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At least 1,351 records · Page 75
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DOE OSTI2018

Auger-induced charge migration

Novel perspectives of controlling molecular systems have recently arisen from the possibility of generating attosecond pulses in the ultraviolet regime and tailoring electron dynamics in its natural time scale. The cornerstone mechanism is the so-called charge migration, he production of a coherent charge transfer with subfemtosecond oscillations across a molecule. Typically, charge migration is induced by the ionization of valence molecular orbitals. However, recent technological developments allow the generation of attosecond pulses in the x-ray regime. Here, in this case, the absorption of photons creates core-hole states. In light elements, core-hole states mainly decay by Auger processes that, driven by electron correlations, involve valence orbitals. We theoretically demonstrate in a fluoroacetylene molecule a double-hole charge migration triggered by attosecond core-electron photoionization, followed by Auger electron relaxations. This opens a new route for inducing with x rays charge transfer processes in the subfemtosecond time scale.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2019

Configuration-interaction many-body perturbation theory for La II electric-dipole transition probabilities

We report that accurate transition probabilities of La II ion are calculated using configuration-interaction many-body perturbation theory with 10 adjustable parameters, seven of which are evaluated from energies of the La III single-valence electron ion. Comparison is given for transitions probabilities and lifetimes with experiments and theories. Close agreement with experiment is observed for most transitions. The theoretical approach can be extended to other divalent atoms and ions with strong valence-core interactions and to more complex atoms. Laslty, the theory will be useful for opacity evaluation and astrophysical applications.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2020

Resonant Soft X-Ray Scattering from Stripe-Ordered La 2 - x Ba x Cu O 4 Detected by a Transition-Edge Sensor Array Detector

Resonant soft x-ray scattering (RSXS) is a leading probe of valence-band order in materials best known for detecting charge-density-wave order in copper-oxide superconductors. One of the biggest limitations on the RSXS technique is the presence of a severe fluorescence background, which, like the RSXS cross section itself, is enhanced under resonant conditions. This background prevents the study of weak signals such as diffuse scattering from glassy or fluctuating order that is spread widely over momentum space. Recent advances in superconducting transition-edge-sensor (TES) detectors have led to major improvements in energy resolution and detection efficiency in the soft x-ray range. Here, we perform a RSXS study of stripe-ordered La 2 - x Ba x Cu O 4 at the Cu L 3 / 2 edge (932.2 eV) using a TES detector with 1.5-eV resolution, to evaluate its utility for mitigating the fluorescence-background problem. We find that, for suitable degree of detuning from the resonance, the TES rejects the fluorescence background, leading to a five to ten times improvement in the statistical quality of the data compared to an equivalent, energy-integrated measurement. We conclude that a TES introduces a promising method to reducing background in RSXS studies and may lead to discoveries in materials exhibiting valence-band order that is fluctuating or glassy.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Discrete Electronic Bands in Semiconductors and Insulators: Potential High-Light-Yield Scintillators

Bulk semiconductors and insulators typically have continuous valence and conduction bands. In this paper, we show that valence and conduction bands of a multinary semiconductor or insulator can be split to narrow discrete bands separated by large energy gaps. This unique electronic structure is demonstrated by first-principles calculations in several quaternary elpasolite compounds, i.e., Cs 2 NaInBr 6 , Cs 2 NaBiCl 6 , and Tl 2 NaBiCl 6 . The narrow discrete band structure in these quaternary elpasolites is due to the large electronegativity difference among cations and the large nearest-neighbor distances in cation sublattices. We further use Cs 2 NaInBr 6 as an example to show that the narrow bands can stabilize self-trapped and dopant-bound excitons (in which both the electron and the hole are strongly localized in static positions on adjacent sites) and promote strong exciton emission at room temperature. The discrete band structure should further suppress thermalization of hot carriers and may lead to enhanced impact ionization, which is usually considered inefficient in bulk semiconductors and insulators. Finally, these characteristics can enable efficient room-temperature light emission in low-gap scintillators and may overcome the light-yield bottleneck in current scintillator research.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Benefits of Carrier-Pocket Anisotropy to Thermoelectric Performance: The Case of p -Type AgBiSe 2

Here we study theoretically the effects of anisotropy on the thermoelectric performance of p-type AgBiSe 2 . We present an apparent realization of the thermoelectric benefits of one-dimensional plate-like carrier pocket anisotropy in the valence band of this material. Based on first principles calculations we find a substantial anisotropy in the electronic structure, likely favorable for thermoelectric performance, in the valence bands of the hexagonal phase of the silver chalcogenide thermoelectric AgBiSe 2 , while the conduction bands are more isotropic, and in our experiments do not attain high performance. AgBiSe 2 has already exhibited a ZT value of 1.5 in a high-temperature disordered fcc phase, but room-temperature performance has not been demonstrated. We develop a theory for the ability of anisotropy to decouple the density-of-states and conductivity effective masses, pointing out the influence of this effect in the high performance thermoelectrics Bi 2 Te 3 and PbTe. From our first principles and Boltzmann transport calculations we find that p-type AgBiSe 2 has substantial promise as a room temperature thermoelectric, and estimate its performance.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Evidence of a Shockley-Read-Hall Defect State Independent of Band-Edge Energy in InAs / In ( As , Sb ) Type-II Superlattices

A set of seven InAs/InAsSb type-II superlattices (T2SLs) were designed to have speci c bandgap energies between 290 meV (4.3 m) and 135 meV (9.2 m) in order to study the e ects of the T2SL bandgap energy on the minority carrier lifetime. A temperature dependent optical pump-probe technique is used to measure the carrier lifetimes, and the e ect of a mid-gap defect level on the carrier recombination dynamics is reported. The Shockley-Read-Hall (SRH) defect state is found to be at energy of approximately -250 12 meV relative to the valence band edge of bulk GaSb for the entire set of T2SL structures, even though the T2SL valence band edge shifts by 155 meV on the same scale. These results indicate that the SRH defect state in InAs/InAsSb T2SLs is singular and is nearly independent of the exact position of the T2SL bandgap or band edge energies. They also suggest the possibility of engineering the T2SL structure such that the SRH state is removed completely from the bandgap, a result that should signi cantly increase the minority carrier lifetime.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Carrier Lifetimes in a I I I - V - N Intermediate-Band Semiconductor

Here we use transient absorption spectroscopy to measure carrier lifetimes in the multiband semiconductor GaP y As 1-x-y N x . These measurements probe the electron populations in the conduction band, intermediate band, and valence band as a function of time after an excitation pulse. Following photoexcitation of GaP 0.32 As 0.67 N 0.01 , we find that the electron population in the conduction band decays exponentially with a time constant τ CB =23 ps. The electron population in the intermediate band exhibits bimolecular recombination with recombination constant r = 2×10 -8 cm 3 /s. In our experiment, an optical pump pulse excites electrons from the valence band to the intermediate and conduction bands, and the change in interband absorption due to absorption saturation and induced absorption is probed with a delayed white-light pulse. We model the optical properties of our samples using the band anticrossing model to extract carrier densities as a function of time. Finally, these results not only identify the short minority-carrier lifetime as a key factor affecting the performance of GaP y As 1-x-y N x -based intermediate-band solar cells but also provide guidance on ways to address this issue.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2017

Electronic Properties, Screening, and Efficient Carrier Transport in NaSbS 2

NaSbS 2 is a semiconductor that was recently shown to have remarkable efficacy as a solar absorber indicating efficient charge collection even in material containing defects. We report first-principles calculations of properties that show (1) an indirect gap only slightly smaller than the direct gap, which may impede the recombination of photoexcited carriers, (2) highly anisotropic electronic and optical properties reflecting a layered crystal structure, (3) a pushed-up valence-band maximum due to repulsion from the Sb 5s states, and (4) cross-gap hybridization between the S p—derived valence bands and the Sb 5p states. This latter feature leads to enhanced Born effective charges that can provide local screening and, therefore, defect tolerance. Finally, these features are discussed in relation to the performance of the compound as a semiconductor with efficient charge collection.

14 SOLAR ENERGY↗
DOE OSTI2017

Hybrid-Functional Calculations of the Copper Impurity in Silicon

We calculate formation energies and transition levels for copper-related defects in silicon using the screened hybrid functional of Heyd, Scuseria, and Ernzerhof HSE06. We consider Cu siting on interstitial sites ( Cu i ), a substitutional site ( Cu Si ), a Cu Si - Cu i pair, a complex formed from substitutional Cu and interstitial hydrogen ( Cu Si - H i ), and a complex formed from a substitutional Cu and three interstitial Cu atoms ( Cu Si - 3 Cu i ). We find that Cu i is a fast diffuser, with a migration barrier of only 0.19 eV, in good agreement with experimental values. Cu i is a shallow donor and its formation energy is lower than that of Cu Si for all Fermi-level positions in the band gap. Cu Si , on the other hand, induces levels in the gap which are related to the occupation of antibonding states originating from the coupling between the Cu 3 d states ( t 2 ( d ) ), resonant in the valence band, and the vacancy-induced gap states ( t 2 ( p ) ). The stable charge states of Cu Si in the gap are + 1 , 0, - 1 , and - 2 . The transition levels of Cu Si - Cu i and Cu Si - H i are closely related to the levels of isolated Cu Si : a donor level ( + / 0 ) near the valence band, an acceptor level near midgap, and a double-acceptor level in the upper part of the gap. Overall, the calculated transition levels are in good agreement with experimental results, and the formation energies explain the observed solubility.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2019

Probing single-unit-cell resolved electronic structure modulations in oxide superlattices with standing-wave photoemission

Control of structural coupling at complex-oxide interfaces is a powerful platform for creating ultrathin layers with electronic and magnetic properties unattainable in the bulk. Yet, with the capability to design and control the electronic structure of such buried layers and interfaces at a unit-cell level, a new challenge emerges to be able to probe these engineered emergent phenomena with depth-dependent atomic resolution as well as element- and orbital selectivity. In this work, we utilize a combination of core-level and valence-band soft x-ray standing-wave photoemission spectroscopy, in conjunction with scanning transmission electron microscopy, to probe the depth-dependent and single-unit-cell resolved electronic structure of an isovalent manganite superlattice [Eu 0.7 Sr 0.3 MnO 3 /La 0.7 Sr 0.3 MnO 3 ]×15 wherein the electronic-structural properties are intentionally modulated with depth via engineered oxygen octahedra rotations/tilts and A-site displacements. Our unit-cell resolved measurements reveal significant transformations in the local chemical and electronic valence-band states, which are consistent with the layer-resolved first-principles theoretical calculations, hence opening the door for future depth-resolved studies of a wide variety of heteroengineered material systems.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2019

Strong magnetoelastic effect in CeCo 1-x Fe x Si as Neel order is suppressed

A very strong magnetoelastic effect in the CeCo 1 – x Fe x Si alloys is reported here. The strength of the magnetostrictive effect can be tuned upon changing x . The moderate low-temperature linear magnetostriction observed at low Fe concentrations becomes very large ( Δ L L 16 T , 2 K = 3 × 10 – 3 ) around the critical concentration x c ≈ 0.23 at which the long-range antiferromagnetic order vanishes. Upon increasing doping through the nonmagnetic region ( x > x c ) , the magnetostriction strength gradually weakens again. The interplay between magnetic order and the Kondo screening appears to cause an enhanced valence susceptibility slightly changing the Ce ions valence, ultimately triggering the large magnetostriction observed around the critical concentration. Previous studies of the evolution of the lattice parameters with x as well as magnetization and x-ray absorption spectroscopy measurements support this hypothesis.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Probing the local electronic structure of isovalent Bi atoms in InP

Cross-sectional scanning tunneling microscopy (X-STM) is used to experimentally study the influence of isovalent Bi atoms on the electronic structure of InP. In this work, we map the spatial pattern of the Bi impurity state, which originates from Bi atoms down to the sixth layer below the surface, in topographic, filled-state X-STM images on the natural {110} cleavage planes. The Bi impurity state has a highly anisotropic bowtielike structure and extends over several lattice sites. These Bi-induced charge redistributions extend along the $\langle$110$\rangle$ directions, which define the bowtielike structures we observe. Local tight-binding calculations reproduce the experimentally observed spatial structure of the Bi impurity state. In addition, the influence of the Bi atoms on the electronic structure is investigated in scanning tunneling spectroscopy measurements. These measurements show that Bi induces a resonant state in the valence band, which shifts the band edge toward higher energies. Furthermore, we show that the energetic position of the Bi-induced resonance and its influence on the onset of the valence band edge depend crucially on the position of the Bi atoms relative to the cleavage plane.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2020

High-order harmonic generation in solid C 60

High-order harmonic generation (HHG) has unleashed the power of strong laser physics in solids. Here we investigate HHG from a large system, solid C 60 , with 240 valence electrons engaging harmonic generation at each crystal momentum. We employ the density functional theory and the time-dependent Liouville equation of the density matrix to compute HHG signals. We find that under a moderately strong laser pulse, HHG signals reach 15th order, consistent with the experimental results from C 60 plasma. The helicity dependence in solid C 60 is weak, due to the high symmetry. In contrast to the general belief, HHG is unsuitable for band structure mapping in C 60 . However, we find a window of opportunity using a long wavelength, where harmonics are generated through multiple-photon excitation. In particular, the fifth-order harmonic energies closely follow the transition energy dispersion between the valence and conduction bands. Finally, this finding is expected to motivate future experimental investigations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Prediction of exotic magnetic states in the alkali-metal quasi-one-dimensional iron selenide compound Na 2 FeSe 2

The magnetic and electronic phase diagram of a model for the quasi-one-dimensional alkali-metal iron selenide compound Na 2 FeSe 2 is presented. The novelty of this material is that the valence of iron is Fe 2+ , contrary to most other iron-chain compounds with valence Fe 3+ . Using first-principles techniques, we developed a three-orbital tight-binding model that reproduces the ab initio band structure near the Fermi level. Including Hubbard and Hund couplings and studying the model via the density-matrix renormalization group and Lanczos methods, we constructed the ground-state phase diagram. A robust region where the block state ↑↑↓↓↑↑↓↓ is stabilized was unveiled. The analog state in iron ladders, employing 2×2 ferromagnetic blocks, is by now well established, but in chains a block magnetic order has not been observed yet in real materials. The phase diagram also contains a large region of canonical staggered spin order ↑↓↑↓↑↓↑ at very large Hubbard repulsion. At the block-to-staggered transition region, an exotic phase is stabilized with a mixture of both states: an inhomogeneous orbital-selective charge density wave with the exotic spin configuration ↑↑↓↑↓↓↑↓. Our predictions for Na 2 FeSe 2 may guide crystal growers and neutron-scattering experimentalists towards the realization of block states in one-dimensional iron selenide chain materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Mapping the unoccupied state dispersions in Ta 2 NiSe 5 with resonant inelastic x-ray scattering

The transition metal chalcogenide Ta 2 NiSe 5 undergoes a second-order phase transition at T c = 328 K involving a small lattice distortion. Below T c , a band gap at the center of its Brillouin zone increases up to about 0.35 eV. In this work, we study the electronic structure of Ta 2 NiSe 5 in its low-temperature semiconducting phase, using resonant inelastic x-ray scattering (RIXS) at the Ni L 3 -edge. In addition to a weak fluorescence response, we observe a collection of intense Raman-like peaks that we attribute to electron-hole excitations. Using density functional theory calculations of its electronic band structure, we identify the main Raman-like peaks as interband transitions between valence and conduction bands. Further, by performing angle-dependent RIXS measurements, we uncover the dispersion of these electron-hole excitations that allows us to extract the low-energy boundary of the electron-hole continuum. From the dispersion of the valence band measured by angle-resolved photoemission spectroscopy, we derive the effective mass of the lowest unoccupied conduction band.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Hybridization effect on the x-ray absorption spectra for actinide materials: Application to PuB 4

Studying the local moment and 5 f -electron occupations sheds insight into the electronic behavior in actinide materials. X-ray absorption spectroscopy (XAS) has been a powerful tool to reveal the valence electronic structure when assisted with theoretical calculations. However, the analysis currently taken in the community on the branching ratio of the XAS spectra generally does not account for the hybridization effects between local f orbitals and conduction states. In this paper, we discuss an approach which employs the density functional theory plus Gutzwiller rotationally invariant slave boson method to obtain a local Hamiltonian for the single-impurity Anderson model, and calculates the XAS spectra by the exact diagonalization (ED) method. A customized numerical routine was implemented for the ED XAS part of the calculation. By applying this technique to the recently discovered 5 f -electron topological Kondo insulator Pu B 4 , we determined the signature of 5 f -electronic correlation effects in the theoretical x-ray spectra. Furthermore, we found that the Pu 5 f - 6 d hybridization effect provides an extra channel to mix the j = 5 / 2 and 7 / 2 orbitals in the 5 f valence. As a consequence, the resulting electron occupation number and spin-orbit coupling strength deviate from the intermediate-coupling regime.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Quasiparticle self-consistent $GW$ energy band calculations for $\mathrm{Ge_3N_4}$ phases

Quasiparticle self-consistent GW (G Green's function, W screened Coulomb interaction) band structure calculations are presented for the α, β, and γ phases of Ge 3 N 4 . The GW corrections to the gap are substantial and the gaps are found to be 3.85, 3.86, and 3.56 eV for α, β, γ respectively, at the experimental lattice constants. Only the β phase has a direct gap. The α and β phases, which are closely related to each other in crystal structure, are consequently also found to have rather similar band structures. Nonetheless, some significant differences are found near the valence band maximum, which are related to the different interlayer interactions in the c direction. In the cubic spinel phase, the conduction band minima of s and p character are found close to each other. Effective masses are calculated for the relevant valence and conduction band edges and for the cubic case analyzed in terms of the Kohn-Luttinger effective Hamiltonian. Finally, the optical response functions from direct interband transitions are calculated.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Phonons, Q-dependent Kondo spin fluctuations, and 4f phonon resonance in YbAl 3

4f intermediate valence (IV) compounds are canonical hosts of correlated electron physics and can contribute to our understanding of the larger class of correlated electron materials. In this work, we study the prototype IV compound YbAl 3 which exhibits a nonintegral valence with a moderately heavy fermion ground state and a large Kondo temperature (T K ~500–600K). To better characterize the correlated physics of YbAl 3 , we have measured the phonon and the magnetic excitation spectra on single crystals of this material by time-of-flight inelastic neutron scattering and inelastic x-ray scattering. We have also performed theoretical calculations of the phonon spectra. We present three findings of these measurements. First, we observe that the measured phonon spectra can be described adequately by a calculation based on standard DFT+U density functional theory. The calculated energies, however, are 10% too low compared to the measured energies. This discrepancy may reflect a hardening of the phonons due to dynamic 4f correlations. Second, the low-temperature spin fluctuations on the Kondo energy scale k B T K have a momentum (Q) dependence similar to that seen recently in the IV compound CePd 3 . For that system, the Q dependence has been attributed to particle-hole excitations in a coherent itinerant 4f correlated ground state. We suggest a similar origin for the momentum dependence seen in YbAl 3 . This Q dependence disappears as the temperature is raised towards room temperature and the 4f electron band states become increasingly incoherent. Such a coherent/incoherent crossover is expected to be generic for correlated electron systems. Third, a low-temperature magnetic peak observed in the neutron scattering near 30 meV shows dispersion identical to a particular optic-phonon branch. This 4f/phonon resonance disappears for T≥150K. The phonon spectrum appears to be unaffected by the resonance. We discuss several possibilities for the origin of this unusual excitation, which may be unique to YbAl 3 . We suggest that the excitation may arise from the large amplitude beating of the light Al atoms against the heavy Yb atoms, resulting in a dynamic 4f/3p hybridization.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗