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At least 1,549 records · Page 86
All sourcesNASA NTRSDOE OSTI
DOE OSTI2012

Effect of Hydrogen Passivation on the Electronic Structure of Ionic Semiconductor Nanostructures

In theoretical studies of thin film and nanostructured semiconductors, pseudohydrogen (PH) is widely used to passivate the surface dangling bonds. Based on these calculations, it is often believed that nanostructured semiconductors, due to quantum confinement, have a larger band gap than their bulk counterparts. Using first-principles band structure theory calculation and comparing systematically the differences between PH-passivated and real-hydrogen-passivated (RH-passivated) semiconductor surfaces and nanocrystals, we show that, unlike PH passivation that always increases the band gap with respect to the bulk value, RH passivation of the nanostructured semiconductors can either increase or decrease the band gap, depending on the ionicity of the nanocompounds. The differences between PH and RH passivations decreases when the covalency of the semiconductor increases and can be explained using a band coupling model. This observation greatly increases the tunability of nanostructured semiconductor properties, especially for wide-gap ionic semiconductors.

08 HYDROGEN↗
DOE OSTI2012

Electronic structure of delta-doped La:SrTiO{sub 3} layers by hard x-ray photoelectron spectroscopy

We have employed hard x-ray photoemission (HAXPES) to study a delta-doped SrTiO{sub 3} layer that consisted of a 3-nm thickness of La-doped SrTiO{sub 3} with 6% La embedded in a SrTiO{sub 3} film. Results are compared to a thick, uniformily doped La:SrTiO{sub 3} layer. We find no indication of a band offset for the delta-doped layer, but evidence of the presence of Ti{sup 3+} in both the thick sample and the delta-layer, and indications of a density of states increase near the Fermi energy in the delta-doped layer. These results further demonstrate that HAXPES is a powerful tool for the non-destructive investigation of deeply buried doped layers.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Electronic Structure and Mechanical Properties of Solvated Montmorillonite Clay Using Large-Scale DFT Method

Montmorillonite clay (MMT) has been widely used in engineering and environmental applications as a landfill barrier and toxic waste repository due to its unique property as an expandable clay mineral that can absorb water easily. This absorption process rendered MMT to be highly exothermic due to electrostatic interactions among molecules and hydrogen bonds between surface atoms. A detailed study of a large supercell model of structural clay enables us to predict long-term nuclear waste storage. Herein, a large solvent MMT model with 4071 atoms is studied using ab initio density functional theory. The DFT calculation and analysis clarify the important issues, such as bond strength, solvation effect, elasticity, and seismic wave velocities. These results are compared to our previous study on crystalline MMT (dry). The solvated MMT has reduced shear modulus (G), bulk modulus (K), and Young’s modulus (E). We observe that the conduction band (CB) in the density of states (DOS) of solvated MMT model has a single, conspicuous peak at –8.5 eV. Moreover, the atom-resolved partial density of states (PDOS) summarizes the roles played by each atom in the DOS. These findings illuminate numerous potential sophisticated applications of MMT clay.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Temperature dependence of the electronic structure of La{sub 2}CuO{sub 4} in the multielectron LDA+GTB approach

The band structure of La{sub 2}CuO{sub 4} in antiferromagnetic and paramagnetic phases is calculated at finite temperatures by the multielectron LDA+GTB method. The temperature dependence of the band spectrum and the spectral weight of Hubbard fermions is caused by a change in the occupation numbers of local multielectron spin-split terms in the antiferromagnetic phase. A decrease in the magnetization of the sublattice with temperature gives rise to new bands near the bottom of the conduction band and the top of the valence band. It is shown that the band gap decreases with increasing temperature, but La{sub 2}CuO{sub 4} remains an insulator in the paramagnetic phase as well. These results are consistent with measurements of the red shift of the absorption edge in La{sub 2}CuO{sub 4} with increasing temperature.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Mixed Tin-Titanium Oxides by Atomic Layer Deposition on Planar Substrates: Physical and Electronic Structure

Ternary atomic layer deposition of Sn-doped TiO x (Sn:TiO x ) and Ti-doped SnO x (Ti:SnO x ) was performed using tetrakisdimethylamidotitanium (IV) and tin(IV) with water at 150 °C on (1 0 0) Si and quartz substrates. The physical structure of the films was investigated using scanning electron, atomic force, and Kelvin probe force microscopies as well as spectroscopic ellipsometry, Raman spectroscopy, and X-ray diffraction. All as-deposited films are amorphous and possessed flat and conformal topographies with low surface roughness (<1 nm). Annealed Sn:TiO x and Ti:SnO x crystallize into the tetragonal anatase TiO 2 and cassiterite SnO 2 structures, respectively, without large variations to the film topography. The chemical composition of the as-deposited and annealed films was investigated through X-ray photoelectron spectroscopy. While dopants are homogenously mixed, the ternary ALD to form Sn:TiO x and Ti:SnO x surprisingly does not follow the rule of mixtures, despite similarities in both the growth rates of binary SnO x and TiO x and the precursors used. This finding is also supported by spectroscopic ellipsometry. Here, we postulate the deviation from the rule of mixtures is due to non-ideal surface chemistry of the binary ALD of SnO x . The optical bandgap of all films was quantified by the Tauc analysis and the valence band position was investigated by valence band X-ray photoelectron spectroscopy. Intra-bandgap states above the valence band maximum were observed for as-deposited Ti:SnO x and Sn:TiO x and ascribed to 5 s states from Sn 2+ ions. The presence of these intra-bandgap states induces enhanced visible absorption and bathochromic shifts to the apparent bandgap for all as-deposited films. Annealing the films removes the intra-bandgap states and increases the optical bandgap. Simplified band diagrams created using the data available demonstrated that the conduction and valence band positions did not vary between the positions of pure TiO 2 or SnO 2 with monotonic increases to the dopant incorporation.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Electronic structure evolution in doping of fullerene (C{sub 60}) by molybdenum trioxide

Molybdenum oxide doping of fullerene has been investigated using ultraviolet photoemission spectroscopy (UPS), X-ray photoemission spectroscopy (XPS), and inverse photoemission spectroscopy (IPES). The lowest unoccupied molecular orbital and the highest occupied molecular orbital (HOMO) can be observed directly with IPES and UPS. It is observed that the Fermi level position in fullerene is modified by molybdenum oxide doping, and the HOMO onset is shifted to less than 0.3 eV below the Fermi level. The energy level shift is found to saturate at doping ratio of 18%. Till this stage, the shift depends on the doping concentration in a semi-logarithmic scale, with a slope substantially higher than that of the traditional semiconductor theory. The XPS results indicate that charge transfer continues beyond the energy level shift saturation till the doping ratio reaches 66% as evidenced by the Mo{sup 5+} component. At higher doping concentration, there is more Mo{sup 6+} component, which indicates the saturation of the charge transfer between MoO{sub x} and C{sub 60}.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2012

Electronic structure of CuCrO{sub 2} thin films grown on Al{sub 2}O{sub 3}(001) by oxygen plasma assisted molecular beam epitaxy

Thin films of CuCrO{sub 2} have been grown on Al{sub 2}O{sub 3}(001) substrates by oxygen plasma assisted molecular beam epitaxy. With a substrate temperature of 700 Degree-Sign C or 750 Degree-Sign C, the films showed an unanticipated (015) orientation but at a higher substrate temperature of 800 Degree-Sign C the expected basal (001) orientation predominates. The optical absorption spectrum of CuCrO{sub 2} shows a direct allowed absorption onset at 3.18 eV together with a weak peak at 2.0 eV which is suppressed by Sn doping. This suggests that the low energy peak should be attributed to 3d{yields}3d excitations associated with Cu{sup 2+} defect states rather than excitations localised on Cr{sup 3+}. Valence band X-ray photoemission spectra of (001) and (015) oriented CuCrO{sub 2} are compared with those obtained from polycrystalline samples.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

A fast, dense Chebyshev solver for electronic structure on GPUs

Matrix diagonalization is almost always involved in computing the density matrix needed in quantum chemistry calculations. In the case of modest matrix sizes (≲4000), performance of traditional dense diagonalization algorithms on modern GPUs is underwhelming compared to the peak performance of these devices. This motivates the exploration of alternative algorithms better suited to these types of architectures. We newly derive, and present in detail, an existing Chebyshev expansion algorithm whose number of required matrix multiplications scales with the square root of the number of terms in the expansion. Focusing on dense matrices of modest size, our implementation on GPUs results in large speed ups when compared to diagonalization. Additionally, we improve upon this existing method by capitalizing on the inherent task parallelism and concurrency in the algorithm. Furthermore, this improvement is implemented on GPUs by using CUDA and HIP streams via the MAGMA library and leads to a significant speed up over the serial-only approach for smaller (≲1000) matrix sizes. Finally, we apply our technique to a model system with a high density of states around the Fermi level, which typically presents significant challenges.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Synthesis, crystal and electronic structure, and optical property of the pentanary chalcohalide Ba{sub 3}KSb{sub 4}S{sub 9}Cl

The pentanary chalcohalide Ba{sub 3}KSb{sub 4}S{sub 9}Cl has been prepared from stoichiometric mixtures of KCl, Ba, Sb, and S in an evacuated silica tube, which is the first example of chalcohalides in the pentanary A/Ae/Sb/Q/X (A=alkali metal; Ae=alkaline-earth metal; Q=S, Se, Te; X=F, Cl, Br, I) system. This material crystallize in the Pnnm space group and its new structure type comprises one-dimensional (1D) [Sb{sub 3}S{sub 7}]{sup 5−} chains running down the [001] direction separated by isolated dimeric Sb{sub 2}S{sub 4} polyhedra, Ba{sup 2+}, K{sup +}, and Cl{sup −}, respectively. The optical gap of 1.99 eV for Ba{sub 3}KSb{sub 4}S{sub 9}Cl was deduced from the UV/vis reflectance spectroscopy and DFT study indicates a indirect band gap with an electronic transfer excitation of S 3p to Sb 5p orbital electrons. - Graphical abstract: The pentanary chalcohalide Ba{sub 3}KSb{sub 4}S{sub 9}Cl has been prepared, which contains one-dimensional (1D) [Sb{sub 3}S{sub 7}]{sup 5−} chains running down the [001] direction separated by isolated dimeric Sb{sub 2}S{sub 4} polyhedra, Ba{sup 2+}, K{sup +}, and Cl{sup −}, respectively. - Highlights: • Ba{sub 3}KSb{sub 4}S{sub 9}Cl is the first example of chalcohalides in the pentanary A/Ae/Sb/Q/X (A=alkali metal; Ae= alkaline-earth metal; Q=S, Se, Te; X=F, Cl, Br, I) system. • This material crystallizes in a new structure type with one-dimensional (1D) [Sb{sub 3}S{sub 7}]{sup 5−} chains running down the [001] direction separated by isolated dimeric Sb{sub 2}S{sub 4} polyhedra, Ba{sup 2+}, K{sup +}, and Cl{sup −}, respectively. • The optical gap of 1.99 eV for Ba{sub 3}KSb{sub 4}S{sub 9}Cl was deduced from UV/Vis reflectance spectroscopy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Single-Particle Insights Into the Electronic Structure and Enhanced Stability of CsPbBr 3 /FAPbBr 3 Core/Crown Nanoplatelets at the Nanometer Scale

Colloidal perovskite nanoplatelets (NPLs), despite their exceptional optoelectronic properties, face significant challenges due to their intrinsic instability and trap-assisted non-radiative recombination. Although many studies employing surface engineering, such as selecting ligands or coating to passivate defects, have demonstrated improved optoelectronic properties, these enhancements are typically inferred from bulk-ensemble measurements; the effects at the single-particle level remain elusive. Here, we conduct single-particle-level studies using scanning tunneling spectroscopy (STS) on a unique core–crown system, CsPbBr 3 @FAPbBr 3 NPLs, where the lateral surfaces of the CsPbBr 3 core are coated with an FAPbBr 3 crown. Experimental density-of-states (DOS) analysis reveals a 47% reduction in deep-trap states in core-crown NPLs compared to core-only NPLs, consistent with nearly two-fold enhancements in photoluminescence quantum yields. Progressive I–V sweep measurements demonstrate superior electrical stability in core-crown NPLs, preserving band structure with minimal degradation, while core-only NPLs exhibit rapid bandgap shrinkage and trap formation. Density functional theory (DFT) calculations indicate that FA incorporation distorts Pb octahedral lattice, widening the bandgap. This study elucidates how surface engineering modulates charge localization, passivates defects, and enhances stability at the single-particle level. Moreover, by uncovering bias-induced trap states in single unpassivated NPLs, this study establishes a precise, robust approach for characterizing emerging perovskite nanocrystals.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2023

Electronic structure of Li 1,2,3 +,0,– and nature of the bonding in Li 2,3 +,0,–

Abstract The current study of the small lithium molecules Li 2 +,0,− and Li 3 +,0,− focuses on the nature of the bonding in these molecules as well as their structures and energetics (bond energies, ionization energies, and electron affinities). Valence CASSCF (2s,2p) calculations incorporate nondynamical electron correlation in the calculations, while the corresponding multireference configuration interaction and coupled cluster calculations incorporate dynamical electron correlation. Treatment of nondynamical correlation is critical for properly describing the Li 2,3 +,0,− molecules as well as the Li − anion with dynamical correlation, in general, only fine‐tuning the predictions. All lithium molecules and ions are bound, with the Li 3 + and Li 2 + ions being the most strongly bound, followed by Li 3 − , Li 2 , Li 2 − and Li 3 . The minimum energy structures of Li 3 +,0,− are, respectively, an equilateral triangle, an isosceles triangle, and a linear structure. The results of SCGVB calculations are analyzed to obtain insights into the nature of the bonding in these molecules. An important finding of this work is that interstitial orbitals, a concept first put forward by McAdon and Goddard in 1985, play an essential role in the bonding of all lithium molecules considered here except for Li 2 . The interstitial orbitals found in the Li 3 +,0 molecules likely give rise to the non‐nuclear attractors/maxima observed in these molecules.

Chemistry↗
DOE OSTI2011

Synthesis and electronic structure of proton-type partially substituted birnessite by period-four transition metal

Highlights: {yields} Partial metal substitutions of birnessite result in three types of crystal structure. {yields} Rhombohedral, monoclinic and hexagonal phase emerged in the substituted birnessite. {yields} The electrical conductivity decreased by substitution of transition metal for Mn. {yields} Partially substitution by Fe, Co and Ni poses splitting of crystal field for MnO{sub 6}. -- Abstract: Partially substituted proton-type birnessite were prepared by solid state reaction and their structures were refined. The formed birnessite with no substitution is identified to rhombohedral phase. In the case of substitution treatment by V and Cr for Mn, birnessite phase was not formed. On substituting Fe, hexagonal phase increased with increase of the amount of the Fe. For Co and Ni-substitution, monoclinic phase emerged at substitution ratio of around 0.37 and 0.02, respectively. For the substitution of Cu, only the monoclinic birnessite formed irrespective of the ratio. The electric conductivity of the partially substituted birnessites was examined at room temperature. The general trend is lower conductivity with increasing ratio of contained substituents. On several mol% of the substitution by Ni and Cu, the conductivity slightly increased. From DOS calculation of these compounds, the partially substitution for Mn by Fe, Co and Ni in the birnessite poses splitting of crystal field to emerge new bands at around -1 and +1 eV by Mn(IV) 3d orbital.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Analysis of superfast encoding performance for electronic structure simulations

In our recent work, we examined various fermion-to-qubit mappings in the context of quantum simulation including the original Bravyi-Kitaev superfast encoding (OSE) as well as a generalized version (GSE). We return to OSE and compare it against the Jordan-Wigner (JW) transform for quantum chemistry considering the number of qubits required, the Pauli weight of terms in the transformed Hamiltonians, and the L 1 norm of the Hamiltonian. We considered a test set of molecular systems known as the Atomization Energy 6 (AE6) as well as hydrogen lattices. Our results showed that the resource efficiency of OSE is strongly affected by the spatial locality of the underlying single-particle basis. We find that OSE is outperformed by JW when the orbitals in the underlying single-particle basis are highly overlapping, which limits its applicability to near-term quantum chemistry simulations utilizing standard basis sets. In contrast, when orbitals are overlapping with only few others, as is the case of hydrogen lattices with very tight orbitals, OSE fares comparatively better. Furthermore, our results illustrate the importance of choosing the right combination of basis sets and fermion-to-qubit mapping to get the most out of a quantum device when simulating physical systems.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2023

Electronic structure in a transition metal dipnictide TaAs 2

Abstract The family of transition-metal dipnictides has been of theoretical and experimental interest because this family hosts topological states and extremely large magnetoresistance (MR). Recently, T a A s 2 , a member of this family, has been predicted to support a topological crystalline insulating state. Here, by using high-resolution angle-resolved photoemission spectroscopy (ARPES), we reveal both closed and open pockets in the metallic Fermi surface (FS) and linearly dispersive bands on the ( 2 ‾ 01 ) surface, along with the presence of extreme MR observed from magneto-transport measurements. A comparison of the ARPES results with first-principles computations shows that the linearly dispersive bands on the measured surface of T a A s 2 are trivial bulk bands. The absence of symmetry-protected surface state on the ( 2 ‾ 01 ) surface indicates its topologically dark nature. The presence of open FS features suggests that the open-orbit fermiology could contribute to the extremely large MR of T a A s 2 .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2019

XAFS Spectroscopy Study of Microstructure and Electronic Structure of Heterosystems Containing Si/GeMn Quantum Dots

Using X-ray absorption near edge structure spectroscopy, extended X-ray absorption fine structure spectroscopy, atomic force microscopy, and Rutherford backscattering spectroscopy, the features of the microstructure and elemental composition of Si/GeMn magnetic systems obtained by molecular beam epitaxy and containing quantum dots are studied. Intense mixing of Ge and Si atoms is found in all samples. The degree of mixing (diffusion) correlates with the conditions of synthesis of Si/GeMn samples. For these systems, direct contacts of germanium atoms with manganese atoms are characterized and the presence of interstitial manganese with tetrahedral coordination and substitution of manganese for germanium and silicon in the lattice sites is found. The presence of stoichiometric phases Ge{sub 8}Mn{sub 11}, Ge{sub 3}Mn{sub 5} is not detected. The correlations of the Ge, Si, and Mn coordination numbers in the Ge environment are determined both with the Mn flux value (evaporator temperature) and with the temperature at which quantum dots are grown, as well as with other synthesis conditions. The manganese concentration in the samples is determined.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2011

Dependence of Electronic Structure of SrRuO3 and the Degree of Correlation on Cation Off-Stoichiometry

We have grown and studied high quality SrRuO{sub 3} films grown by MBE as well as PLD. By changing the oxygen activity during deposition we were able to make SrRuO{sub 3} samples that were stoichiometric (low oxygen activity) or with ruthenium vacancies (high oxygen activity). Samples with strontium vacancies were found impossible to produce since the ruthenium would precipitate out as RuO{sub 2}. The volume of the unit cell of SrRuO{sub 3} becomes larger as more ruthenium vacancies are introduced. The residual resistivity ratio (RRR) and room temperature resistivity were found to systematically depend on the volume of the unit cell and therefore on the amount of ruthenium vacancies. The RRR varied from {approx}30 for stoichiometric samples to less than two for samples that were very ruthenium poor. The room temperature resistivity varied from 190 {micro}{Omega} cm for stoichoimetric samples to over 300 {micro}{Omega} cm for very ruthenium poor samples. UPS spectra show a shift of weight from the coherent peak to the incoherent peak around the Fermi level when samples have more ruthenium vacancies. Core level XPS spectra of the ruthenium 3d lines show a strong screened part in the case of stoichiometric samples. This screened part disappears when ruthenium vacancies are introduced. Both the UPS and the XPS results are consistent with the view that correlation increases as the amount of ruthenium vacancies increase.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2014

Ab initio study of the RbSr electronic structure: Potential energy curves, transition dipole moments, and permanent electric dipole moments

Excited states and the ground state of the diatomic molecule RbSr were calculated by post Hartree-Fock molecular orbital theory up to 22 000 cm{sup −1}. We applied a multireference configuration interaction calculation based on multiconfigurational self-consistent field wave functions. Both methods made use of effective core potentials and core polarization potentials. Potential energy curves, transition dipole moments, and permanent electric dipole moments were determined for RbSr and could be compared with other recent calculations. We found a good agreement with experimental spectra, which have been obtained recently by helium nanodroplet isolation spectroscopy. For the lowest two asymptotes (Rb (5s {sup 2}S) + Sr (5s4d {sup 3}P°) and Rb (5p {sup 2}P°) + Sr (5s{sup 2} {sup 1}S)), which exhibit a significant spin-orbit coupling, we included relativistic effects by two approaches, one applying the Breit-Pauli Hamiltonian to the multireference configuration interaction wave functions, the other combining a spin-orbit Hamiltonian and multireference configuration interaction potential energy curves. Using the results for the relativistic potential energy curves that correspond to the Rb (5s {sup 2}S) + Sr (5s4d {sup 3}P°) asymptote, we have simulated dispersed fluorescence spectra as they were recently measured in our lab. The comparison with experimental data allows to benchmark both methods and demonstrate that spin-orbit coupling has to be included for the lowest states of RbSr.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

DFT investigation on structure, electronic and magnetic properties of Cr{sub n} (n=2-8) clusters

A density functional investigation on the series of chromium clusters, i.e., Cr{sub n} (n=2-8) is performed for finding their lowest energy structures and various electronic and magnetic properties. For electronic properties, we have predicted binding energy, HOMO-LUMO (HLG), chemical hardness (η) etc., and also for magnetic behavior, we have predicted the magnetic moments of the lowest energy cluster isomers. A systematic search imposing all possible initial magnetic configurations of the clusters is considered for finding lowest energy structures. All the calculations is carried out using a very popular GGA functional Perdew, Burke and Ernzerhof (PBE), as implemented in the VASP code.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗