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At least 1,711 records · Page 95
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Structural and optical study of γ –BIMEVOX; ME: Ba{sup 2+} and Sr{sup 2+}

Bismuth oxide based compounds, such as Bi{sub 4}V{sub 2}O{sub 11-δ} (BIVOX), exhibit Aurivillus type of interleaving arrangement of (Bi{sub 2}O{sub 2}){sup 2+} and (VO{sub 3}□{sub 0.5}){sup 2-} (□: oxygen vacancies). Bi{sub 4}V{sub 2}O{sub 11-δ,} is known to have three kinds of temperature dependent interconvertible polymorphs α (monoclinic), β (orthorhombic) and γ (tetragonal). Out of all the three phases, the γ – phase is highly disordered and hence, is the most conductive one which can be stabilized by proper lower valence cation (ME) doping at V site. Bi{sub 4}V{sub 1.90}ME{sub 0.20}O{sub 11-δ} (ME: Ba{sup 2+} and Sr{sup 2+}) were prepared via splat quenching technique. The required compositions were melted at 1250 °C in an electric furnace. The as quenched samples were sintered at 800 °C for 12 hours (h). The formed phases were analyzed using X-ray diffraction on quenched and sintered samples, the peak at 32{sup °} is found to be singlet in all the samples which confirms the presence of γ-phase. Hence, the stabilization of γ-phase with tetragonal structure was found to have taken place with doping and quenching. These samples are also studied by FT-IR and UV/vis spectroscopy to investigate the effect of dopants on structure and band gaps respectively.

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

Optical conductivity of cuprates in the pseudogap state: Yang-Rice-Zhang model and antiferromagnetic spin waves

In the underdoped regime of the cuprate phase diagram, the modified version of the Resonance Valence Bond (RVB) model by Yang, Rice and Zhang (YRZ) captures the strong electronic correlation effects very well as corroborated by the ARPES and many other experiments. However, under a non-equilibrium transport setting, YRZ says nothing about the scattering mechanisms of the charge carriers. In the present investigation we include, in a very simplified way, the scattering of charge carriers due to antiferromagnetic type spin waves (ASW). The effect of ASW excitations on conductivity has been studied by changing combined life times of the included process. It has been found that there is a qualitative change in the conductivity in the right direction. The theoretical conductivity reproduces qualitatively the experimental one.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

The ionic states of iodobenzene studied by photoionization and ab initio configuration interaction and DFT computations

New valence electron photoelectron spectra of iodobenzene obtained using synchrotron radiation have been recorded. Ionization energies (IEs) determined using multi-configuration SCF calculation (MCSCF) procedures confirmed the adiabatic IE order as: X{sup 2}B{sub 1}<A{sup 2}A{sub 2}<B{sup 2}B{sub 2}<C{sup 2}B{sub 1}. Although it is convenient to retain C{sub 2v} labelling, there is an evidence that minor distortion to C{sub S} symmetry occurs at the MCSCF level for the C state. The fifth ionization process shown to be D{sup 2}A{sub 1} exhibits dissociation to C{sub 6}H{sub 5}{sup +} + I both in the experimental and theoretical studies. The calculated Franck-Condon vibrational spectral envelopes, including hot band contributions, for the first four ionic states reproduce the observed peak positions and intensities with reasonable accuracy. In order to simulate the observed spectra, different bandwidths are required for different states. The increase in the required bandwidths for the A{sup 2}A{sub 2} and B{sup 2}B{sub 2} states is attributed to internal conversion to lower-lying states. The presence of relatively high intensity sequence bands leads to asymmetry of each of the X{sup 2}B{sub 1} state bands.

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

Interpretation of the vacuum ultraviolet photoabsorption spectrum of iodobenzene by ab initio computations

Identification of many Rydberg states in iodobenzene, especially from the first and fourth ionization energies (IE{sub 1} and IE{sub 4}, X{sup 2}B{sub 1} and C{sup 2}B{sub 1}), has become possible using a new ultraviolet (UV) and vacuum-ultraviolet (VUV) absorption spectrum, in the region 29 000-87 000 cm{sup −1} (3.60-10.79 eV), measured at room temperature with synchrotron radiation. A few Rydberg states based on IE{sub 2} (A{sup 2}A{sub 2}) were found, but those based on IE{sub 3} (B{sup 2}B{sub 2}) are undetectable. The almost complete absence of observable Rydberg states relating to IE{sub 2} and IE{sub 3} (A{sup 2}A{sub 2} and B{sup 2}B{sub 2}, respectively) is attributed to them being coupled to the near-continuum, high-energy region of Rydberg series converging on IE{sub 1}. Theoretical studies of the UV and VUV spectra used both time-dependent density functional (TDDFT) and multi-reference multi-root doubles and singles-configuration interaction methods. The theoretical adiabatic excitation energies, and their corresponding vibrational profiles, gave a satisfactory interpretation of the experimental results. The calculations indicate that the UV onset contains both 1{sup 1}B{sub 1} and 1{sup 1}B{sub 2} states with very low oscillator strength, while the 2{sup 1}B{sub 1} state was found to lie under the lowest ππ{sup ∗} 1{sup 1}A{sub 1} state. All three of these {sup 1}B{sub 1} and {sup 1}B{sub 2} states are excitations into low-lying σ{sup ∗} orbitals. The strongest VUV band near 7 eV contains two very strong ππ{sup ∗} valence states, together with other weak contributors. The lowest Rydberg 4b{sub 1}6s state (3{sup 1}B{sub 1}) is very evident as a sharp multiplet near 6 eV; its position and vibrational structure are well reproduced by the TDDFT results.

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

Structural changes and conductance thresholds in metal-free intrinsic SiO{sub x} resistive random access memory

We present an investigation of structural changes in silicon-rich silicon oxide metal-insulator-metal resistive RAM devices. The observed unipolar switching, which is intrinsic to the bulk oxide material and does not involve movement of metal ions, correlates with changes in the structure of the oxide. We use atomic force microscopy, conductive atomic force microscopy, x-ray photoelectron spectroscopy, and secondary ion mass spectroscopy to examine the structural changes occurring as a result of switching. We confirm that protrusions formed at the surface of samples during switching are bubbles, which are likely to be related to the outdiffusion of oxygen. This supports existing models for valence-change based resistive switching in oxides. In addition, we describe parallel linear and nonlinear conduction pathways and suggest that the conductance quantum, G{sub 0}, is a natural boundary between the high and low resistance states of our devices.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Performance enhancement of perovskite solar cells with Mg-doped TiO{sub 2} compact film as the hole-blocking layer

In this letter, we report perovskite solar cells with thin dense Mg-doped TiO{sub 2} as hole-blocking layers (HBLs), which outperform cells using TiO{sub 2} HBLs in several ways: higher open-circuit voltage (V{sub oc}) (1.08 V), power conversion efficiency (12.28%), short-circuit current, and fill factor. These properties improvements are attributed to the better properties of Mg-modulated TiO{sub 2} as compared to TiO{sub 2} such as better optical transmission properties, upshifted conduction band minimum (CBM) and downshifted valence band maximum (VBM), better hole-blocking effect, and higher electron life time. The higher-lying CBM due to the modulation with wider band gap MgO and the formation of magnesium oxide and magnesium hydroxides together resulted in an increment of V{sub oc}. In addition, the Mg-modulated TiO{sub 2} with lower VBM played a better role in the hole-blocking. The HBL with modulated band position provided better electron transport and hole blocking effects within the device.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2015

Photoelectron spectroscopy and theoretical studies of gaseous uranium hexachlorides in different oxidation states: UCl{sub 6}{sup q−} (q = 0–2)

Uranium chlorides are important in actinide chemistry and nuclear industries, but their chemical bonding and many physical and chemical properties are not well understood yet. Here, we report the first experimental observation of two gaseous uranium hexachloride anions, UCl{sub 6}{sup −} and UCl{sub 6}{sup 2−}, which are probed by photoelectron spectroscopy in conjunction with quantum chemistry calculations. The electron affinity of UCl{sub 6} is measured for the first time as +5.3 eV; its second electron affinity is measured to be +0.60 eV from the photoelectron spectra of UCl{sub 6}{sup 2−}. We observe that the detachment cross sections of the 5f electrons are extremely weak in the visible and UV energy ranges. It is found that the one-electron one-determinental molecular orbital picture and Koopmans’ theorem break down for the strongly internally correlated U-5f{sup 2} valence shell of tetravalent U{sup +4} in UCl{sub 6}{sup 2−}. The calculated adiabatic and vertical electron detachment energies from ab initio calculations agree well with the experimental observations. Electronic structure and chemical bonding in the uranium hexachloride species UCl{sub 6}{sup 2−} to UCl{sub 6} are discussed as a function of the oxidation state of U.

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

Quantum anomalous Hall effect and a nontrivial spin-texture in ultra-thin films of magnetic topological insulators

We study the evolution of quantum anomalous Hall (QAH) effect for a Z{sub 2} topological insulator (TI) thin films in a proximity induced magnetic phase by a realistic layered k·p model with interlayer coupling. We examine three different magnetic configurations in which ferromagnetic (FM) layer(s) is added either from one side (FM-TI), from both sides (FM-TI-FM), or homogeneously distributed (magnetically doped) in a TI slab. We map out the thickness-dependent topological phase diagram under various experimental conditions. The critical magnetic exchange energy for the emergence of QAH effect in the latter two cases decreases monotonically with increasing number of quintuple layers (QLs), while it becomes surprisingly independent of the film thickness in the former case. The gap size of the emergent QAH insulator depends on the non-magnetic “parent” gap of the TI thin film and is tuned by the FM exchange energy, opening a versatile possibility to achieve room-temperature QAH insulator in various topological nanomaterials. Finally, we find that the emergent spin-texture in the QAH effect is very unconventional, non-“hedgehog” type; and it exhibits a chiral out-of-plane spin-flip texture within the same valence band which is reminiscent of dynamical “skyrmion” pattern, except our results are in the momentum space.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Optically induced transport through semiconductor-based molecular electronics

A tight binding model is used to investigate photoinduced tunneling current through a molecular bridge coupled to two semiconductor electrodes. A quantum master equation is developed within a non-Markovian theory based on second-order perturbation theory with respect to the molecule-semiconductor electrode coupling. The spectral functions are generated using a one dimensional alternating bond model, and the coupling between the molecule and the electrodes is expressed through a corresponding correlation function. Since the molecular bridge orbitals are inside the bandgap between the conduction and valence bands, charge carrier tunneling is inhibited in the dark. Subject to the dipole interaction with the laser field, virtual molecular states are generated via the absorption and emission of photons, and new tunneling channels open. Interesting phenomena arising from memory are noted. Such a phenomenon could serve as a switch.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Two-dimensional semiconductor HfSe{sub 2} and MoSe{sub 2}/HfSe{sub 2} van der Waals heterostructures by molecular beam epitaxy

Using molecular beam epitaxy, atomically thin 2D semiconductor HfSe{sub 2} and MoSe{sub 2}/HfSe{sub 2} van der Waals heterostructures are grown on AlN(0001)/Si(111) substrates. Details of the electronic band structure of HfSe{sub 2} are imaged by in-situ angle resolved photoelectron spectroscopy indicating a high quality epitaxial layer. High-resolution surface tunneling microscopy supported by first principles calculations provides evidence of an ordered Se adlayer, which may be responsible for a reduction of the measured workfunction of HfSe{sub 2} compared to theoretical predictions. The latter reduction minimizes the workfunction difference between the HfSe{sub 2} and MoSe{sub 2} layers resulting in a small valence band offset of only 0.13 eV at the MoSe{sub 2}/HfSe{sub 2} heterointerface and a weak type II band alignment.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Simulation of circularly polarized luminescence spectra using coupled cluster theory

We report the first computations of circularly polarized luminescence (CPL) rotatory strengths at the equation-of-motion coupled cluster singles and doubles (EOM-CCSD) level of theory. Using a test set of eight chiral ketones, we compare both dipole and rotatory strengths for absorption (electronic circular dichroism) and emission to the results from time-dependent density-functional theory (TD-DFT) and available experimental data for both valence and Rydberg transitions. For two of the compounds, we obtained optimized geometries of the lowest several excited states using both EOM-CCSD and TD-DFT and determined that structures and EOM-CCSD transition properties obtained with each structure were sufficiently similar that TD-DFT optimizations were acceptable for the remaining test cases. Agreement between EOM-CCSD and the Becke three-parameter exchange function and Lee-Yang-Parr correlation functional (B3LYP) corrected using the Coulomb attenuating method (CAM-B3LYP) is typically good for most of the transitions, though agreement with the uncorrected B3LYP functional is significantly worse for all reported properties. The choice of length vs. velocity representation of the electric dipole operator has little impact on the EOM-CCSD transition strengths for nearly all of the states we examined. For a pair of closely related β, γ-enones, (1R)-7-methylenebicyclo[2.2.1]heptan-2-one and (1S)-2-methylenebicyclo[2.2.1]heptan-7-one, we find that EOM-CCSD and CAM-B3LYP agree with the energetic ordering of the two possible excited-state conformations, resulting in good agreement with experimental rotatory strengths in both absorption and emission, whereas B3LYP yields a qualitatively incorrect result for the CPL signal of (1S)-2-methylenebicyclo[2.2.1]heptan-7-one. Finally, we predict that one of the compounds considered here, trans-bicyclo[3.3.0]octane-3,7-dione, is unique in that it exhibits an achiral ground state and a chiral first excited state, leading to a strong CPL signal but a weak circular dichroism signal.

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

The Fowler-Nordheim behavior and mechanism of photo-sensitive field from SnS{sub 2} nanosheets

Here in, we report photo-sensitive field emission measurements of SnS{sub 2} nanosheets at base pressure of ∼1×10{sup −8} mbar are reported. The nonlinear Fowler-Nordheim (F-N) plot is elucidate according to a (F-N) model of calculation based on shift in a saturation of conduction band current density after light illumination and prevalence of valence band current density at high electric field values. The model of calculation suggests that the slope variation before and after visible light illumination of the F-N plot, in the high-field and low-field regions, does not depend on the magnitude of saturation but also depend on charge carrier (electron) concentration get increased in conduction band. The F-N model of calculation is important for the fundamental understanding of the photo-sensitive field emission mechanism of semiconducting SnS{sub 2}. The replicate F-N plots exhibit similar features to those observed experimentally. The model calculation suggests that the nonlinearity of the F-N plot is a characteristic of the photo-enhanced energy band structure of the photo-sensitive semiconductor material.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Effect of high pressure on the electrical resistivity of Ge−Te−In glasses

The variation in the electrical resistivity of the chalcogenide glasses Ge{sub 15}Te{sub 85-x}In{sub x} has been studied as a function of high pressure for pressures up to 8.5GPa. All the samples studied undergo a semi-conductor to metallic transition in a continuous manner at pressures between 1.5-2.5GPa. The transition pressure at which the samples turn metallic increases with increase in percentage of Indium. This increase is a direct consequence of the increase in network rigidity with the addition of Indium. At a constant pressure of 0.5GPa, the normalized resistivity shows some signature of the existence of the intermediate phase. Samples recovered after a pressure cycle remain amorphous suggesting that the semi-conductor to metallic transition arises from a reduction of the band gap due to pressure or the movement of the Fermi level into the conduction or valence band.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Synthesis and characterization of electron doped La{sub 0.85}Te{sub 0.15}MnO{sub 3} thin film grown on LaAlO{sub 3} substrate by pulsed laser deposition technique

We report the structural, morphological and magneto-transport properties of electron doped La{sub 0.85}Te{sub 0.15}MnO{sub 3} (LTMO) thin film grown on (001) LaAlO{sub 3} single crystal substrate by pulsed laser deposition (PLD). X-ray diffraction (XRD) results confirm that the film has good crystalline quality, single phase, and c-axis orientation. The atomic force microscopy (AFM) results have revealed that the film consists of grains with the average size in a range of 20–30 nm and root-mean square (rms) roughness of 0.27nm. The resistivity versus temperature measurement exhibits an insulator to metal transition (MIT). We have noticed a huge value of magnetoresistance (∼93%) close to MIT in presence of 8T field. X-ray photoemission spectroscopy confirms the electron doping and suggests that Te ions could be in the Te{sup 4+} state, while the Mn ions stay in the Mn{sup 2+} and Mn{sup 3+} valence state.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Pseudogap behaviour in FeTe and FeSe probed by photoemission

This study reports the valence band photoelectron spectroscopic studies of FeTe and FeSe. A doping induced and temperature dependent pseudogap occur near the Fermi level. The spectral weight transfer occurs due to the change in chalcogen height due to lowering of temperature. This result is in analogy with the reduction in chalcogen height due to the replacement of Te by Se.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Stability and electronic properties of SiC nanowire adsorbed on MoS{sub 2} monolayer

Structural stability and electronic properties of silicon carbide (SiC) nano-wire on MoS{sub 2} monolayer are investigated within the framework of density functional theory (DFT). The preferred binding site for the SiC nano-wire is predicted to be hollow site of monolayer. In the electronic band structure the states in valence band near Fermi level are mainly due to nano-wire leading to reduction of band gap relative to monolayer. These results provide a platform for their applications in optoelectronic devices.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

IUPAC-NIST Solubility Data Series. 100. Rare Earth Metal Fluorides in Water and Aqueous Systems. Part 3. Heavy Lanthanides (Gd–Lu)

This is the third part of the volume devoted to solubility data for the rare earth metal (REM) fluorides in water and in aqueous ternary and multicomponent systems. It covers experimental results of trivalent fluorides of Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu (so-called heavy lanthanides), since no quantitative data on solubilities of TbF{sub 4} and YbF{sub 2} (the most stable compounds at these valencies) are available. The related literature has been covered through the end of 2014. Compilations of all available papers with the solubility data are introduced for each REM fluoride with a corresponding critical evaluation. Every such assessment contains a collection of all solubility results in aqueous solution, a selection of suggested solubility data, a solubility equation, and a brief discussion of the multicomponent systems. Only simple fluorides (no complexes or double salts) are treated as the input substances in this report. General features of the systems, such as nature of the equilibrium solid phases, solubility as a function of temperature, influence of ionic strength, solution pH, mixed solvent medium on the solubility, quality of the solubility results, and the solubility as a function of REM atomic number, have already been presented in Part 1 of the volume.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

High hole concentration in p-type AlGaN by indium-surfactant-assisted Mg-delta doping

High hole concentration was achieved in Mg-doped Al{sub x}Ga{sub 1−x}N (x ∼ 0.4) by using indium-surfactant-assisted delta doping method. A maximum carrier concentration of 4.75 × 10{sup 18 }cm{sup −3} was obtained, which is three times higher than that of the conventionally delta-doped sample. Sheet resistivity as low as 2.46 × 10{sup 4} Ω/sq was realized, benefiting from the high hole concentration (p). Analysis results show that the Mg incorporation is effectively enhanced, while the compensation ratio and acceptor activation energy (E{sub A}) are significantly reduced by using In surfactant. It was also found that the In surfactant may induce stronger valence-band modulation, contributing to the decrease of E{sub A} and the increase of p.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗