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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Atomic-Site-Specific Surface Valence-Band Structure from X-Ray Standing-Wave Excited Photoemission

X-ray standing-wave (XSW) excited photoelectron emission was used to measure the site-specific valence band (VB) for ½ monolayer (ML) Pt grown on a SrTiO 3 (001) surface. The XSW induced modulations in the core level (CL), and VB photoemission from the surface and substrate atoms were monitored for three ℎ⁡kl substrate Bragg reflections. The XSW CL analysis shows the Pt to have a face-centered-cubic-like cube-on-cube epitaxy with the substrate. The XSW VB information compares well to a density functional theory calculated projected density of states from the surface and substrate atoms. Altogether, this Letter represents a novel method for determining the contribution to the density of states by valence electrons from specific atomic surface sites.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2021

Experimental determination of the valence band offsets of ZnGeN 2 and (ZnGe) 0.94 Ga 0.12 N 2 with GaN

A predicted type-II staggered band alignment with an approximately 1.4 eV valence band offset at the ZnGeN 2 /GaN heterointerface has inspired novel band-engineered III-N/ZnGeN 2 heterostructure-based device designs for applications in high performance optoelectronics. We report on the determination of the valence band offset between metalorganic chemical vapor deposition grown (ZnGe) 1- x Ga 2 x N 2 , for x = 0 and 0.06, and GaN using x-ray photoemission spectroscopy. The valence band of ZnGeN 2 was found to lie 1.45–1.65 eV above that of GaN. This result agrees well with the value predicted by first-principles density functional theory calculations using the local density approximation for the potential profile and quasiparticle self-consistent GW calculations of the band edge states relative to the potential. For (ZnGe) 0.94 Ga 0.12 N 2 the value was determined to be 1.29 eV, ~10%–20% lower than that of ZnGeN 2 . The experimental determination of the large band offset between ZnGeN 2 and GaN provides promising alternative solutions to address challenges faced with pure III-nitride-based structures and devices.

Physics↗
NASA NTRS1987

Determination of a natural valence-band offset - The case of HgTe and CdTe

A method to determine a natural valence-band offset (NVBO), i.e., the change in the valence-band maximum energy which is intrinsic to the bulk band structures of semiconductors is proposed. The HgTe-CdTe system is used as an example in which it is found that the valence-band maximum of HgTe lies 0.35 + or - 0.06 eV above that of CdTe. The NVBO of 0.35 eV is in good agreement with the X-ray photoemission spectroscopy measurement of the heterojunction offset. The procedure to determine the NVBO between semiconductors, and its implication on the heterojunction band lineup and the electronic structures of semiconductor alloys, are discussed.

Shih, C. K.↗
DOE OSTI2024

First-Principles Treatment of Vibrational Broadening in X-Ray Excited Valence Band Spectra for n-SrTiO 3 (001)

The valence band maximum (VBM) is an important quantity for semiconductors as it locates the Fermi level relative to the band edge. Accurate measurement of this quantity in near-surface regions of semiconductors by photoemission is a first step toward determining the electronic properties of heterostructures involving these materials. While extrapolating the leading edge of the valence band to the energy axis in photoemission spectra is a widely used way to find the VBM, this method can be ambiguous if the leading edge exhibits multiple slopes. Another way to determine the VBM is to fit the leading edge to an appropriately broadened, cross-section modulated theoretical density of states (DOS). Three kinds of broadening that should be included for maximum accuracy are those due to: (1) finite instrumental resolution, (2) valence hole lifetime, and (3) vibrational excitations. While steps (1) and (2) are straightforward to implement, (3) is more difficult because the appropriate amount of broadening is not known a priori. Here, we demonstrate that explicit inclusion of vibrational broadening using ab initio molecular dynamics facilitates accurate VBM determination for n-SrTiO 3 (001). The total DOS is constructed by summing time-averaged projections at elevated temperature onto s - , p - , and d orbitals for the constituent atoms and modulating with the associated photoemission cross sections. Subsequent convolutions of the total DOS, first with a Gaussian of width equal to the experimental energy resolution and second with a Lorentzian to simulate valence hole lifetime effects, yield line shapes that reproduce the experimental leading edges rather well. The VBM is then given by the energy at which the vibrationally broadened total DOS (prior to the convolutions) goes to zero. The VBMs generated by this method quantitatively agree with those resulting from extrapolating from the middle of the measured leading edge for SrTiO 3 .

36 MATERIALS SCIENCE↗
DOE OSTI2021

Attosecond intra-valence band dynamics and resonant-photoemission delays in W(110)

Time-resolved photoelectron spectroscopy with attosecond precision provides new insights into the photoelectric effect and gives information about the timing of photoemission from different electronic states within the electronic band structure of solids. Electron transport, scattering phenomena and electron-electron correlation effects can be observed on attosecond time scales by timing photoemission from valence band states against that from core states. However, accessing intraband effects was so far particularly challenging due to the simultaneous requirements on energy, momentum and time resolution. Here we report on an experiment utilizing intracavity generated attosecond pulse trains to meet these demands at high flux and high photon energies to measure intraband delays between sp- and d- band states in the valence band photoemission from tungsten and investigate final-state effects in resonant photoemission.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2024

Valence-band hybridization in sulphides

The hybridization state in solids often defines the critical chemical and physical properties of a compound. However, it is difficult to spectroscopically detect and evaluate hybridization beyond just general fingerprint signatures. Here, the valence-band hybridization of metal d-derived bands (short: “metal d bands”) in selected metal sulphides is studied with a combined spectroscopic and theoretical approach to derive deeper insights into the fundamental nature of such compounds. The valence bands of the studied sulphides are comprised of hybrid bands derived from the metal d, S 3s, and S 3p states. Employing S K and L 2,3 X-ray emission spectroscopy and spectra calculations based on density functional theory, the degree of hybridization (i.e., the covalency) of these bands can be directly probed as a function of their relative energies. We find that the relative intensity of the “metal d band” features in the spectra scales with the inverse square of the energy separation to the respective sulfur-derived bands, which can be analytically derived from a simple two-orbital model. This study demonstrates that soft X-ray emission spectroscopy is a powerful tool to study valence state hybridization, in particular in combination with hard X-ray emission spectroscopy, promising a broad impact in many research fields.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Measurement of Conduction and Valence Bands g -Factors in a Transition Metal Dichalcogenide Monolayer

The electron valley and spin degree of freedom in monolayer transition-metal dichalcogenides can be manipulated in optical and transport measurements performed in magnetic fields. The key parameter for determining the Zeeman splitting, namely, the separate contribution of the electron and hole g factor, is inaccessible in most measurements. Here we present an original method that gives access to the respective contribution of the conduction and valence band to the measured Zeeman splitting. It exploits the optical selection rules of exciton complexes, in particular the ones involving intervalley phonons, avoiding strong renormalization effects that compromise single particle g -factor determination in transport experiments. These studies yield a direct determination of single band g factors. We measure g c1 = 0.86 ± 0.1, g c2 = 3.84 ± 0.1 for the bottom (top) conduction bands and g v = 6.1 ± 0.1 for the valence band of monolayer WSe 2 . These measurements are helpful for quantitative interpretation of optical and transport measurements performed in magnetic fields. In addition, the measured g factors are valuable input parameters for optimizing band structure calculations of these 2D materials.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Strong Valence Band Convergence to Enhance Thermoelectric Performance in PbSe with Two Chemically Independent Controls

We present an effective approach to favorably modify the electronic structure of PbSe using Ag doping coupled with SrSe or BaSe alloying. The Ag 4d states make a contribution to in the top of the heavy hole valence band and raise its energy. The Sr and Ba atoms diminish the contribution of Pb 6s2 states and decrease the energy of the light hole valence band. This electronic structure modification increases the density-of-states effective mass, and strongly enhances the thermoelectric performance. Furthermore, the Ag-rich nanoscale precipitates, discordant Ag atoms, and Pb/Sr, Pb/Ba point defects in the PbSe matrix work together to reduce the lattice thermal conductivity, resulting a record high average ZT avg of around 0.86 over 400–923 K.

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

Strong Valence Band Convergence to Enhance Thermoelectric Performance in PbSe with Two Chemically Independent Controls

Abstract We present an effective approach to favorably modify the electronic structure of PbSe using Ag doping coupled with SrSe or BaSe alloying. The Ag 4d states make a contribution to in the top of the heavy hole valence band and raise its energy. The Sr and Ba atoms diminish the contribution of Pb 6s 2 states and decrease the energy of the light hole valence band. This electronic structure modification increases the density‐of‐states effective mass, and strongly enhances the thermoelectric performance. Moreover, the Ag‐rich nanoscale precipitates, discordant Ag atoms, and Pb/Sr, Pb/Ba point defects in the PbSe matrix work together to reduce the lattice thermal conductivity, resulting a record high average ZT avg of around 0.86 over 400–923 K.

Luo, Zhong‐Zhen↗
DOE OSTI2023

Sensitivity of the MnTe valence band to the orientation of magnetic moments

An effective model of the hexagonal (NiAs-structure) manganese telluride valence band in the vicinity of the A point of the Brillouin zone is derived. It is shown that whereas for the usual antiferromagnetic order (magnetic moments on the basal plane) band splitting at A is small, their out-of-plane rotation enhances the splitting dramatically (to about 0.5 eV). Here we propose extensions of recent experiments where such inversion of magnetocrystalline anisotropy has been observed in Li-doped MnTe to confirm this unusual sensitivity of a semiconductor band structure to magnetic order.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Cation-size mismatch as a predictive descriptor for structural distortion, configurational disorder, and valence-band splitting in II-IV-N2 semiconductors

The II-IV-N2 class of heterovalent ternary nitrides has gained significant interest as alternatives to the III-nitrides for electronic and optoelectronic applications. In this study, we apply first-principles calculations based on density functional theory to systematically investigate the effects of structural distortions due to cation size mismatch on the configurational disorder of the cation sublattice and the valence band structure in this class of materials. We find that larger size mismatch between the group-II and the group-IV cations results in stronger lattice distortions from the ideal hexagonal ratio, which in turn inhibits the propensity of these materials toward octet-rule violating cation disorder. We also demonstrate that the formation energy of a single cation antisite pair, which is fast and simple to calculate, is a strong indicator of a material's propensity toward disorder. Furthermore, the breaking of in-plane symmetry leads to a splitting of the top three valence bands at Γ, which is also directly related to the magnitude of structural distortions. Our work demonstrates that the structural and functional properties of the II-IV-N2 materials can be finely tuned through controllable structural distortions that stem from the choice of cations.

Kute, Malhar (ORCID:0000000214364564)↗
NASA NTRS1991

The role of valence-band excitation in laser ablation of KCl

We present recent measurements of excited-atom and ion emission from KCl surfaces illuminated by vacuum-ultraviolet synchrotron radiation (h-nu = 8-28 eV) and ultraviolet laser light (h-nu = 4 eV). At low intensities characteristic of the synchrotron experiments, excited atoms are desorbed by simple valence-band excitation process involving the metallization of the KCl surface. At the higher intensities typical of laser desorption and ablation, we observe a strong decrease in K emission as a function of the number of laser shots, but an essentially constant yield of Cl. K(+) and Cl(-) emission at high intensities show similar behavior. The energetics of these desorption phenomena can be treated in a bond-orbital model which shows that creation of a single valence hole is sufficient to excite an ion to an anti-bonding state.

Haglund, Richard F., Jr.↗
DOE OSTI2020

Valence band electronic structure of the van der Waals ferromagnetic insulators: VI 3 and CrI 3

Ferromagnetic van der Waals (vdW) insulators are of great scientific interest for their promising applications in spintronics. It has been indicated that in the two materials within this class, CrI 3 and VI 3 , the magnetic ground state, the band gap, and the Fermi level could be manipulated by varying the layer thickness, strain or doping. To understand how these factors impact the properties, a detailed understanding of the electronic structure would be required. However, the experimental studies of the electronic structure of these materials are still very sparse. Here, we present the detailed electronic structure of CrI 3 and VI 3 measured by angle-resolved photoemission spectroscopy (ARPES). Our results show a band-gap of the order of 1 eV, sharply contrasting some theoretical predictions such as Dirac half-metallicity and metallic phases, indicating that the intra-atomic interaction parameter (U) and spin-orbit coupling (SOC) were not properly accounted for in the calculations. We also find significant differences in the electronic properties of these two materials, in spite of similarities in their crystal structure. In CrI 3 , the valence band maximum is dominated by the I 5p, whereas in VI 3 it is dominated by the V 3d derived states. Our results represent valuable input for further improvements in the theoretical modeling of these systems.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Influence of Bi alloying on GaAs valence band structure

Bi alloying is predicted to transform GaAs from a semiconductor to a topological insulator or semimetal. To date, studies of the GaAs 1−x Bi x alloy band structure have been limited, and the origins of Bi-induced enhancement of the spin-orbit splitting energy, Δ SO , are unresolved. Here, in this study, we present high-resolution angle-resolved photoemission spectroscopy of droplet-free epitaxial GaAs 1−x Bi x films with x Bi = 0.06. In addition to quantifying the Bi-induced shifts of the light-hole and heavy-hole valence bands, we probe the origins of the Bi-enhanced Δ SO . Using exact-two-component density functional theory calculations, we identify the key role of Bi p-orbitals in the upward shift of the light-hole and heavy-hole bands that results in the Bi-enhanced Δ SO .

Cooper, Joshua J. P. [Univ. of Michigan, Ann Arbor↗
DOE OSTI2021

Determining valence band offsets in heterojunctions using a single core-level x-ray photoelectron spectrum

The behavior and functionality of semiconductor heterojunctions depend critically on the alignments of the valence and conduction bands at the various interfaces. Traditionally band alignment has been measured by x-ray photoelectron spectroscopy using pairs of distinct core levels, one from each side of the interface, to track the valence band maxima in the two materials. Here, we demonstrate that it is possible to determine band alignment using a single core-level photoelectron spectrum for an element that is common to both materials. The energy splitting between the photoemission features originating in the two materials is shown to be dominated by the difference in electrostatic potential across the interface, leading to a reliable determination of the band alignment.

Wang, Le↗
NASA NTRS1982

Chemical bonding and charge redistribution - Valence band and core level correlations for the Ni/Si, Pd/Si, and Pt/Si systems

Via a systematic study of the correlation between the core and valence level X-ray photoemission spectra, the nature of the chemical bonding and charge redistribution for bulk transition metal silicides has been examined. Particular emphasis is placed on Pt2Si and PtSi. It is observed that the strength of the metal (d)-silicon (p) interaction increases in the order Ni2Si, Pd2Si, Pt2Si. It is also observed that both the metal and silicon core lines shift to higher binding energy as the silicides are formed. The notion of charge redistribution for metallic bonds is invoked to explain these data.

Grunthaner, P. J.↗