Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “La(HO)3”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

A comprehensive approach for elucidating the interplay between 4f n +1 and 4f n 5d 1 configurations in Ln 2+ complexes

Lanthanides (Ln) are typically found in the +3 oxidation state. However, in recent decades, their chemistry has been expanded to include the less stable +2 oxidation state across the entire series except promethium (Pm), facilitated by the coordination of ligands such as trimethylsilylcyclopentadienyl, C 5 H 4 SiMe 3 (Cp'). The [LnCp' 3 ] complexes have been the workhorse for the synthesis and theoretical study of the fundamental aspects of divalent lanthanide chemistry, where experimental and computational evidence have suggested the existence of different ground state (GS) configurations, 4f n+1 or 4f n 5d 1 , depending on the specific metal. Standard reduction potentials and 4f n+1 to 4f n 5d 1 promotion energies have been two factors usually considered to rationalize the occurrence of these variable GS configurations, however the driving force behind this phenomenon is still not clear. In this work we present a comprehensive theoretical approach to shed light on this matter using the [LnCp 3 ] - model systems. We begin by calculating 4f n+1 to 4f n 5d 1 promotion energies and successfully correlate them with existing experimental data. Furthermore, we analyze how changes in the GS charge distribution between the Ln ions, LnCp 3 and the reduced [LnCp 3 ] - complexes (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) correlate with experimental trends in redox potentials and the calculated promotion energies. For this purpose, a comprehensive theoretical work that includes relativistic ligand field density functional theory (LFDFT) and relativistic ab initio wavefunction methods was performed. This study will help the rational design of suitable environments to tune the different GS configurations as well as modulating the spectroscopic properties of new Ln 2+ complexes.

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

Materials Data on LaHoO3 by Materials Project

LaHoO3 crystallizes in the monoclinic P2_1/c space group. The structure is three-dimensional. there are two inequivalent Ho3+ sites. In the first Ho3+ site, Ho3+ is bonded to six O2- atoms to form corner-sharing HoO6 octahedra. The corner-sharing octahedra tilt angles range from 37–40°. There are a spread of Ho–O bond distances ranging from 2.23–2.28 Å. In the second Ho3+ site, Ho3+ is bonded to six O2- atoms to form corner-sharing HoO6 octahedra. The corner-sharing octahedral tilt angles are 37°. There are a spread of Ho–O bond distances ranging from 2.25–2.27 Å. La3+ is bonded in a 3-coordinate geometry to seven O2- atoms. There are a spread of La–O bond distances ranging from 2.30–3.06 Å. There are three inequivalent O2- sites. In the first O2- site, O2- is bonded to two Ho3+ and two equivalent La3+ atoms to form distorted corner-sharing OLa2Ho2 tetrahedra. In the second O2- site, O2- is bonded in a 4-coordinate geometry to two equivalent Ho3+ and two equivalent La3+ atoms. In the third O2- site, O2- is bonded in a 3-coordinate geometry to two equivalent Ho3+ and three equivalent La3+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Mechanism and Kinetics of Ethanol–Acetaldehyde Conversion to 1,3-Butadiene over Isolated Lewis Acid La Sites in Silanol Nests in Dealuminated Beta Zeolite

Biomass-derived ethanol (EtOH) and acetaldehyde (AcH) conversion to 1,3-butadiene (1,3-BD) is an alternative process for 1,3-BD production. The present investigation reports the preparation and characterization of isolated La sites introduced into the silanol nests in DeAlBEA as well as detailed studies of the mechanism and kinetics for the conversion of an EtOH-AcH mixture to 1,3-BD. La sites supported on DeAlBEA are found to be present as (≡SiO) 2 La-OH groups that are H-bonded with adjacent Si-OH groups, possessing high C-C coupling activity and stability, superior to state-of-the-art Y-DeAlBEA. La sites supported on silica (La-SiO 2 ) with a similar chemical structure but no H-bonding interaction with Si-OH groups were prepared for comparison. Lewis acid La sites promote AcH aldol condensation, and the activity of such sites is nearly identical for both La-DeAlBEA and La-SiO 2 . Further, the rate of C 4 product formation increases by a factor of 4.8 upon addition of EtOH to the feed of AcH over La-DeAlBEA, whereas that over La/SiO 2 remains unchanged. Investigation of the mechanism and kinetics of AcH aldol condensation and EtOH-AcH conversion to 1,3-BD revealed two C-C bond forming pathways-AcH aldol condensation by Lewis acid La sites and direct coupling of EtOH-AcH over H-bonded (≡SiO) 2 La-OH···HO-Si≡ sites. This study provides important information about the role of the local environment of isolated Lewis acid sites and their effects on the direct coupling of EtOH and AcH to form 1,3-BD.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Synthesis and characterization of the rare-earth chloride complexes with N,N,N',N' -tetramethylmalonamide

Exploration of the solid-state chemistry of the f-elements and their coordination chemistry can assist in understanding the speciation of these elements in solution, which, in turn, can aid in the interpretation of their chemical behavior in complex liquid-liquid separations. Within these separation processes, malonamides are common organic extractants that are used for complexing both lanthanides and actinides, thus it is relevant to understand the malonamide ligand complexation under various conditions. In this work, we investigate solid-state complexes of the rare-earth chlorides with N,N,N',N' -tetramethylmalonamide (TMMA) across the entire lanthanide series. Here, we isolated two structural families of compounds Ln(TMMA) 2 Cl 3 Ln = La–Dy and [Ln(TMMA) 2 (H 2 O) 4 ]Cl 3 • x H 2 O x = 0,4 Ln = Ho–Lu, showing differences in chloride coordination from the inner-sphere complex for early lanthanides to outer-sphere for the late lanthanides. Both structural series were additionally analyzed by both IR and Raman spectroscopy confirming similarities in malonamide ligand coordination modes, while showing differences in vibrational features associated with chloride and aqua ligand coordination.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Crystal Growth and Phase Formation of High-Entropy Rare-Earth Aluminum Perovskites

In this work, we demonstrate for the first time the crystal growth of high-entropy rare-earth (RE) aluminum perovskites (REAlO 3 ) using the micro-pulling-down method to inform future exploration of functional crystals. To determine how composition affects phase formation, we formulate equiatomic compositions containing five REs from the following list: Lu, Yb, Tm, Er, Y, Ho, Dy, Tb, Gd, Eu, Sm, Nd, Pr, Ce, La. To test whether combinations of REs with similar ionic radii may favor a single phase, compositions containing REs with consecutive or nonconsecutive ionic radius values were formulated. Powder and single-crystal X-ray diffraction indicate that crystals containing only REs with similar ionic radii that form orthorhombic single-RE REAlO 3 are a single phase. Crystals containing REs with dissimilar ionic radii or mixtures of REs that form orthorhombic, rhombohedral, and tetragonal single-RE REAlO 3 are a mixture of phases. The elemental distribution in single-phase crystals analyzed via electron probe microanalysis confirms no evidence of preferential incorporation of any of the constituent REs. The distribution and composition of secondary phases were analyzed via scanning electron microscopy and energy dispersive spectroscopy; secondary phases were seen as a small region in the center of the crystals with branching features closer to the outer surface.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Comprehensive Synthesis and Structural Trends in Tetramethyl Diglycolamide (TMDGA) Nitrate Complexes with Lanthanides and Americium

Complexes of N,N,N',N'-tetramethyl diglycolamide (TMDGA), a hydrophilic diglycolamide (DGA) proposed as an aqueous phase holdback reagent, have been crystallized for the majority of the lanthanide series (excluding promethium), yttrium, and americium to deepen our structural understanding of trivalent metal ion (M 3+ ) DGA coordination compounds in the presence of nitrate counter-anions. The presented collection of 16 complexes with accompanying single-crystal structures, taking formulas [M(TMDGA) 3 ][M(NO 3 ) 6 ] (M = La, Ce, Pr, Nd, Sm, Am), [M(TMDGA) 3 ][M(NO 3 ) 5 (H 2 O)] 1–x [M(NO 3 ) 4 (H 2 O) 2 ] x (NO 3 ) 1+x (M = Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb), [M(TMDGA) 3 ] 2 [M(NO 3 ) 4 (H 2 O) 2 ] 0.75 [M(NO 3 ) 5 (H 2 O)] 1.25 (NO 3 ) 2.75 ·H 2 O (M = Lu), and [M(TMDGA) 3 ][M(NO 3 ) 5 (H 2 O)](NO 3 )·CH 3 OH (M = Y) were all synthesized via solvent diffusion of reaction mixtures containing the metal nitrate M(NO 3 ) 3 ·nH 2 O and TMDGA. Single-crystal X-ray diffraction analyses of these new structures show that each TMDGA complex comprises of three TMDGA ligands coordinating the metal ion via carbonyl and etheric oxygen atoms forming [M(TMDGA) 3 ] 3+ cations. Spectroscopy measurements under high pressure displayed notable differences in the f → f transition shifting between that of Nd(III) and Am(III). Shifting of transitions by 2.0 nm were observed in Nd up to 8.50 ± 0.09 GPa, while Am saw shifting between 11.0 to 13.5 nm at pressures up to 20.06 ± 1.90 GPa. The local geometry in these complexes is a distorted spherical capped square antiprism (CSAPR-9) except for of the yttrium complex, which exhibits a distorted spherical tricapped trigonal prismatic (TCTPR-9) geometry. Further, the anions that form concomitantly with the TMDGA complexes are composed of hexanitrato species for the early lanthanide ions (lanthanum to samarium); whereas the remaining smaller lanthanides did not possess sufficiently large ionic radii to coordinate six bidentate nitrate anions, instead, one or two nitrate anions are situated in the outer sphere. The systematic progression of changes in the anionic environments of these complexes outlines the changing coordination habits afforded by the lanthanide contraction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Effect of f -element complexation on the radiolysis of 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP])

A systematic study of the impact on the chemical reactivity of the oxidising n-dodecane radical cation (RH˙ + ) with f-element complexed 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) has been undertaken utilizing time-resolved electron pulse radiolysis/transient absorption spectroscopy and high-level quantum mechanical calculations. Lanthanide ion complexed species, [Ln((HEH[EHP]) 2 ) 3 ], exhibited vastly increased reactivity (over 10× faster) in comparison to the non-complexed ligand in n-dodecane solvent, whose rate coefficient was k = (4.66 ± 0.22) × 10 9 M -1 s -1 . Similar reactivity enhancement was also observed for the corresponding americium ion complex, k = (5.58 ± 0.30) × 10 10 M -1 s -1 . The vastly increased reactivity of these f-element complexes was not due to simple increased diffusion-control of these reactions; rather, enhanced hole transfer mechanisms for the complexes were calculated to become energetically more favourable. Interestingly, the observed reactivity trend with lanthanide ion size was not linear; instead, the rate coefficients showed an initial increase (Lu to Yb) followed by a decrease (Tm to Ho), followed by another increase (Dy to La). This behaviour was excellently predicted by the calculated reaction volumes of these complexes. In conclusion, complementary cobalt-60 gamma irradiations for select lanthanide complexes demonstrated that the measured kinetic differences translated to increased ligand degradation at steady-state timescales, affording ~38% increase in ligand loss of a 1:1 [La((HEH[EHP]) 2 ) 3 ]: HEH[EHP] ratio system.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Machine learning guided discovery of ternary compounds involving La and immiscible Co and Pb elements

Abstract Ternary compounds with an immiscible pair of elements are relatively unexplored but promising for novel quantum materials discovery. Exploring what third element and its ratio that can be added to make stable ternary compounds out of an immiscible pair of elements remains a great challenge. In this work, we combine a machine learning (ML) method with ab initio calculations to efficiently search for the energetically favorable ternary La-Co-Pb compounds containing immiscible elements Co and Pb. Three previously reported structures are correctly captured by our approach. Moreover, we predict a ground state La 3 CoPb compound and 57 low-energy La-Co-Pb ternary compounds. Attempts to synthesize La 3 CoPb via multiple techniques produce mixed or multi-phases samples with, at best, ambiguous signals of the predicted lowest-energy La 3 CoPb and the second lowest-energy La 18 Co 28 Pb 3 phases. The calculated results of Gibbs free energy are consistent with experiments, and will provide very useful guidance for further experimental synthesis.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Pyridinium Salts of Dehydrated Lanthanide Polychlorides

The reaction of lanthanide (Ln) chloride hydrates ([Ln(H 2 O) n (Cl) 3 ]) with pyridine (py) yielded a set of dehydrated pyridinium (py-H) Ln-polychloride salts. These species were crystallographically characterized as [[py-H-py][py-H] 2 [LnCl 6 ]] (Ln-6; Ln = La, Ce, Pr, Nd, Sm, Eu, Gd) or [[py-H] 2 [LnCl 5 (py)]] ((Ln-5; Ln = Tb, Dy, Ho, Er, Tm, Yb, Lu). The Ln-6 metal centers adopt an octahedral (OC-6) geometry, binding six Cl ligands. The -3 charge is off-set by two py-H moieties and a di-pyridinium (py-H-py) ion. For the Ln-5 species, an OC-6 anion is formed by the Ln cation binding a single py and five Cl ligands. The remaining -2 charge is offset by two py-H + cations that H-bond to the anion. Significant H-bonding occurs between the various cation/anion moieties inducing the molecular stability. The change in structure from the Ln-6 to Ln-5 is believed to be due to the Ln-contraction producing a smaller unit cell, which prevents formation of the py-H-py + cation, leading to the loss of the H-bonding-induced stability. Based on this, it was determined that the Ln-5 structures only exist when the lattice energy is small. While dehydrated polychloride salts can be produced by simply mixing in pyridine, the final structures adopted result from a delicate balance of cation size, Coulombic charge, and stabilizing H-bonding.

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

Adsorption of Rare Earth Elements onto DNA-Functionalized Mesoporous Carbon

The recovery and separation of rare earth elements (REEs) are of national importance owing to the specific usages, high demand, and low supply of these elements. In this research, we have investigated the adsorption of rare earth elements onto DNA-functionalized mesoporous carbons with a BET surface area of 605 m2/g and a median mesopore width of 48 Å. Additionally, three types of single-stranded DNA, one with 100 base units of thymine, another with 20 units of thymine, and the third, a 2000 unit long DNA from salmon milt were grafted on the carboxylated mesoporous carbon surface. All of the DNA-functionalized mesoporous carbons demonstrated higher adsorption of REEs compared to pristine mesoporous carbon and DNA grafted with 100 units of thymine demonstrated slightly higher adsorbed amounts compared to others. Pure neodymium (Nd(III)) adsorption in the aqueous phase demonstrated an adsorbed amount of 110.4 mg/g with respect to the initial concentration of 500 mg/g. A pH variation study with pure Nd(III) demonstrated that the adsorbed amount is higher at elevated pH compared to that at lower pH, thereby suggesting possible recovery at lower pH. Adsorption of a mixture of 16 REEs, including Sc, Lu, Tm, Yb, Er, Ho, Tb, Dy, Y, Eu, Gd, Sm, Ce, Nd, Pr, and La revealed that the adsorbed amount increased with an increase in the atomic weight and metallic radii of elements within the lanthanides. The calculation of the distribution coefficients for all of the equilibrium adsorption amounts suggested that adsorption is more effective in the lower concentration region. The Nd L3-edge X-ray absorption near edge structure (XANES) confirmed a 3+ oxidation state of Nd in the adsorbed phase. The extended X-ray absorption fine structure (EXAFS) confirmed the local atomic structure relaxation of Nd complexes in the adsorbed phase and shortening of the Nd–O bond distance by about 0.03–0.04 Å, which may be associated with their local complexation at the carbon surface.

36 MATERIALS SCIENCE↗
NASA NTRS1999

Cepheid Calibration of the Peak Brightness of SNe Ia.: SN 1989B in NGC 3627 - 9

Repeated imaging observations have been made of NGC 3627 with the Hubble Space Telescope in 1997/98, over an interval of 58 days. Images were obtained on 12 epochs in the F555W band and on five epochs in the F8141,V band. The galaxy hosted the prototypical, "Branch normal", type la supernova SN 1989B. A total of 83 variables have been found, of which 68 are definite Cepheid variables with periods ranging from 75 days to 3.85 days. The de-reddened distance modulus is determined to be (m - M)(sub 0) = 30.22 +/- 0.12 (internal uncertainty) using a subset of the Cepheid data whose reddening and error parameters are secure. The photometric data of Wells et al. (1994), combined with the Cepheid data for NGC 3627 give MB(max) = -19.36 +/- 0.18 and M(sub V)(max) = -19.34 +/- 0.16 for SN 1989B. Combined with the previous six calibrations in this program, plus two additional calibrations determined by others gives the mean absolute magnitudes at maximum of (M(sub B)) = -19.48 +/- 0.07 for "Brunch normal" SNe Ia at this interim stage in the calibration program. Using the argument by Wells et al. (1994) that SN 1989B here is virtually identical in decay rate and colors at maximum with SN 198ON in NGC 1316 in the Fornax cluster, and that such identity means nearly identical absolute magnitude, it follows that the difference in the distance modulus of NGC 3627 and NGC 1316 is 1.62 +/- 0.03 mag. Thus the NGC 3627 modulus implies that (m - M)(sub 0) = 31.84 for NGC 1316. The second parameter correlations of M(max) of blue SNe la with decay rate, color at maximum, and Hubble type are re-investigated. The dependence of (M(max)) on decay rate is non-linear, showing a minimum for decay rates between 1.0 less than ADelta(sub m)15 less than 1.6. Magnitudes corrected for decay rate show no dependence on Hubble type, but a dependence on color remains. Correcting both the fiducial sample of 34 SNe la with decay-rate data and the current eight calibrating SNe la for the correlation with decay rate as well as color gives H(sub 0) = 60 +/- 2 (internal) km/s Mpc, in both B and V. The same value to within 4% is obtained if only the SNe la in spirals (without second parameter corrections) are considered. The correlation of SNe la color at maximum with M(max) cannot be due to internal absorption because the slope coefficients in B, V, and I with the change in magnitude are far from or even opposite to the canonical reddening values. The color effect must be intrinsic to the supernova physics. "Absorption" corrections of distant blue SNe la will lead to incorrect values of H(sub 0). The Cepheid distances used in this series are insensitive to metallicity differences. The zeropoint of the P-L relation is based on an assumed LMC modulus of (m - M)(sub 0) = 18.50. As this may have to be increased by 0(sup m).06 to 0(sup m).08, all distances in this paper will follow and Ho will decrease by 3 - 4%.

Saha, A.↗
DOE OSTI2026

Coupled Chemical and Mechanical Control of Phase Stability in Lanthanide-Substituted BiVO 4

Doping is widely used to enhance the photoelectrochemical performance of BiVO 4 , yet solubility limits and polymorphic stability constrain compositional tuning. Here, in this study, the role of trivalent cation substitution (Ln = La, Nd, Dy, Ho, Y) on pressure-induced phase transformations in Bi 1–x Ln x VO 4 (x ≤ 0.5) is described. Powder X-ray and neutron diffraction reveal that increasing Ln content stabilizes the tetragonal zircon-type polymorph under ambient conditions, while applied pressures of up to ∼5 GPa promote conversion to the monoclinic fergusonite-type polymorph. In-situ neutron diffraction on Bi 0.8 La 0.2 VO 4 shows a reversible monoclinic to tetragonal transition near 2–3 GPa with a bulk modulus of 147 GPa. The extent of conversion depends strongly on dopant identity, concentration, and synthetic route, with mixed-phase solid-state samples converting more efficiently than phase-pure coprecipitated materials. These results demonstrate pressure as a viable pathway to access metastable, doped BiVO 4 compositions beyond conventional solubility limits.

Sypkes, Kathryn I. [University of Sydney, NSW (Aus↗
DOE OSTI2022

Machine Learning-Guided Discovery of Ternary Compounds Containing La, P, and Group 14 Elements

In this work, we integrate a deep machine learning (ML) method with first-principles calculations to efficiently search for the energetically favorable ternary compounds. Using La–Si–P as a prototype system, we demonstrate that ML-guided first-principles calculations can efficiently explore crystal structures and their relative energetic stabilities, thus greatly accelerate the pace of material discovery. A number of new La–Si–P ternary compounds with formation energies less than 30 meV/atom above the known ternary convex hull are discovered. Among them, the formation energies of La 5 SiP 3 and La 2 SiP phases are only 2 and 10 meV/atom, respectively, above the convex hull. These two compounds are dynamically stable with no imaginary phonon modes. Moreover, by replacing Si with heavier-group 14 elements in the eight lowest-energy La–Si–P structures from our ML-guided predictions, a number of low-energy La–X–P phases (X = Ge, Sn, Pb) are predicted.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1995

Satellite observations of upper-layer variabilities in the western Pacific warm pool

The variabilities of the upper layer of the western Pacific warm pool (WPWP) were observed using satellite infrared data from 1982 to 1991 and altimeter data from November 1986 to September 1989. The warm pool was defined as the area where the sea surface temperatures are above 28 C. The eastern boundary oscillation, the centroid movement, and the upper-layer volume variation of the WPWP were intensively studied. Spectral analysis revealed that the eastern boundary oscillation of the WPWP was related to the El Nino event and the annual cycle. The centroid of the WPWP traced an ellipselike trajectory during a year and moved counterclockwise in most years. However, in 1982 and 1986, the years of the onset of El Nino events, the movements were clockwise. The upper-layer volume of the WPWP was divided latitudinally into three sections. The annual cycles in the northern (from 3 deg to 30 deg N) and southern (from 3 deg to 30 deg S) sections were dominant. No annual cycle was found in the equatorial section (from 3 deg S to 3 deg N), but the volume of warm water in the equatorial Pacific increased during the 1986/87 El Nino event. The equatorial section was further divided into the eastern and western sectors along 165 deg W. During the 1986/87 El Nino event, the volume of warm water increased in the eastern sector, but the variation was smaller in the western sector than that in the eastern sector. During the 1988 La Nina event, the warm water volumes decreased in both sectors.

Ho, Chung-Ru↗
DOE OSTI2020

Materials Data on La4(HoS2)11 by Materials Project

La4(HoS2)11 crystallizes in the monoclinic C2/m space group. The structure is three-dimensional. there are six inequivalent Ho3+ sites. In the first Ho3+ site, Ho3+ is bonded to seven S2- atoms to form distorted HoS7 pentagonal bipyramids that share corners with three HoS6 octahedra, edges with two equivalent HoS6 octahedra, and edges with four equivalent HoS7 pentagonal bipyramids. The corner-sharing octahedra tilt angles range from 40–50°. There are a spread of Ho–S bond distances ranging from 2.70–2.89 Å. In the second Ho3+ site, Ho3+ is bonded to six S2- atoms to form a mixture of corner and edge-sharing HoS6 octahedra. The corner-sharing octahedra tilt angles range from 49–59°. There are a spread of Ho–S bond distances ranging from 2.65–2.78 Å. In the third Ho3+ site, Ho3+ is bonded to six S2- atoms to form HoS6 octahedra that share corners with three equivalent HoS6 octahedra, corners with two equivalent HoS7 pentagonal bipyramids, and edges with four HoS6 octahedra. The corner-sharing octahedra tilt angles range from 51–63°. There are a spread of Ho–S bond distances ranging from 2.66–2.80 Å. In the fourth Ho3+ site, Ho3+ is bonded to six S2- atoms to form HoS6 octahedra that share corners with three equivalent HoS6 octahedra, a cornercorner with one HoS7 pentagonal bipyramid, edges with four equivalent HoS6 octahedra, and edges with two equivalent HoS7 pentagonal bipyramids. The corner-sharing octahedra tilt angles range from 51–63°. There are a spread of Ho–S bond distances ranging from 2.67–2.77 Å. In the fifth Ho3+ site, Ho3+ is bonded to six S2- atoms to form a mixture of corner and edge-sharing HoS6 octahedra. The corner-sharing octahedra tilt angles range from 49–59°. There are a spread of Ho–S bond distances ranging from 2.66–2.78 Å. In the sixth Ho3+ site, Ho3+ is bonded to six S2- atoms to form a mixture of corner and edge-sharing HoS6 octahedra. The corner-sharing octahedral tilt angles are 55°. There are two shorter (2.73 Å) and four longer (2.74 Å) Ho–S bond lengths. There are two inequivalent La+2.75+ sites. In the first La+2.75+ site, La+2.75+ is bonded in a 8-coordinate geometry to eight S2- atoms. There are a spread of La–S bond distances ranging from 2.94–3.07 Å. In the second La+2.75+ site, La+2.75+ is bonded in a 7-coordinate geometry to eight S2- atoms. There are a spread of La–S bond distances ranging from 2.93–3.49 Å. There are eleven inequivalent S2- sites. In the first S2- site, S2- is bonded to three Ho3+ and two equivalent La+2.75+ atoms to form distorted SLa2Ho3 trigonal bipyramids that share corners with four SLa2Ho3 trigonal bipyramids, corners with two SLaHo3 trigonal pyramids, edges with six SLa2Ho3 trigonal bipyramids, and edges with two equivalent SHo4 trigonal pyramids. In the second S2- site, S2- is bonded in a rectangular see-saw-like geometry to four Ho3+ atoms. In the third S2- site, S2- is bonded in a 3-coordinate geometry to three Ho3+ and one La+2.75+ atom. In the fourth S2- site, S2- is bonded to three Ho3+ and two equivalent La+2.75+ atoms to form distorted SLa2Ho3 trigonal bipyramids that share corners with six SLa2Ho3 trigonal bipyramids, corners with two equivalent SLaHo3 trigonal pyramids, edges with two equivalent SLa2Ho3 square pyramids, edges with four SLa2Ho3 trigonal bipyramids, and an edgeedge with one SLaHo3 trigonal pyramid. In the fifth S2- site, S2- is bonded to three Ho3+ and two equivalent La+2.75+ atoms to form distorted SLa2Ho3 square pyramids that share corners with two equivalent SLa2Ho3 square pyramids, corners with four SLa3Ho2 trigonal bipyramids, edges with three SLa2Ho3 square pyramids, edges with three SLa2Ho3 trigonal bipyramids, and edges with two equivalent SLaHo3 trigonal pyramids. In the sixth S2- site, S2- is bonded to three Ho3+ and two equivalent La+2.75+ atoms to form distorted SLa2Ho3 square pyramids that share corners with four SLa2Ho3 square pyramids, corners with two equivalent SLa3Ho2 trigonal bipyramids, corners with two equivalent SLaHo3 trigonal pyramids, edges with four SLa2Ho3 square pyramids, and edges with three SLa3Ho2 trigonal bipyramids. In the seventh S2- site, S2- is bonded to two equivalent Ho3+ and three La+2.75+ atoms to form distorted SLa3Ho2 trigonal bipyramids that share corners with four SLa2Ho3 square pyramids, corners with two equivalent SLa2Ho3 trigonal bipyramids, corners with four equivalent SHo4 trigonal pyramids, edges with two SLa2Ho3 square pyramids, edges with six SLa2Ho3 trigonal bipyramids, and edges with three SLaHo3 trigonal pyramids. In the eighth S2- site, S2- is bonded to three Ho3+ and one La+2.75+ atom to form distorted SLaHo3 trigonal pyramids that share corners with two equivalent SLa2Ho3 square pyramids, corners with four SLa2Ho3 trigonal bipyramids, corners with five SLaHo3 trigonal pyramids, edges with two equivalent SLa2Ho3 square pyramids, and edges with three SLa3Ho2 trigonal bipyramids. In the ninth S2- site, S2- is bonded in a rectangular see-saw-like geometry to four Ho3+ atoms. In the tenth S2- site, S2- is bonded to four Ho3+ atoms to form distorted SHo4 trigonal pyramids that share corners with five SLa2Ho3 trigonal bipyramids, corners with five SLaHo3 trigonal pyramids, edges with three SLa2Ho3 trigonal bipyramids, and edges with two equivalent SHo4 trigonal pyramids. In the eleventh S2- site, S2- is bonded to two equivalent Ho3+ and three La+2.75+ atoms to form distorted SLa3Ho2 trigonal bipyramids that share corners with two equivalent SLa2Ho3 square pyramids, corners with four SLa2Ho3 trigonal bipyramids, a cornercorner with one SLaHo3 trigonal pyramid, edges with two equivalent SLa2Ho3 square pyramids, and edges with six SLa2Ho3 trigonal bipyramids.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Tuning the interfacial spin-orbit coupling with ferroelectricity

Detection and manipulation of spin current lie in the core of spintronics. Here we report an active control of a net spin Hall angle, θ SHE (net), in Pt at an interface with a ferroelectric material PZT (PbZr 0.2 Ti 0.8 O 3 ), using its ferroelectric polarization. The spin Hall angle in the ultra-thin Pt layer is measured using the inverse spin Hall effect with a pulsed tunneling current from a ferromagnetic La 0.67 Sr 0.33 MnO 3 electrode. The effect of the ferroelectric polarization on θ SHE (net) is enhanced when the thickness of the Pt layer is reduced. When the Pt layer is thinner than 6 nm, switching the ferroelectric polarization even changes the sign of θ SHE (net). This is attributed to the reversed polarity of the spin Hall angle in the 1 st -layer Pt at the PZT/Pt interface when the ferroelectric polarization is inverted, as supported by the first-principles calculations. These findings suggest a route for designing future energy efficient spin-orbitronic devices using ferroelectric control.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗