Enhanced electron correlations at the SrxCa1-xVO3 surface

We report hard x-ray photoemission spectroscopy measurements of the electronic structure of the prototypical correlated oxide SrxCa1-xVO3. By comparing spectra recorded at different excitation energies, we show that 2.2 keV photoelectrons contain a substantial surface component, whereas 4.2 keV photoelectrons originate essentially from the bulk of the sample. Bulk-sensitive measurements of the O 2p valence band are found to be in good agreement with ab initio calculations of the electronic structure, with some modest adjustments to the orbital-dependent photoionization cross sections. The evolution of the O 2p electronic structure as a function of the Sr content is dominated by A-site hybridization. Near the Fermi level, the correlated V 3d Hubbard bands are found to evolve in both binding energy and spectral weight as a function of distance from the vacuum interface, revealing higher correlation at the surface than in the bulk

New Correction Procedure for X-Ray Spectroscopic Fluorescence Data: Simulations and Experiment.

X-ray fluorescence spectroscopy is a widely used method for determining the electronic configuration and local structure of dilute species with high sensitivity. In the dilute limit, and for thin films, the X-ray fluorescence signal is directly proportional to the atomic sub-shell absorption coefficient. However, for concentrated samples, the well-documented self-absorption effect often leads to the severe suppression of XANES (X-ray Absorption Near-Edge Structure) and EXAFS (Extended X-ray Absorption Fine-Structure) amplitudes. Thus to recover the real value of the sub-shell absorption coefficient, it is important to apply correction procedures to the measured fluorescence spectra. In this paper, we describe a new straightforward method to correct for self-absorption effects (the difference in the measured fluorescence signal compared to that of the true sub-shell photoabsorption coefficient) in XANES and EXAFS fluorescence measurements. Using a variety of sample and detector configurations, this method is used to extract the sub-shell absorption coefficient on elemental nickel and thick single-crystals of Gd{sub 3}Ga{sub 5}O{sub 12} and LaAlO{sub 3}

Design and Performance of the Advanced-Light-Source Double-crystal Monochromator

A new “Cowan type” double-crystal monochromator, based on the boomerang design used at National Synchrotron Light Source (NSLS) beamline X-24A, has been developed for beamline 9.3.1 at the Advanced Light Source (ALS), a windowless ultrahigh vacuum beamline covering the 1-6 keV photon-energy range. Beamline 9.3.1 is designed to simultaneously achieve the goals of high energy resolution, high flux, and high brightness at the sample. The mechanical design of the monochromator has been simplified, and recent developments in technology have been included. Measured mechanical precision of the monochromator shows significant improvement over existing designs. In tests with x-rays at NSLS beamline X-23Ʌ2, maximum deviations in the intensity of monochromatic light were just 7% during scans of several hundred eV in the vicinity of the Cr K edge (6 keV) with the monochromator operating without intensity feedback. Such precision is essential because of the high brightness of the ALS radiation and the overall length of beamline 9.3.1 (26 m)

Strain Relaxation Mechanisms and Local Structural Changes in Si_{1-x}$Ge_{x} Alloys

In this work, we address issues pertinent to the understanding of the structural and electronic properties of Si_{1-x} Ge_{x}alloys, namely, (i) how does the lattice constant mismatch between bulk Si and bulk Ge manifests itself in the alloy system? and (ii) what are the relevant strain release mechanisms? To provide answers to these questions, we have carried out an in-depth study of the changes in the local geometric and electronic structures arising from the strain relaxation in Si_{1-x} Ge_{x} alloys using an ab initio molecular dynamics scheme. The optimized lattice constant, while exhibiting a general trend of linear dependence on the composition (Vegard's law), shows a negative deviation from Vegard's law in the vicinity of x=0.5. We delineate the mechanisms responsible for each one of the above features. We show that the radial-strain relaxation through bond stretching is responsible for the overall trend of linear dependence of the lattice constant on the composition. On the other hand, the negative deviation from Vegard's law is shown to arise from the angular-strain relaxation.Comment: 21 pages, 7 figure

Subtle local structural variations in oxygen deficient niobium germanate thin film glasses as revealed by x-ray absorption spectroscopy

6 págs.; 4 figs.; 2 tabs. 16th International Conference on X-ray Absorption Fine Structure (XAFS16) ; Open Access funded by Creative Commons Atribution Licence 3.0The local electronic and crystal structure of niobium-lead-germanate, Nb2O5-PbO- GeO2 (NPG), glass thin films on silicon substrates were probed by XANES and EXAFS. NPG glasses are promising candidates for applications in nonlinear optical devices because they exhibit interesting optical characteristics such as high nonlinear third order optical susceptibility. In this work NPG glasses were prepared with pulsed laser deposition method with varying oxygen partial pressure to induce thin films with different oxygen stoichiometry. Previously, it was shown that oxygen stoichiometry has a very important effect to produce unusual high optical susceptibility. Detailed EXAFS and XANES analyses in a series of NPG thin films revealed the subtle variations in the local environment around Nb atoms and the Nb oxidation states caused by oxygen deficiencies. Published under licence by IOP Publishing LtdPeer Reviewe

Hybridization and Bond-Orbital Components in Site-Specific X-Ray Photoelectron Spectra of Rutile TiO\u3csub\u3e2\u3c/sub\u3e

We have determined the Ti and O components of the rutile TiO2 valence band using the method of sitespecific x-ray photoelectron spectroscopy. Comparisons with calculations based on pseudopotentials within the local density approximation reveal the hybridization of the Ti 3d, 4s, and 4p states, and the O 2s and 2p states on each site. These chemical effects are observed due to the large differences between the angular-momentum dependent matrix elements of the photoelectron process