Electronic structure of high-Tc Ba0.6K0.4BiO3 by x-ray photoelectron spectroscopy

We have investigated the electronic structure of Ba1-xKxBiO3 (0x-ray photoelectron spectroscopy. The Bi(4f) core levels show a normal valency of +3 as in Bi2O3 and we find no evidence for the disproportionation of Bi4+ to Bi3+ and Bi5+. Instead, we find that BaBiO3 has mixed valent O2- and O1- ions. As the potassium doping is increased, the binding energy of the O2- ions in the O(1s) photoelectron spectra steadily decreases from 529.7 to 528.8 eV. The effect of lowering the O(1s) binding energy is to raise the O(2p) band towards EF and at the superconducting composition a finite density of O(2p) states is observed near EF. Similarly, the Ba(5p) binding energies decrease with potassium doping, indicating increased metallicity. The behavior of the O(1s), Ba(5p), and the valence band resembles that of all the cuprate superconductors and we conclude that in all these oxide superconductors, a hole in the (filled) O(2p) band is the carrier responsible for superconductivity, which predicts hole conduction in the Ba-K-Bi-O and Ba-Pb-Bi-O systems.

Transition metal oxide perovskites by photoelectron and x-ray absorption spectroscopy

X-ray and ultraviolet photoelectron spectroscopy as well as x-ray absorption spectroscopy have been employed to investigate transition metal oxide perovskites of the general formula ABOs (A=La or rare-earth ion, B=trivalent transition metalion). Systematics in the core levels and in the valence bands in the series of LaBOa compounds have been discussed. Lanthanum chemical shifts in the x-ray absorption spectra in this series show interesting trends. Photoelectron spectra of the solid solutions, LaNil_x Coxes, LaNix_x FexO8 and LaFel_x Coxes show that the rigid band model is applicable to these systems. It is shown that x-ray photoelectron spectroscopy can be employed to identify multiple oxidation states of transition metal ions in oxide perovskites.

Metal-insulator transitions in Cr-doped V2O3 by x-ray and ultraviolet photoelectron spectroscopy

X-ray and ultraviolet photoelectron spectroscopy have been employed to investigate the high temperature metal-insulator transitions in V2O3 and (V0.99Cr0.01)2O3. The high temperature transitions are associated with more gradual changes in the 3d bands compared to the low-temperature transitions

A Study of copper-compounds by x-Ray Absorption-spectroscopy

Chemical shifts, ΔE, of the K-absorption discontinuity in several compounds of copper possessing formal oxidation states between 0 and III have been measured. The shifts show a parabolic dependence on the formal oxidation state as well as on the effective atomic charge, q, on copper. Anomalous chemical shifts shown by some of the compounds are discussed in terms of the bonding in these compounds. The ΔE values have also been correlated with the core electron binding energies obtained from X-ray photoelectron spectroscopy.

1, 2-Bis (diphenylphosphino) etane bridged dinuclear copper (I) complexes: Investigations of solid state and solution structures by CP/MAS31P NMR spectroscopy, X-ray crystallography, IR spectroscopy and solution 31P NMR and 63Cu NMR spectroscopy

Three different complexes of copper (I) with bridging 1, 2-bis(diphenylphosphino)ethane (dppe), namely [Cu2 (mu-dppe) (CH3CN)6] (ClO4)2 (1), [Cu2 (mu-dppe)2 (CH3 CN)2] (ClO4)2 (2), and [Cu2 (mu-dppe) (dppe)2 (CH3CN)2] (ClO4)2 (3) have been prepared. The structure of [Cu2 (mu-dppe) (dPPe)2 (CH3CH)2] (ClO4)2 has been determined by X-ray crystallography. It crystallizes in the space group PT with a=12.984(6) angstrom, b=13.180(6) angstrom, c=14.001(3) angstrom, alpha=105.23(3), beta=105.60(2), gamma=112.53 (4), V=1944 (3) angstrom3, and Z=1. The structure was refined by least-squares method with R=0.0365; R(w)=0.0451 for 6321 reflections with F0 greater-than-or-equal-to 3 sigma (F0). The CP/MAS P-31 and IR spectra of the complexes have been analysed in the light of available crystallographic data. IR spectroscopy is particularly helpful in identifying the presence of chelating dppe. P-31 chemical shifts observed in solid state are very different from those observed in solution, and change significantly with slight changes in structure. In solution, complex 1 remains undissociated but complexes 2 and 3 undergo extensive dissociation. With a combination of room temperature H-1, Cu-63, and variable temperature P-31 NMR spectra, it is possible to understand the various processes occurring in solution.

Chiral polyhydroxylated tetrahydrothiophene derivatives: novel synthesis and structural elucidation by X-ray crystallography, NMR spectroscopy and molecular mechanics calculations

The dideoxygenation reaction of 1,3;4,6-di-O-alkylidene-2,5-di-S-methylthiocarbonyl-D-mannitol derivatives under Barton-McCombie reaction conditions gave the hexahydrodipyranothiophenes 4 and 7 instead of the expected 2,5-dideoxy products. Structural and conformational information on these novel derivatives has been obtained by NMR spectroscopy, single-crystal X-ray crystallography and molecular mechanics calculations.

Evidence for correlation effects in Sr2RuO4 from resonant and x-ray photoemission spectroscopy

We study the electronic structure of Sr2RuO4, a noncuprate layered superconductor (T-c=0.93 K), using electron spectroscopy. X-ray photoemission spectroscopy shows that the single particle occupied density of states (DOS) is in fair agreement with the calculated DOS. However, resonant photoemission spectroscopy across the Ru 4p-4d threshold establishes the existence of a correlation satellite to the Ru 4d band. The results indicate substantial charge-transfer character at the Fermi level, with on-site correlations U-dd comparable in magnitude to the Ru-O hopping integral, like the cuprates.

Structure of 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorodecyl 1,10-ditosylate by X-ray crystallography and F-19-NMR spectroscopy

2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorodecyl 1,10-ditosylate and its precursors were synthesized and characterized by H-1- and F-19-NMR spectroscopic methods and X-ray crystallography. These compounds are building blocks for the syntheses of the surfactants containing polyperfluoromethylene spacer. The molecule has extended all-trans conformation with molecular symmetry (1) over bar (C-i). There is a reasonably strong C-H ... O interaction in the crystal and there are two F ... F intermolecular contact distances less than the sum of van der Waals radii. (C) 1999 Elsevier Science B.V. All rights reserved.

A kinetic study of the phase transformations in Al2O3 and Na2O · 6Al2O3 by a combined use of 27Al MAS NMR spectroscopy and x-ray diffraction: Importance of nucleation

Phase transformations of Al2O3 and Na2O · 6Al2O3 prepared by the gel route have been investigated for the first time by 27Al MAS NMR spectroscopy in combination with x-ray diffraction. Of particular interest in the study is the kinetics of the γ → α and γ → β transformations, respectively, in these two systems. Analysis of the kinetic data shows the important role of nucleation in both these transformations.

Band alignment studies in InN/p-Si(100) heterojunctions by x-ray photoelectron spectroscopy

The band offsets in InN/p-Si heterojunctions are determined by high resolution x-ray photoemission spectroscopy. The valence band of InN is found to be 1.39 eV below that of Si. Given the bandgap of 0.7 eV for InN, a type-III heterojunction with a conduction band offset of 1.81 eV was found. Agreement between the simulated and experimental data obtained from the heterojunction spectra was found to be excellent, establishing that the method of determination was accurate. The charge neutrality level (CNL) model provided a reasonable description of the band alignment of the InN/p-Si interface and a change in the interface dipole by 0.06 eV was observed for InN/p-Si interface.

Band-Structure Lineup at In0.2Ga0.8N/Si Heterostructures by X-ray Photoelectron Spectroscopy

In0.2Ga0.8N layers were directly grown on Si(111) substrate by plasma-assisted molecular beam epitaxy (PAMBE). Structural characteristics of the as-grown InGaN epilayers were evaluated high resolution X-ray diffraction and composition of InGaN was estimated from photoluminescence spectra using the standard Vegard's law. High-resolution X-ray photoemission spectroscopy measurements were used to determine the band offset of wurtzite-In0.2Ga0.8N/Si(111) heterojunctions. The valence band of InGaN is found to be 2.08 +/- 0.04 eV below that of Si. The conduction band offset (CBO) of InGaN/Si heterojunction is found similar to 0.74 eV and a type-II heterojunction. (C) 2012 The Japan Society of Applied Physics

Determination of MBE grown wurtzite GaN/Ge3N4/Ge heterojunctions band offset by X-ray photoelectron spectroscopy

Hexagonal Ge3N4 layer was prepared on Ge surface by in situ direct atomic source nitridation and it is promising buffer layer to grow GaN on Ge (111). The valence band offset (VBO) of GaN/Ge3N4/Ge heterojunctions is determined by X-ray photoemission spectroscopy. The valence band (VB) of Ge3N4 is found to be 0.38?+/-?0.04?eV above the GaN valance band and 1.14?+/-?0.04?eV below the Ge. The GaN/Ge3N4 and Ge3N4/Ge are found type-II and type-I heterojunctions, respectively. The exact measurements of the VBO and conduction band offset (CBO) are important for use of GaN/Ge3N4/Ge (111) heterosystems.

X-ray photoelectron spectroscopy: a unique tool to determine the internal heterostructure of nanoparticles

We review the existing literature on the application of X-ray photoelectron spectroscopy in the study of nanocrystals. The unique ability of this technique to provide quantitative and reliable descriptions of highly complex internal structures of a variety of nanocrystals has been discussed in detail. We show that an accurate description of the nanocrystal internal structure is crucial and a prerequisite to understand many different properties, particularly optical properties, of such nanocrystal systems. We also discuss limitations and future outlook of this technique.

X-ray diffraction and Mossbauer spectroscopy studies of cementite dissolution in cold-drawn pearlitic steel

Cementite dissolution in cold-drawn pearlitic steel (0.8 wt.% carbon) wires has been studied by quantitative X-ray diffraction (XRD) and Mossbauer spectroscopy up to drawing strain 1.4. Quantification of cementite-phase fraction by Rietveld analysis has confirmed more than 50% dissolution of cementite phase at drawing strain 1.4. It is found that the lattice parameter of the ferrite phase determined by Rietveld refinement procedure remains nearly unchanged even after cementite dissolution. This confirms that the carbon atoms released after cementite dissolution do not dissolve in the ferrite lattice as Fe-C interstitial solid solution. Detailed analysis of broadening of XRD line profiles for the ferrite phase shows high density of dislocations (approximate to 10(15)/m(2)) in the ferrite matrix at drawing strain 1.4. The results suggest a dominant role of 111 screw dislocations in the cementite dissolution process. Post-deformation heat treatment leads to partial annihilation of dislocations and restoration of cementite phase. Based on these experimental observations, further supplemented by TEM studies, we have suggested an alternative thermodynamic mechanism of the dissolution process.

A transmission electron microscopy and X-ray photoelectron spectroscopy study of annealing induced gamma-phase nucleation, clustering, and interfacial dynamics in reactively sputtered amorphous alumina thin films

Pure alpha-Al2O3 exhibits a very high degree of thermodynamical stability among all metal oxides and forms an inert oxide scale in a range of structural alloys at high temperatures. We report that amorphous Al2O3 thin films sputter deposited over crystalline Si instead show a surprisingly active interface. On annealing, crystallization begins with nuclei of a phase closely resembling gamma-Alumina forming almost randomly in an amorphous matrix, and with increasing frequency near the substrate/film interface. This nucleation is marked by the signature appearance of sharp (400) and (440) reflections and the formation of a diffuse diffraction halo with an outer maximal radius of approximate to 0.23 nm enveloping the direct beam. The microstructure then evolves by a cluster-coalescence growth mechanism suggestive of swift nucleation and sluggish diffusional kinetics, while locally the Al ions redistribute slowly from chemisorbed and tetrahedral sites to higher anion coordinated sites. Chemical state plots constructed from XPS data and simple calculations of the diffraction patterns from hypothetically distorted lattices suggest that the true origins of the diffuse diffraction halo are probably related to a complex change in the electronic structure spurred by the a-gamma transformation rather than pure structural disorder. Concurrent to crystallization within the film, a substantially thick interfacial reaction zone also builds up at the film/substrate interface with the excess Al acting as a cationic source. (C) 2015 AIP Publishing LLC.