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

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At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Theory of optical responses in clean multi-band superconductors

Electromagnetic responses in superconductors provide valuable information on the pairing symmetry as well as physical quantities such as the superfluid density. However, at the superconducting gap energy scale, optical excitations of the Bogoliugov quasiparticles are forbidden in conventional Bardeen-Cooper-Schrieffer superconductors when momentum is conserved. Accordingly, far-infrared optical responses have been understood in the framework of a dirty-limit theory by Mattis and Bardeen for over 60 years. Here we show, by investigating the selection rules imposed by particle-hole symmetry and unitary symmetries, that intrinsic momentum-conserving optical excitations can occur in clean multi-band superconductors when one of the following three conditions is satisfied: (i) inversion symmetry breaking, (ii) symmetry protection of the Bogoliubov Fermi surfaces, or (iii) simply finite spin-orbit coupling with unbroken time reversal and inversion symmetries. This result indicates that clean-limit optical responses are common beyond the straightforward case of broken inversion symmetry. We apply our theory to optical responses in FeSe, a clean multi-band superconductor with inversion symmetry and significant spin-orbit coupling. This result paves the way for studying clean-limit superconductors through optical measurements.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Search for Q ~0 Order near a Forbidden Bragg Position in Bi 2.1 Sr 1.9 CaCu 2 O 8+x with Resonant Soft X-ray Scattering

Identifying what broken symmetries are present in the cuprates has become a major area of research. Many authors have reported evidence for so-called “Q ~ 0” order that involves broken inversion, mirror, chiral, or time-reversal symmetry that is uniform in space. Not all these observations are well understood and new experimental probes are needed. Here we use resonant soft x-ray scattering (RSXS) to search for Q ~ 0 order in Bi 2.1 Sr 1.9 CaCu 2 O 8+x (Bi-2212) by measuring the region of a forbidden Bragg peak, (0,0,3), which is normally extinguished by symmetry but may become allowed on resonance if valence band order is present. Using circularly polarized light, we found that this reflection becomes allowed on the CuL 3 resonance for temperatures T c < T < T*, though remains absent in linear polarization and at other temperatures. This observation suggests the existence of spatially uniform valence band order near the pseudogap temperature. In addition, we observed periodic oscillations in the specular reflectivity from the sample surface that resemble thin film interference fringes, though no known film is present. These fringes are highly resonant, appear in all polarizations, and exhibit a period that depends on the location where the beam strikes the sample surface. We speculate that these fringes arise from interaction between some intrinsic valence band instability and extrinsic structural surface morphologies of the material. Our study supports the existence of some kind of Q ~ 0 broken symmetry state in Bi-2212 at intermediate temperatures. Further studies using a microfocused beam, which could disentangle microscopic effects from macroscopic heterogeneities, are needed to ascertain the universality of the effect.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Quasiparticle self-consistent GW band structures and phase transitions of LiAlO 2 in tetrahedrally and octahedrally coordinated structures

In this work, a first-principles computational study is presented of various phases of LiAlO 2 . The relative total energies and equations of state of the α, β, and γ phases are determined after structural relaxation of each phase. The β and γ tetrahedral phases are found to be very close in energy and lattice volume with the γ phase having the lowest energy. The octahedral α phase is a high-pressure phase and the transition pressure from the γ and β phases to α is determined to be about 1 GPa. The electronic band structures of each phase at their own equilibrium volume are determined using the quasiparticle self-consistent (QS) GW method as well as using the 0.8 Σ approach in which the QS GW self-energy is reduced by a factor of 0.8 to correct for the underscreening of W in QS GW. The effective masses of the band edges and the nature of the band gaps are presented. The lowest energy γ phase is found to have a pseudodirect gap of 7.69 eV. The gap is direct at Γ but corresponds to a dipole forbidden transition. The imaginary part of the dielectric function and the absorption coefficient are calculated in the long-wavelength limit and the random phase approximation, without local field or electron-hole interaction effects for each phase, and their anisotropies are discussed. Si doping on the Al site is investigated as a possible n-type dopant in γ-LiAlO 2 using a 128-atom supercell corresponding to 3.125% Si on the Al sublattice in the generalized gradient approximation and a smaller 16-atom cell with 25% Si in the QS GW approximation. The Si is found to significantly perturb the conduction band and lower the gap but a clearly separated deep donor defect level is not found. However, the donor binding energy is still expected to be relatively deep, on the order of a few tenths eV in the hydrogenic effective mass approximation.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Color center in β -Ga 2 O 3 emitting at the telecom range

Transition metal (TM) ions incorporated into a host from a wide bandgap semiconductor are recognized as a promising system for quantum technologies with enormous potential. In this work, we report on a TM color center in β-Ga 2 O 3 with physical properties attractive for quantum information applications. The center is found to emit at 1.316 μm and exhibits weak coupling to phonons, with optically addressable higher-lying excited states, beneficial for single-photon emission within the telecom range (O-band). Using magneto-photoluminescence (PL) complemented by time-resolved PL measurements, we identify the monitored emission to be internal 1 E→ 3 A 2 spin-forbidden transitions of a 3d 8 TM ion with a spin-triplet ground state—a possible candidate for a spin qubit. We tentatively attribute this color center to a complex involving a sixfold coordinated Cu 3+ ion.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Magneto-optical Evidence of the Tilting Effect in Coupled Weyl Bands

Theories have revealed the universality of the band tilting effect in topological Weyl semimetals (WSMs) and its implications for the material physical properties. However, the experimental identification of tilted Weyl bands remains less explored. Here, we report the magneto-optical evidence of the tilting effect in WSM niobium phosphide. Specifically, we observe Landau level transitions with rich features that are well reproduced within a model of coupled tilted Weyl points. Our analysis indicates that the tilting effect relaxes the selection rules and leads to transitions that would otherwise be forbidden in the non-tilt case. Additionally, we observe unconventional interband transitions with flat and negative magnetic field dispersions, highlighting the importance of coupling between Weyl points. Our results not only emphasize the significance of the tilting effect in the optical responses of WSMs but also demonstrate magneto-optics as an effective tool for probing the tilting effect in electronic band structures.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2024

Dark states of electrons in a quantum system with two pairs of sublattices

A quantum state of matter that is forbidden to interact with photons and is therefore undetectable by spectroscopic means is called a dark state. This basic concept can be applied to condensed matter where it suggests that a whole band of quantum states could be undetectable across a full Brillouin zone. Here we report the discovery of such condensed-matter dark states in palladium diselenide as a model system that has two pairs of sublattices in the primitive cell. By using angle-resolved photoemission spectroscopy, we find valence bands that are practically unobservable over the whole Brillouin zone at any photon energy, polarization and scattering plane. Our model shows that two pairs of sublattices located at half-translation positions and related by multiple glide-mirror symmetries make their relative quantum phases polarized into only four kinds, three of which become dark due to double destructive interference. This mechanism is generic to other systems with two pairs of sublattices, and we show how the phenomena observed in cuprates, lead halide perovskites and density wave systems can be resolved by the mechanism of dark states. Our results suggest that the sublattice degree of freedom, which has been overlooked so far, should be considered in the study of correlated phenomena and optoelectronic characteristics.

electronic properties and materials↗
DOE OSTI2023

Satellite-Dominated Sulfur L 2,3 X-ray Emission of Alkaline Earth Metal Sulfides

The sulfur L 2,3 X-ray emission spectra of the alkaline earth metal sulfides BeS, MgS, CaS, SrS, and BaS are investigated and compared with spectra calculations based on density functional theory. Very distinct spectral shapes are found for the different compounds. With decreasing electronegativity of the cation, that is, increasing ionic bonding character, the upper valence band width and its relative spectral intensity decrease. These general trends are qualitatively reproduced by the spectra calculations, which give quite an accurate description of the spectral shapes in the upper valence band region. On the low energy side of the sulfur 3s → 2p transition dominating the spectra, we find strong satellites caused by "semi-Auger" decays involving configuration interaction. These satellites, previously believed to be energetically forbidden for sulfur L 2,3 emission and only observed for the L 2,3 emission of Cl to Cr, increase in intensity as the bonding character becomes more ionic and dominate the spectra for SrS and BaS. The intensities, energies, and widths of the satellites vary strongly between the investigated compounds, giving a very specific spectral fingerprint that can be used for speciation analysis.

36 MATERIALS SCIENCE↗
DOE OSTI2020

A far‐red‐emitting (Gd,Y) 3 (Ga,Al) 5 O 12 :Mn 2+ ceramic phosphor with enhanced thermal stability for plant cultivation

Abstract As for plants, far‐red (FR) light with wavelength from 700 nm to 740 nm is critical for processes of photosynthesis and photomorphogenesis. Light‐controlled development depends on light to control cell differentiation, structural and functional changes, and finally converge into the formation of tissues and organs. Phosphor converted FR emission under LED excitation is a cost‐effective and high‐efficient way to provide artificial FR light source. With the aim to develop an efficient FR phosphor that can promote the plant growth, a series of gadolinium yttrium gallium garnet (GYGAG) transparent ceramic phosphors co‐doped with Mn 2+ and Si 4+ have been fabricated via chemical co‐precipitation method, followed sintered in O 2 and hot isostatic pressing in this work. Under UV excitation, the phosphor exhibited two bright and broadband red emission spectra due to Mn 2+ : 4 T 1 → 6 A 1 spin‐forbidden transition, and one of which located in the right FR region. And then, Ce 3+ ions were co‐doped as the activator to enhance the absorption at blue light region and the emission of Mn 2+ . It turns out that the emission band of GYGAG transparent ceramic phosphors matches well with the absorption band of phytochrome P FR , which means they are promising to be applied in plant cultivation light‐emitting diodes (LEDs) for modulating plant growth. Besides, the thermal stability of this material was investigated systematically, and an energy transferring model involves defects was also proposed to explain the phenomenon of abnormal temperature quenching.

Qiu, Xuting↗
DOE OSTI2021

Dynamic Rashba-Dresselhaus Effect

The Rashba-Dresselhaus effect is the splitting of doubly degenerate band extrema in semiconductors, accompanied by the emergence of counterrotating spin textures and spin-momentum locking. Here we investigate how this effect is modified by lattice vibrations. We show that, in centrosymmetric nonmagnetic crystals, for which a bulk Rashba-Dresselhaus effect is symmetry-forbidden, electron-phonon interactions can induce a phonon-assisted, dynamic Rashba-Dresselhaus spin splitting in the presence of an out-of-equilibrium phonon population. In particular, we show how Rashba, Dresselhaus, or Weyl spin textures can selectively be established by driving coherent infrared-active phonons, and we perform ab initio calculations to quantify this effect for halide perovskites.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2022

Real- and momentum-space description of the excitons in bulk and monolayer chromium tri-halides

Excitons with large binding energies ~2–3 eV in CrX 3 have been characterized as being localized (Frenkel) excitons that emerge from the atomic d – d transitions between the Cr-3d-t 2g and e g orbitals. The argument has gathered strength in recent years as the excitons in recently made monolayers are found at almost the same energies as the bulk. The Laporte rule, which restricts such parity forbidden atomic transitions, can relax if a symmetry-breaking mechanism is present. While what can be classified as a purely Frenkel exciton is a matter of definition, we show using an advanced first principles parameter-free approach that these excitons in CrX 3 , in both its bulk and monolayer variants, have band origin and it is the dp hybridization between Cr and X that primarily acts as the symmetry-breaking mechanism that relaxes the Laporte rule. We show that the character of these excitons is mostly determined by the Cr-d orbital manifold, nevertheless, the fractions of the spectral weight shared with the ligand halogen states increases as the dp hybridization enhances. The hybridization enhances as the halogen atom becomes heavier, bringing the X-p states closer to the Cr-d states in the sequence Cl → Br → I, with an attendant increase in exciton intensity and a decrease in binding energy. By applying a range of different kinds of perturbations that qualitatively mimics the effects originating from the missing vertex in self-energy, we show that moderate changes to the two-particle Hamiltonian that essentially modifies the Cr-d-X-p hybridization, can alter both the intensities and positions of the exciton peaks. A detailed analysis of several deep-lying excitons, with and without strain, elucidates the fact that the exciton is most Frenkel-like in CrCl 3 and CrBr 3 and acquires mixed Frenkel–Wannier character in CrI 3 , making the excitons in CrI 3 most susceptible to environmental screening and spin–orbit coupling.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Electronic Melting of Silicon in Nanostructures using X-ray Forbidden Bragg Reflections

Abstract We carried out a short beamtime at the Pohang Accelerator Laboratory x-ray Free Electron Laser to perform a pump-probe (PP) laser excitation diffraction experiment on the silicon (222) forbidden Bragg peak. To limit the x-ray penetration, we used a “device layer” silicon film wafer bonded to a silicon substrate. The sample, specially fabricated by MEMC Electronic Materials, had a Si(100) substrate bonded to a 170 nm Si(100) film rotated at 45° for crystallographic isolation. A second sample was reactive-ion-etched down to 52 nm thickness. In the silicon lattice, the covalent bonds are seen exclusively at the 222 reflection. Upon laser excitation, these electrons are expected to be excited to the valence band on femtosecond electronic time scales. The Si(222) reflection is therefore expected to be extinguished on this fast time scale, while the electron–phonon coupled acoustic response is determined by the lattice dynamics. The latter is determined by the speed of sound over the device thickness, which is in the mid-picosecond range.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2020

The Outburst of the Young Star Gaia19bey

We report photometry and spectroscopy of the outburst of the young stellar object Gaia19bey. We have established the outburst light curve with archival Gaia “G,” ATLAS “Orange,” Zwicky Transient Facility r-band, and Pan-STARRS “rizy”-filter photometry, showing an outburst of ~4 yr duration, longer than typical EX Lupi objects but shorter than FU Orionis objects. Its pre-outburst spectral energy distribution shows a flat far-infrared spectrum, confirming the early evolutionary state of Gaia19bey and its similarity to other deeply embedded young stars experiencing outbursts. A lower limit to the peak outburst luminosity is ~182 L{sub ⊙} at an assumed distance of 1.4 kpc, the minimum plausible distance. Infrared and optical spectroscopy near maximum light show an emission line spectrum, including H i lines, strong red Ca ii emission, other metal emission lines, infrared CO bandhead emission, and a strong infrared continuum. Toward the end of the outburst, the emission lines have all but disappeared and the spectrum has changed into an almost pure continuum spectrum. This indicates a cessation of magnetospheric accretion activity. The near-infrared colors have become redder as Gaia19bey has faded, indicating a cooling of the continuum component. Near the end of the outburst, the only remaining strong emission lines are forbidden shock-excited emission lines. Adaptive optics integral-field spectroscopy shows the H{sub 2} 1–0 S(1) emission with the morphology of an outflow cavity and the extended emission in the [Fe ii] line at 1644 nm with the morphology of an edge-on disk. However, we do not detect any large-scale jet from Gaia19bey.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

Nebular Models of Sub-Chandrasekhar Mass Type Ia Supernovae: Clues to the Origin of Ca-rich Transients

In this work we use non-local thermal equilibrium radiative transport modeling to examine observational signatures of sub-Chandrasekhar mass double detonation explosions in the nebular phase. Results range from spectra that look like typical and subluminous Type Ia supernovae (SNe) for higher mass progenitors to spectra that look like Ca-rich transients for lower mass progenitors. This ignition mechanism produces an inherent relationship between emission features and the progenitor mass as the ratio of the nebular [Ca II ]/[Fe III ] emission lines increases with decreasing white dwarf mass. Examining the [Ca II ]/[Fe III ] nebular line ratio in a sample of observed SNe we find further evidence for the two distinct classes of SNe Ia identified in Polin et al. by their relationship between Si ii velocity and B-band magnitude, both at time of peak brightness. This suggests that SNe Ia arise from more than one progenitor channel, and provides an empirical method for classifying events based on their physical origin. Furthermore, we provide insight to the mysterious origin of Ca-rich transients. Low-mass double detonation models with only a small mass fraction of Ca (1%) produce nebular spectra that cool primarily through forbidden [Ca II ] emission.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

Inert Gas Element as Active Infrared‐Absorption Source and Donor in Silicon for Forbidden‐Wavelength Sensing

Intrinsic silicon (Si) is forbidden for infrared (IR) sensing at the communication wavelength like 1.31 or 1.55 µm due to the well‐known bandgap limitation. In this work, an unexpected physical picture of using argon (Ar) is identified, which is usually inert to the surrounding chemical environment and used as a protective agent in semiconductor processing, to overcome the IR‐sensing‐forbidden problem in Si. Here, in this work, it is shown by an analysis of a dynamic secondary ion mass spectrometer that such a Si, when exposed to laser pulse in Ar gas, can contain a very high dose of Ar up to 10 20 cm −3 even after 1300 days. First‐principles calculations, molecular dynamics, and Hall effect measurements reveal that, due to both steric and dynamic repulsions by Ar orbitals to Si dangling bonds, the Ar‐filled‐vacancy produces a much wider defect band inside the gap, which is not only responsible for strong infrared absorption, but also causes a significant increase in n‐type conductivity, both in line with experiments. The study proves that originally inert elements in fact can act as active impurities in semiconductors for advanced applications, which updates the current knowledge of defect physics.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Accessing One-Dimensional Chains of Halogenoindates(III) in Organic–Inorganic Hybrids

Organic-inorganic hybrids of halogenoindates(III) are typically represented by one of the zero-dimensional units: InX 4 – , InX 5 2– , InX 6 3– , or In 2 X 11 5– . Higher dimensional anionic forms, although not forbidden, have remained almost elusive. Here, in this study, we report for the first time In 3+ -based organic–inorganic hybrids, (C 4 H 5 N 2 S) 2 InCl 5 and (C 4 H 5 N 2 S) 2 InBr 5 , with 1D anionic chains of trans-halide-bridged InX 6 octahedra whose formation is guided by 2-mercaptopyrimidinium cations (C 4 H 5 N 2 S + ). The chains are characterized by the significant ease of deformation, which is reflected in the elongation of the bridging bonds or the displacement of In 3+ ions. The materials show a robust band gap predominantly governed by C 4 H 5 N 2 S + cations. Dielectric relaxation processes in (C 4 H 5 N 2 S) 2 InBr 5 arise from the cations’ dynamics and suggest the ability of the brominated system to accommodate even larger cations. Our work represents a successful attempt to expand the structural diversity of halogenoindates(III) and opens a pathway to reach multifunctional 1D In 3+ -based hybrids.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Photoelectron spectroscopy of cryogenically cooled NiO 2 – via slow photoelectron velocity-map imaging

In this work, high-resolution anion photoelectron spectra of cryogenically cooled NiO 2 – anions, obtained using slow photoelectron velocity-map imaging (cryo-SEVI), are presented in tandem with coupled cluster electronic structure calculations including relativistic effects. The experimental spectra encompass the $\tilde{\text{X}}^1Σ_{\text{g}}^+ ← \tilde{\text{X}}^2Π_{\text{g}}, ã^3Π{\text{g}} ← \tilde{\text{X}}^2Π_{\text{g}}$, and $\tilde{\text{A}}^1Π_{\text{g}} ← \tilde{\text{X}}^2Π_{\text{g}}$ photodetachment transitions of linear ONiO 0/– , revealing previously unobserved vibrational structure in all three electronic bands. The high-resolution afforded by cryo-SEVI allows for the extraction of vibrational frequencies for each state, consistent with those previously measured in the ground state and in good agreement with scalar-relativistic coupled-cluster calculations. Previously unobserved vibrational structure is observed in the $ã^3Π_{\text{g}}$ and $Ã^1Π_{\text{g}}$ states and is tentatively assigned. Further, a refined electron affinity of 3.0464(7) eV for NiO 2 is obtained as well as precise term energies for the ã and à states of NiO 2 of 0.3982(7) and 0.7422(10) eV, respectively. Numerous Franck–Condon forbidden transitions involving the doubly degenerate $ν_2$ bending mode are observed and ascribed to Herzberg-Teller coupling to an excited electronic state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Oxygen vacancy-induced ferroelectric effect in (111) strontium titanate single crystals controls photoelectrochemical water oxidation

Ferroelectric materials, such as tetragonal BaTiO 3 , have a permanent electric polarization that can be controlled with an external electric field, however, a ferroelectric polarization in cubic SrTiO 3 is forbidden by the higher symmetry of the lattice. Here we demonstrate that hydrogen annealed SrTiO 3−x single crystals can be polarized electrically, and that the polarization controls the activity for photoelectrochemical water oxidation, a pathway to solar hydrogen fuel. Specifically, it is observed that the anodic water oxidation photocurrent increases from 0.99 to 2.22 mA cm −2 at 1.23 V RHE (60 mW cm −2 , UV illumination) or decreases to 0.50 mA cm −2 after electric polarization of hydrogen-annealed (111) SrTiO 3−x single crystals in forward or reverse direction. The polarization also modifies the surface photovoltage signal of the material and its flat band potential, based on Mott–Schottky measurements. These observations are attributed to the formation of an electric dipole at the (111) SrTiO 3−x surface, which alters the potential drop across the depletion layer at the solid–liquid junction, and with it the electron transfer barrier. Density functional theory calculations confirm that an electric dipole can result from the movement of oxygen vacancies between the surface or sub-surface layers of SrTiO 3−x . The filling of these surface oxygen vacancies is the probable cause for the observed disappearance of the electric polarization after 24 h storage in air and 48 h in argon. Overall, this work establishes a new surface-based ferroelectric effect in SrTiO 3−x and its use for solar energy conversion during photoelectrochemical water oxidation. Because oxygen vacancy defects are common, similar electric polarization effects are to be expected in other metal oxides.

Assavachin, Samutr [University of California, Davi↗
DOE OSTI2020

Aperiodically ordered nano-graphene on the quasicrystalline substrate

Designing exotic structures in low dimensions is key in today's quest to tailor novel quantum states in materials with unique symmetries. Particularly intriguing materials in this regard are low dimensional aperiodic structures with non-conventional symmetries that are otherwise forbidden in translation symmetric crystals. In our work, we focus on the link between the structural and electronic properties of aperiodically ordered aromatic molecules on a quasicrystalline surface, which has largely been neglected so far. As an exemplary case, we investigate the self-assembly and the interfacial electronic properties of the nano-graphene-like molecule coronene on the bulk truncated icosahedral (i) Al–Pd–Mn quasicrystalline surface using multiple surface sensitive techniques. We find an aperiodically ordered coronene monolayer (ML) film on the i-Al–Pd–Mn surface that is characterized by the same local motifs of the P1 Penrose tiling model as the bare i-Al–Pd–Mn surface. The electronic valence band structure of the coronene/i-Al–Pd–Mn system is characterized by the pseudogap of thebare i-Al–Pd–Mn, which persists the adsorption of coronene confirming the quasiperiodic nature of the interface. In addition, we find a newly formed interface state of partial molecular character that suggests an at least partial chemical interaction between the molecule and the quasicrystalline surface. We propose that this partial chemical molecule–surface interaction is responsible for imprinting the quasicrystalline order of the surface onto the molecular film.

36 MATERIALS SCIENCE↗