

Collaborative R&D with REEL Solar Inc (REEL) to Understand and Overcome Performance Limitations in CdTe Solar Cells: Cooperative Research and Development (Final Report)

This CRADA will focus on processing, advanced characterization, and testing of photovoltaic materials and devices to understand and improve REEL CdTe solar technology. This will include examining process variations and different buffer, absorber, and contact layers from REEL and NLR to maximize performance. The unique and diverse advanced characterization tools at NLR, such as time-resolved photoluminescence, capacitance-voltage measurements, electron beam scattered diffraction, cathodoluminescence, electron microscopy, TOF-SIMS, and other measurements will be applied to characterize REEL processing to improve understanding and guide experimental directions. Accelerated stability and potential induced degradation tests will be used to analyze metastability, short-and-long term degradation, and improve bankability. A second and major thrust this period will be joint development of Si/CdTe tandem solar cells to overcome industry wide terrestrial solar efficiency limits with the two lowest cost and manufacturable solar materials today. This will include developing novel transparent back contacts that can be incorporated into tandem structures and other novel solar applications, detailed analysis of designs and configurations for CdTe/Si tandem modules, and prototyping REEL CdTe Technology with Si bottom cells in tandem structures.

14 SOLAR ENERGY↗

Multilayer diffraction at 104 keV

We have measured the diffraction peak of a W:Si synthetic multilayer reflector at 104 keV using the High Energy Bonse-Hart Camera at the X-17B hard X-ray wiggler beam line of the National Synchrotron Light Source at Brookhaven National Laboratory. The characteristics of the diffraction peak are described and compared to theory.

Krieger, Allen S.↗

Friction and Wear Properties of As-Deposited and Carbon Ion-Implanted Diamond Films

Recent work on the friction and wear properties of as-deposited and carbon ion-implanted diamond films was reviewed. Diamond films were produced by the microwave plasma chemical vapor deposition (CVD) technique. Diamond films with various grain sizes and surface roughnesses were implanted with carbon ions at 60 keV ion energy, resulting in a dose of 1.2 x 10(exp 17) carbon ions per cm(exp 2). Various analytical techniques, including Raman spectroscopy, proton recoil analysis, Rutherford backscattering, transmission and scanning electron microscopy, X-ray photoelectron spectroscopy, and X-ray diffraction, were utilized to characterize the diamond films. Sliding friction experiments were conducted with a polished natural diamond pin in contact with diamond films in the three environments: humid air (40% relative humidity), dry nitrogen (less than 1 percent relative humidity), and ultrahigh vacuum (10(exp -7) Pa). The CVD diamond films indeed have friction and wear properties similar to those of natural diamond in the three environments. The as-deposited, fine-grain diamond films can be effectively used as self-lubricating, wear-resistant coatings that have low coefficients of friction (0.02 to 0.04) and low wear rates (10(exp -7) to lO(exp -8) mm(exp 3) N(exp -1) m(exp -1)) in both humid air and dry nitrogen. However, they have high coefficients of friction (1.5 to 1.7) and a high wear rate (10(exp -4) mm(exp 7) N(exp -1) m(exp -1)) in ultrahigh vacuum. The carbon ion implantation produced a thin surficial layer (less than 0.1 micron thick) of amorphous, non-diamond carbon on the diamond films. In humid air and dry nitrogen, the ion-implanted, fine and coarse-grain diamond films have a low coefficient of friction (around 0.1) and a low wear rate (10(exp -7) mm(exp 3) N(exp -1) m(exp-1)). Even in ultrahigh vacuum, the presence of the non-diamond carbon layer reduced the coefficient of friction of fine-grain diamond films to 0.1 or lower and the wear rate to 10(exp -6) mm(exp 3) N(exp -1) m(exp -1). Thus, the carbon ion-implanted, fine-grain diamond films can be effectively used as wear-resistant, self-lubricating coatings not only in air and dry nitrogen, but also in ultrahigh vacuum.

Miyoshi, Kazuhisa↗

Magnesium-Aluminum-Zirconium Oxide Amorphous Ternary Composite: A Dense and Stable Optical Coating

In the present work, the process parameter dependent optical and structural properties of MgO-Al(2)O(3)-ZrO(2) ternary mixed-composite material have been investigated. Optical properties were derived from spectrophotometric measurements. The surface morphology, grain size distributions, crystallographic phases and process dependent material composition of films have been investigated through the use of Atomic Force Microscopy (AFM), X-ray diffraction analysis and Energy Dispersive X- ray (EDX) analysis. EDX analysis made evident the correlation between the optical constants and the process dependent compositions in the films. It is possible to achieve environmentally stable amorphous films with high packing density under certain optimized process conditions.

Sahoo, N. K.↗

Growth of Homoepitaxial ZnO Semiconducting Films

As a high temperature semiconductor, ZnO has been used for many applications such as wave-guide, solar cells, and surface acoustic wave devices. Since the ZnO material has an energy gap of 3.3 eV at room temperature and an excitonic binding energy (60 meV) that is possible to make excitonic lasering at room temperature a recent surge of interest is to synthesize ZnO films for electro-optical devices. These applications require films with a smooth surface, good crystal quality, and low defect density. Homoepitaxial films have been studied in terms of morphology, crystal structure, and electrical and optical properties. ZnO single crystals are grown by the hydrothermal method. Substrates are mechanically polished and annealed in air for four hours before deposited films. The annealing temperature-dependence of ZnO substrates is studied. Films are synthesized by the off-axis reactive sputtering deposition. The films have very smooth surface with a roughness </= 5 nm on a 5 micrometers x 5 micrometers area. The full width at half maximum of film theta rocking curves measured by the x-ray diffraction is slightly larger than the crystal substrate. The film quality is determined by measuring the film resistivity, the Hall mobility, carrier densities and the energy band gap. The properties of ZnO films grown of (0001) ZnO and (0001) sapphire substrates will be also compared and discussed in the presentation.

Zhu, Shen↗

Growth of Homoepitaxial ZnO Semiconducting Films

As a high temperature wide-band-gap (3.3 eV at room temperature) semiconductor, ZnO has been used for many applications such as wave-guides, solar cells, and surface acoustic wave devices, Since ZnO has a 60 meV excitonic binding energy that makes it possible to produce excitonic lasing at room temperature, a recent surge of interest is to synthesize ZnO films for UV/blue/green laser diodes. These applications require films with a smooth surface, good crystal quality, and low defect density. Thus, homoepitaxial film growth is the best choice. Homoepitaxial films have been studied in terms of morphology, crystal structure, and electrical and optical properties. ZnO single crystal substrates grown by the hydrothermal method are mechanically polished and annealed in air for four hours before the films are deposited. The annealing temperature-dependence on ZnO substrate morphology and electrical properties is investigated. Films are synthesized by off-axis reactive sputtering deposition. This produces films that have very smooth surfaces with roughness less than or equal to 5 nm on a 5 microns x 5 microns area. The full width at half maximum of film theta rocking curves measured by the x-ray diffraction is slightly larger than that of the crystal substrate. Films are also characterized by measuring resistivity, optical transmittance, and photoluminescence. The properties of ZnO films grown on (0001) ZnO and (0001) sapphire substrates will also be compared and discussed.

Zhu, Shen↗

Rare-Earth Garnets and Perovskites for Space-Based ADR Cooling at High T and Low H

Future NASA satellite detector systems must be cooled to the 0.1 K temperature range to meet the stringent energy resolution and sensitivity requirements demanded by mid-term astronomy missions. The development of adiabatic demagnetization refrigeration (ADR) materials that can efficiently cool from the passive radiative cooling limit of approx. 30 K down to sub-Kelvin under low magnetic fields (H less than or equal to 3 T) would represent a significant improvement in space-based cooling technology. Governed by these engineering goals, our efforts have focused on quantifying the change in magnetic entropy of rare-earth garnets and perovskites. Various compositions within the gadolinium gallium iron garnet solid solution series (GGIG, Gd3Ga(5-x)Fe(x)O12, 0.00 less than or equal to X less than or equal to 5.00) and gadolinium aluminum perovskite (GAP, GdAlO3) have been synthesized via an organometallic complex approach and confirmed with powder x-ray diffraction. The magnetization of the GGIG and GAP materials has been measured as a function of composition (0.00 less than or equal to X less than or equal to 5.00), temperature (2 K less than or equal to T less than or equal to 30 K) and applied magnetic field (0 T less than or equal to H less than or equal to 3 T). The magnetic entropy change (DeltaS(sub mag)) between 0 T and 3 T was determined from the magnetization data. In the GGIG system, DeltaS(sub mag) was compositionally dependent; Fe(sup 3+) additions up to X less than or equal to 2.44 increased DeltaS(sub mag) at T > 5 K. For GAP, DeltaS(sub mag) was similar to that of GGIG, X = 0.00, both in terms of magnitude and temperature dependence at T > 10 K. However, the DeltaS(sub mag) of GAP at T < 10 K was less than the endmember GGIG composition, X = 0.00, and exhibited maximum approx. 5 K.

King, T. T.↗

Potential Evaporite Biomarkers from the Dead Sea

The Dead Sea is located on the northern branch of the African-Levant Rift systems. The rift system, according to one model, was formed by a series of strike slip faults, initially forming approximately two million years ago. The Dead Sea is an evaporite basin that receives freshwater from springs and from the Jordan River. The Dead Sea is different from other evaporite basins, such as the Great Salt Lake, in that it possesses high concentrations of magnesium and has an average pH of 6.1. The dominant cation in the Great Salt Lake is sodium, and the pH is 7.7. Calcium concentrations are also higher in the Dead Sea than in the Great Salt Lake. Both basins are similar in that the dominant anion is chlorine and the salinity levels are approximately 20 %. Other common cations that have been identified from the waters of the Dead Sea and the Great Salt Lake include sodium and potassium. A variety of Archea, Bacteria, and a single genus of a green algal, Dunaliella, has been described from the Dead Sea. Earlier studies concentrated on microbial identification and analysis of their unique physiology that allows them to survive in this type of extreme environment. Potential microbial fossilization processes, microbial fossils, and the metallic ions associated with fossilization have not been studied thoroughly. The present study is restricted to identifying probable microbial morphologies and associated metallic ions. XRD (X Ray Diffraction) analysis indicates the presence of halite, quartz, and orthoclase feldspar. In addition to these minerals, other workers have reported potassium chloride, magnesium bromide, magnesium chloride, calcium chloride, and calcium sulfate. Halite, calcium sulfate, and orthoclase were examined in this report for the presence of microbes, microbially induced deposits or microbial alteration. Neither the gypsum nor the orthoclase surfaces possesses any obvious indications of microbial life or fossilization. The sand-sized orthoclase particles are weathered with 122 extensive fan-shaped mineral deposits. The gypsum deposits are associated with halite minerals and also exhibit extensive weathering. Halite minerals represent the only substrates that have probable rod-shaped microbial structures with long, filamentous, apical extensions. EDS (energy dispersive x-ray) analysis of the putative microbes indicates elevated calcium levels that are enriched with magnesium. The rod-shaped structures exhibit possible fossilization stages. Rhombohedralshaped minerals of magnesium-enriched calcium carbonate are deposited on the microbial surfaces, and eventually coat the entire microbial surface. The sodium chloride continues to crystallize on nearby halite surface and even crystallizes on the fossilized microbial remains. The putative fossils are found exclusively on halite surfaces, and all contained elevated levels of calcium magnesium cations. Both of these metallic cations are associated with microbial activity and fossilization. Their morphological diversity is low in comparison with the reported living Dead Sea microbial population. If we examine the fossil record for multicellular organisms, fossilization rates are lower for soft-bodied organisms than for those possessing hard parts, i.e. shells, bones. For example, smaller, single celled organisms would have a smaller chance of fossilization; their fossilized shapes could be mistaken for abiotic products. Another consideration is that dead organisms in the water column are probably utilized as a food source by other microbes before fossilization processes are completed. This may be an important consideration as we attempt to model and interpret ancient microbial environments either on Earth or on Mars.

Morris, Penny A.↗

A Transmission Electron Microscopy Study of a Refractory Metal Grain from a Calcium-Aluminum-Rich Inclusion in the Leoville CV3 Chondrite

Introduction: Calcium-aluminum-rich inclusions (CAIs) are an important component of chondritic meteorites. They can contain materials that are thermodynamically predicted and isotopically age dated to be among the first-formed solids in our solar system [1-5]. Observed in some CAIs are micron to sub-micron sized inclusions rich in Fe, Ni, and high-Z elements such as Pt, Os, Ir and W, in the form of refractory metal nuggets (RMNs), fremdlinges, and ‘nugget like objects’ (NLOs) [1,6]. Refractory siderophile elements such as Os, Ir and Ru are thermodynamically predicted to condense at temperatures well in excess of the major CAI phases such as melilite, perovskite, spinel and hibonite [2,7-9]. These refractory metal inclusions in CAIs can therefore serve as probes into the thermodynamic landscape of the early solar protoplanetary disk. Here we report on a refractory grain identified in a CAI of the Leoville CV3 chondrite. This work is part of an ongoing effort to gain insight into the thermochemistry of the early solar system through systematic analyses of the structure and chemistry of various components in CAIs [10-13]. Sample and Analytical Techniques: A fluffy type A CAI (Fig. 1A) was identified in a section of the Leoville, CV3 chondrite (Center for Meteorite Studies, Arizona State University collection, #821_C_3) using a JOEL-JXA 8530F electron microprobe at Arizona State University. Backscattered electron (BSE) imaging and energy-dispersive X-ray spectroscopy (EDS) were used to identify refractory metal grains in the CAI using a Thermo Fisher (formerly FEI) Helios NanoLab 660 G3 focused-ion-beam scanning-electron microscope (FIBSEM) located at the Kuiper Materials Imaging and Characterization Facility (KMICF) at the Lunar and Planetary Laboratory, University of Arizona. The FIB is equipped with an EDAX EDS system. We selected one of the larger (micron-sized) refractory metal grains, designated as ‘Spud’ (Fig. 1B) for further analysis. ‘Spud’ was extracted and thinned to electron transparency (<100 nm) using the FIB-SEM located in KMICF, following methods described by [14- 15]. The FIB section was analyzed using a 200 keV Hitachi HF5000 scanning transmission electron microscope (S/TEM) located at KMICF. The HF5000 is equipped with cold-field emission gun, 3rd-order spherical aberration corrector for STEM imaging, and an Oxford Instruments X-Max N 100 TLE energydispersive spectroscopy (EDS) system with dual 100 mm2 windowless silicon-drift detectors (Ω = 2.0 sr). Selected-area electron-diffraction (SAED) patterns were acquired to aid in determination of crystallinity and phase. Results: The mineralogy, texture, and morphology of the CAI are consistent with that of a fluffy type A (FTA) CAI [16]. BSE imaging at high magnifications revealed grains with high contrast, indicative of compositions rich in elements of higher atomic number relative to surrounding material. These high-Z grains have sizes that range from ∼250 nm to 4 µm. EDS analyses confirm that the bright grains are metal-rich inclusions. A minor fraction of the grains are composed of only Fe and Ni, but the majority (∼60%) of the identified inclusions also contained various refractory siderophiles including Os, Ru, Zr, Ir and Mo. EDS analysis on the FIB-SEM of Spud shows that it contains Fe, Ni, Mo and Ru. High-angle annular dark-field (HAAFD) imaging and EDS mapping in the TEM (Fig. 2) show that Spud occurs in melilite (Ca1.9Al1.99Si1.06O7). Spud contains a subhedral to anhedral morphology and is compositionally heterogenous (polyphasic, Fig. 2). Local spatial correlation occurs among Fe, Ni, and Pt, and also among Os, Ru, and Mo. SAED patterns show that the Fe-Ni-Pt, Fe-Os-Mo-Ru and Fe-Pt regions are crystalline. Discussion: CAIs can contain various types of inclusions rich in Fe, Ni and refractory siderophiles such as Os, Ru, W and Pt [1]. RMNs are micron-sized, single phase alloy grains and can contain Os, Ir, Ru and Rh [1,7,17]. NLOs are also micron-sized inclusions, but contain two phases, a refractory metal, and an oxide [6]. Fremdlinge are the largest of such inclusions (tens of microns in size) and are complex aggregates of Fe-Ni alloy, silicates, oxides, and sulfides [1,17]. While the size of Spud matches previous descriptions of RMNs and NLOs, Spud is neither a single-phase alloy like RMNs, nor does it contain one metal phase and one oxide like NLOs. Spud does not match the above described categories of refractory metal inclusions. The presence of refractory siderophiles such as Mo, Os, Ru, and Pt suggests a high-temperature origin. Thermodynamic modelling by [7] indicates condensation temperatures of 1917 K, 1693 K, 1613 K and 1415 K for Os, Mo, Ru and Pt respectively. These models also show that following the initial condensation of a refractory metal, alloying of solutes such as Fe, Ni and W, occurs in levels proportional to their partial pressures in the surrounding gas. Such alloying occurs at temperatures above the condensation temperatures of common CAI phases such as melilite (1529 K), perovskite (1441 K), spinel (197 K) and forsterite (1354 K) [2]. The polyphasic nature of Spud could be the result of such high-temperature alloying, possibly shortly after the condensation of Mo and Ru at 1693 K and 1613 K respectively. That Spud occurs as an inclusion is consistent with it having formed prior to and at temperature above that of its host melilite in this FTA CAI, which is qualitatively consistent with such prior thermodynamic modeling. Further, the polyphasic nature of Spud is similar to refractory grains from a FTA CAI in the Northwest Africa (NWA) 8323, CV3 chondrite [11-13]. These data suggest that such refractory metal grains could have been widespread in the inner and early solar protoplanetary disk and represent some of the earliest formed solids to have condensed. Acknowledgments: Research and instrumentation supported by NASA grants #NNX12AL47G, #NNX15AJ22G and #80NSSC19K0509, and NSF grants #1531243 and #0619599. Fig 2. STEM data on ‘Spud’. HAADF Image (Top) False-color EDS Maps (Bottom) References: [1] MacPherson G. J. (2014) T. of Geochem. Vol I: Met. And Cosmochem. Processes, 139-179. [2] Lodders K. (2003) ApJ, 591, 1220-1247. [3] Ebel D. S. (2006) Met. & the Early S. Sys. II., 253- 277. [4] Amelin Y. (2002) Science, 297, 1678-1683. [5] Connelly J.N. et.al. (2012) Science, 338, 651-655. [6] Schwander D. et al. (2015) GCA, 18, 70-87. [7] Palme H. and Wlotzka F. (1976) EPSL, 33, 45-60. [8] Berg T. et al. (2009) ApJ, 702, 172-176. [9] Liffman K. et al. (2021) Icarus, 221, 89-105. [10] Zega T.J. et al. (2021) PSJ, 2, 115. [11] Ramprasad T. et al. (2020) LPSC LI, Abstract #2472. [12] Ramprasad T. et al. (2021) Microscopy & Microanalysis, S1, 2792-2794. [13] Ramprasad T. et al. (2021) 84th MetSoc, Abstract #6123. [14] Zega T.J. et al. (2007) MAPS, 42, 1373-1386. [15] Ramprasad T. et al. (2022) MAPS, in revision. [16] Grossman L. (1975), GCA, 39, 433-454. [17] El Goresy A. et al. (1978) LPSC IX, Abstract#1100

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