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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 1,675 records · Page 93
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Schottky barrier height reduction for holes by Fermi level depinning using metal/nickel oxide/silicon contacts

We report the experimental demonstration of Fermi level depinning using nickel oxide (NiO) as the insulator material in metal-insulator-semiconductor (M-I-S) contacts. Using this contact, we show less than 0.1 eV barrier height for holes in platinum/NiO/silicon (Pt/NiO/p-Si) contact. Overall, the pinning factor was improved from 0.08 (metal/Si) to 0.26 (metal/NiO/Si). The experimental results show good agreement with that obtained from theoretical calculation. NiO offers high conduction band offset and low valence band offset with Si. By reducing Schottky barrier height, this contact can be used as a carrier selective contact allowing hole transport but blocking electron transport, which is important for high efficiency in photonic applications such as photovoltaics and optical detectors.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Band structure of ABC-trilayer graphene superlattice

We investigate the effect of one-dimensional periodic potentials on the low energy band structure of ABC trilayer graphene first by assuming that all the three layers have the same potential. Extra Dirac points having the same electron hole crossing energy as that of the original Dirac point are generated by superlattice potentials with equal well and barrier widths. When the potential height is increased, the numbers of extra Dirac points are increased. The dispersions around the Dirac points are not isotropic. It is noted that the dispersion along the k{sub y} direction for k{sub x} = 0 oscillates between a non-linear dispersion and a linear dispersion when the potential height is increased. When the well and barrier widths are not identical, the symmetry of the conduction and valence bands is broken. The extra Dirac points are shifted either upward or downward depending on the barrier and well widths from the zero energy, while the position of the central Dirac point oscillates with the superlattice potential height. By considering different potentials for different layers, extra Dirac points are generated not from the original Dirac points but from the valleys formed in the energy spectrum. Two extra Dirac points appear from each pair of touched valleys, so four Dirac points appeared in the spectrum at particular barrier height. By increasing the barrier height of superlattice potential two Dirac points merge into the original Dirac point. This emerging and merging of extra Dirac points is different from the equal potential case.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2014

Highly spin-polarized current in Co-substituted Fe{sub 3}O{sub 4} epitaxial thin films at room temperature

Epitaxial thin films of cobalt ferrite Co{sub x}Fe{sub 3−x}O{sub 4} (x = 0.0, 0.5, and 1.0) were fabricated on α-Al{sub 2}O{sub 3} (001) substrates using pulsed laser deposition. It was found that the coercive force of the cobalt ferrite films could be tuned by changing the Co content. The films prepared under low oxygen pressure (1.0 × 10{sup −6 }Pa) showed semiconducting behavior even for x = 1.0. X-ray photoelectron spectroscopy revealed that the Co ions were 2{sup +} for all compositions. On the other hand, it was found that the Fe ions were in the Fe{sup 2+}/Fe{sup 3+} valence state, which may cause small-polaron hopping among the Fe-3d electrons in the films. An anomalous Hall effect was observed in the Co{sub 0.5}Fe{sub 2.5}O{sub 4} film even at 300 K, suggesting that carriers in the films were highly spin-polarized at room temperature.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Occupied and unoccupied electronic structure of Na doped MoS{sub 2}(0001)

The influence of sodium on the band structure of MoS{sub 2}(0001) and the comparison of the experimental band dispersion with density functional theory show excellent agreement for the occupied states (angle-resolved photoemission) and qualitative agreement for the unoccupied states (inverse photoemission spectroscopy). Na-adsorption leads to charge transfer to the MoS{sub 2} surface causing an effect similar to n-type doping of a semiconductor. The MoS{sub 2} occupied valence band structure shifts rigidly to greater binding with little change in the occupied state dispersion. Likewise, the unoccupied states shift downward, approaching the Fermi level, yet the amount of the shift for the unoccupied states is greater than that of the occupied states, effectively causing a narrowing of the MoS{sub 2} bandgap.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Investigation of the oxidation states of Cu additive in colored borosilicate glasses by electron energy loss spectroscopy

Three optically transparent colorful (red, green, and blue) glasses were synthesized by the sol-gel method. Nano-sized precipitates were found in scanning electron microscopy images. The precipitates were analyzed by transmission electron microscopy (TEM) and high resolution TEM. The measured lattice parameters of these precipitates were found to fit the metallic copper in red glass but deviate from single valenced Cu oxides in green and blue glasses. The chemistry of these nano-sized particles was confirmed by electron energy loss spectroscopy (EELS). By fitting the EELS spectra obtained from the precipitates with the linear combination of reference spectra from Cu reference compounds, the oxidation states of Cu in the precipitates have been derived. First principle calculations suggested that the Cu nano-particles, which are in the similar oxidation states as our measurement, would show green color in the visible light range.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2015

Single photon simultaneous K-shell ionization and K-shell excitation. I. Theoretical model applied to the interpretation of experimental results on H{sub 2}O

We present in detail a theoretical model that provides absolute cross sections for simultaneous core-ionization core-excitation (K{sup −2}V ) and compare its predictions with experimental results obtained on the water molecule after photoionization by synchrotron radiation. Two resonances of different symmetries are assigned in the main K{sup −2}V peak and comparable contributions from monopolar (direct shake-up) and dipolar (conjugate shake-up) core-valence excitations are identified. The main peak is observed with a much greater width than the total experimental resolution. This broadening is the signature of nuclear dynamics.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2015

Canonical-ensemble state-averaged complete active space self-consistent field (SA-CASSCF) strategy for problems with more diabatic than adiabatic states: Charge-bond resonance in monomethine cyanines

This paper reviews basic results from a theory of the a priori classical probabilities (weights) in state-averaged complete active space self-consistent field (SA-CASSCF) models. It addresses how the classical probabilities limit the invariance of the self-consistency condition to transformations of the complete active space configuration interaction (CAS-CI) problem. Such transformations are of interest for choosing representations of the SA-CASSCF solution that are diabatic with respect to some interaction. I achieve the known result that a SA-CASSCF can be self-consistently transformed only within degenerate subspaces of the CAS-CI ensemble density matrix. For uniformly distributed (“microcanonical”) SA-CASSCF ensembles, self-consistency is invariant to any unitary CAS-CI transformation that acts locally on the ensemble support. Most SA-CASSCF applications in current literature are microcanonical. A problem with microcanonical SA-CASSCF models for problems with “more diabatic than adiabatic” states is described. The problem is that not all diabatic energies and couplings are self-consistently resolvable. A canonical-ensemble SA-CASSCF strategy is proposed to solve the problem. For canonical-ensemble SA-CASSCF, the equilibrated ensemble is a Boltzmann density matrix parametrized by its own CAS-CI Hamiltonian and a Lagrange multiplier acting as an inverse “temperature,” unrelated to the physical temperature. Like the convergence criterion for microcanonical-ensemble SA-CASSCF, the equilibration condition for canonical-ensemble SA-CASSCF is invariant to transformations that act locally on the ensemble CAS-CI density matrix. The advantage of a canonical-ensemble description is that more adiabatic states can be included in the support of the ensemble without running into convergence problems. The constraint on the dimensionality of the problem is relieved by the introduction of an energy constraint. The method is illustrated with a complete active space valence-bond (CASVB) analysis of the charge/bond resonance electronic structure of a monomethine cyanine: Michler’s hydrol blue. The diabatic CASVB representation is shown to vary weakly for “temperatures” corresponding to visible photon energies. Canonical-ensemble SA-CASSCF enables the resolution of energies and couplings for all covalent and ionic CASVB structures contributing to the SA-CASSCF ensemble. The CASVB solution describes resonance of charge- and bond-localized electronic structures interacting via bridge resonance superexchange. The resonance couplings can be separated into channels associated with either covalent charge delocalization or chemical bonding interactions, with the latter significantly stronger than the former.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Materials News: Interfacial chemistry and atomic arrangement of ZrO{sub 2} − La{sub 2/3}Sr{sub 1/3}MnO{sub 3} pillar-matrix structures

We studied ZrO{sub 2} − La{sub 2/3}Sr{sub 1/3}MnO{sub 3} pillar–matrix thin films which were found to show anomalous magnetic and electron transport properties. With the application of an aberration-corrected transmission electron microscope, interfacial chemistry, and atomic-arrangement of the system, especially of the pillar–matrix interface were revealed at atomic resolution. Minor amounts of Zr were found to occupy Mn positions within the matrix. The Zr concentration reaches a minimum near the pillar–matrix interface accompanied by oxygen vacancies. La and Mn diffusion into the pillar was revealed at atomic resolution and a concomitant change of the Mn valence state was observed.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Effect of geometry and composition on the intraband transitions of holes in quantum dots

The effect of shape and size anisotropy on unipolar intraband transitions of holes in quantum dots (QDs) is studied. The optical matrix elements are calculated for transitions of holes in valence band. To get the optical matrix elements, energy eigenvalues and eigenvectors are calculated using 4 × 4 Luttinger Hamiltonian in the effective mass approximation. The formulation is applied to InGaAs/GaAs QD with parabolic confinement potential in xy-plane. The optical matrix elements for intraband hole transitions are calculated for x and y polarised light. The transitions are considered from ground state to other excited states. The effect of In concentration on optical matrix elements is also investigated. It is important to note that the transitions of holes are governed by the character of initial and final states for different light polarisations that give specific transition selection rules. It is found that the polarisation is strongly dependent on the in-plane anisotropy of the QDs.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Restricted Hartree Fock using complex-valued orbitals: A long-known but neglected tool in electronic structure theory

Restricted Hartree Fock using complex-valued orbitals (cRHF) is studied. We introduce an orbital pairing theorem, with which we obtain a concise connection between cRHF and real-valued RHF, and use it to uncover the close relationship between cRHF, unrestricted Hartree Fock, and generalized valence bond perfect pairing. This enables an intuition for cRHF, contrasting with the generally unintuitive nature of complex orbitals. We also describe an efficient computer implementation of cRHF and its corresponding stability analysis. By applying cRHF to the Be + H{sub 2} insertion reaction, a Woodward-Hoffmann violating reaction, and a symmetry-driven conical intersection, we demonstrate in genuine molecular systems that cRHF is capable of removing certain potential energy surface singularities that plague real-valued RHF and related methods. This complements earlier work that showed this capability in a model system. We also describe how cRHF is the preferred RHF method for certain radicaloid systems like singlet oxygen and antiaromatic molecules. For singlet O{sub 2}, we show that standard methods fail even at the equilibrium geometry. An implication of this work is that, regardless of their individual efficacies, cRHF solutions to the HF equations are fairly commonplace.

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

The nature of interfaces and charge trapping sites in photocatalytic mixed-phase TiO{sub 2} from first principles modeling

Mixed phase rutile/anatase catalysts show increased reactivity compared with the pure phases alone. However, the mechanism causing this effect is not fully understood. The electronic properties of the interface and the relative energy of the electron in each phase play a key role in lowering the rate of recombination of electron hole pairs. Using density functional theory and the +U correction, we calculated the bands offsets between the phases taking into account the effect of the interface. Our model included several thousands atoms, and thus is a good representation of an interface between actual nanoparticles. We found rutile to have both higher conduction and valence band offsets than rutile, leading to an accumulation of electrons in the anatase phase accompanied by hole accumulation in the rutile phase. We also probed the electronic structure of our heterostructure and found a gap state caused by electrons localized in undercoordinated Ti atoms which were present within the interfacial region. Interfaces between bulk materials and between exposed surfaces both showed electron trapping at undercoordinated sites. These undercoordinated (typically four) atoms present localized electrons that could enable reduction reactions in the interfacial region, and could explain the increased reactivity of mixed-phase TiO{sub 2} photocatalyst materials.

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

Quantum dynamics study on the CHIPR potential energy surface for the hydroperoxyl radical: The reactions O + OH⇋O{sub 2} + H

Quantum scattering calculations of the O({sup 3}P)+OH({sup 2}Π)⇌O{sub 2}({sup 3}Σ{sub g}{sup −})+H({sup 2}S) reactions are presented using the combined-hyperbolic-inverse-power-representation potential energy surface [A. J. C. Varandas, J. Chem. Phys. 138, 134117 (2013)], which employs a realistic, ab initio-based, description of both the valence and long-range interactions. The calculations have been performed with the ABC time-independent quantum reactive scattering computer program based on hyperspherical coordinates. The reactivity of both arrangements has been investigated, with particular attention paid to the effects of vibrational excitation. By using the J-shifting approximation, rate constants are also reported for both the title reactions.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Role of electron transfer in Ce{sup 3+} sensitized Yb{sup 3+} luminescence in borate glass

In a Ce{sup 3+}-Yb{sup 3+} system, two mechanisms are proposed so far namely, the quantum cutting mechanism and the electron transfer mechanism explaining Yb{sup 3+} infrared luminescence under Ce{sup 3+} excitation. Among them, the quantum cutting mechanism, where one Ce{sup 3+} photon (ultraviolet/blue) gives rise to two Yb{sup 3+} photons (near infrared) is widely sought for because of its huge potential in enhancing the solar cell efficiency. In present study on Ce{sup 3+}-Yb{sup 3+} codoped borate glasses, Ce{sup 3+} sensitized Yb{sup 3+} luminescence at ∼1 μm have been observed on Ce{sup 3+} 5d state excitation. However, the intensity of sensitized Yb{sup 3+} luminescence is found to be very weak compared to the strong quenching occurred in Ce{sup 3+} luminescence in Yb{sup 3+} codoped glasses. Moreover, the absolute luminescence quantum yield also showed a decreasing trend with Yb{sup 3+} codoping in the glasses. The overall behavior of the luminescence properties and the quantum yield is strongly contradicting with the quantum cutting phenomenon. The results are attributed to the energetically favorable electron transfer interactions followed by Ce{sup 3+}-Yb{sup 3+} ⇌ Ce{sup 4+}-Yb{sup 2+} inter-valence charge transfer and successfully explained using the absolute electron binding energies of dopant ions in the studied borate glass. Finally, an attempt has been presented to generalize the electron transfer mechanism among opposite oxidation/reduction property dopant ions using the vacuum referred electron binding energy (VRBE) scheme for lanthanide series.

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

Short-range stabilizing potential for computing energies and lifetimes of temporary anions with extrapolation methods

The energy of a temporary anion can be computed by adding a stabilizing potential to the molecular Hamiltonian, increasing the stabilization until the temporary state is turned into a bound state, and then further increasing the stabilization until enough bound state energies have been collected so that these can be extrapolated back to vanishing stabilization. The lifetime can be obtained from the same data, but only if the extrapolation is done through analytic continuation of the momentum as a function of the square root of a shifted stabilizing parameter. This method is known as analytic continuation of the coupling constant, and it requires—at least in principle—that the bound-state input data are computed with a short-range stabilizing potential. In the context of molecules and ab initio packages, long-range Coulomb stabilizing potentials are, however, far more convenient and have been used in the past with some success, although the error introduced by the long-rang nature of the stabilizing potential remains unknown. Here, we introduce a soft-Voronoi box potential that can serve as a short-range stabilizing potential. The difference between a Coulomb and the new stabilization is analyzed in detail for a one-dimensional model system as well as for the {sup 2}Π{sub u} resonance of CO{sub 2}{sup −}, and in both cases, the extrapolation results are compared to independently computed resonance parameters, from complex scaling for the model, and from complex absorbing potential calculations for CO{sub 2}{sup −}. It is important to emphasize that for both the model and for CO{sub 2}{sup −}, all three sets of results have, respectively, been obtained with the same electronic structure method and basis set so that the theoretical description of the continuum can be directly compared. The new soft-Voronoi-box-based extrapolation is then used to study the influence of the size of diffuse and the valence basis sets on the computed resonance parameters.

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

Evidence of ion intercalation mediated band structure modification and opto-ionic coupling in lithium niobite

The theoretically suggested band structure of the novel p-type semiconductor lithium niobite (LiNbO{sub 2}), the direct coupling of photons to ion motion, and optically induced band structure modifications are investigated by temperature dependent photoluminescence. LiNbO{sub 2} has previously been used as a memristor material but is shown here to be useful as a sensor owing to the electrical, optical, and chemical ease of lithium removal and insertion. Despite the high concentration of vacancies present in lithium niobite due to the intentional removal of lithium atoms, strong photoluminescence spectra are observed even at room temperature that experimentally confirm the suggested band structure implying transitions from a flat conduction band to a degenerate valence band. Removal of small amounts of lithium significantly modifies the photoluminescence spectra including additional larger than stoichiometric-band gap features. Sufficient removal of lithium results in the elimination of the photoluminescence response supporting the predicted transition from a direct to indirect band gap semiconductor. In addition, non-thermal coupling between the incident laser and lithium ions is observed and results in modulation of the electrical impedance.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

A study of transport properties in Cu and P doped ZnSb

ZnSb samples have been doped with copper and phosphorus and sintered at 798 K. Electronic transport properties are interpreted as being influenced by an impurity band close to the valence band. At low Cu dopant concentrations, this impurity band degrades the thermoelectric properties as the Seebeck coefficient and effective mass are reduced. At carrier concentrations above 1 × 10{sup 19 }cm{sup −3}, the Seebeck coefficient in Cu doped samples can be described by a single parabolic band.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗