Depth dependent local structures in thin films unraveled by grazing incidence x-ray absorption spectroscopy

A method of using X-ray absorption spectroscopy (XAS) together with resolved grazing incidence geometry for depth profiling atomic, electronic, chemical or magnetic local structures in thin films is presented. The quantitative deconvolution of thickness-dependent spectral features is performed by fully considering both scattering and absorption formalisms. Surface oxidation and local structural depth profiles in nanometric FePt films are determined, exemplifying the application of the method.Comment: 5 pages, 3 figure

Local tetragonal distortion in La_{0.7}Sr_{0.3}MnO_3 strained thin films probed by x-ray absorption spectroscopy

We report on an angular resolved X-ray Absorption Spectroscopy study of $La_{0.7}Sr_{0.3}MnO_{3}$ thin films epitaxially grown by pulsed laser deposition on slightly mismatched substrates which induce tensile or compressive strains. XANES spectra give evidence of tetragonal distortion within the $MnO_{6}$ octahedra, with opposite directions for tensile and compressive strains. Quantitative analysis has been done and a model of tetragonal distortion reflecting the strain has been established. EXAFS data collected in plane for tensile substrate confirm the change in the $Mn-O$ average bond distance and the increase of $Mn-Mn$ length matching with the enlargement of the cell parameter. From these results we conclude that there is no significant change in the $Mn-O-Mn$ angle. Our observations conflict with the scenarios which this angle is the main driving parameter in the sensitivity of manganite films properties to external strains and suggest that the distortion within the octahedra plays a key role in the modification of the transport and magnetic properties.Comment: 8 pages, 6 figure

Stability of the Ni sites across the pressure-induced metallization in YNiO3

The local environment of nickel atoms in Y NiO3 across the pressure- induced insulator to metal (IM) transition was studied using X-ray absorption spectroscopy (XAS) supported by ab initio calculations. The monotonic contraction of the NiO6 units under applied pressure observed up to 13 GPa, stops in a limited pressure domain around 14 GPa, before resuming above 16 GPa. In this narrow pressure range, crystallographic modifications basically occur in the medium/long range, not in the NiO6 octahedron, whereas the evolution of the near-edge XAS features can be associated to metallization. Ab initio calculations show that these features are related to medium range order, provided that the Ni-O-Ni angle enables a proper overlap of the Ni eg and O 2p orbitals. Metallization is then not directly related to modifications in the average local geometry of the NiO6 units but more likely to an inter-octahedra rearrangement. These outcomes provides evidences of the bandwidth driven nature of the IM transition.Comment: 6 pages with figure

Energy-dispersive X-ray absorption spectroscopy at LNLS: Investigation on strongly correlated metal oxides

An energy-dispersive X-ray absorption spectroscopy beamline mainly dedicated to X-ray magnetic circular dichroism (XMCD) and material science under extreme conditions has been implemented in a bending-magnet port at the Brazilian Synchrotron Light Laboratory. Here the beamline technical characteristics are described, including the most important aspects of the mechanics, optical elements and detection set-up. The beamline performance is then illustrated through two case studies on strongly correlated transition metal oxides: an XMCD insight into the modifications of the magnetic properties of Cr-doped manganites and the structural deformation in nickel perovskites under high applied pressure. © 2010 International Union of Crystallography. Printed in Singapore - all rights reserved.Fil: Cezar, Julio C.. Laboratorio Nacional de Luz Síncrotron; BrasilFil: Souza Neto, Narcizo M.. Laboratorio Nacional de Luz Síncrotron; BrasilFil: Piamonteze, Cínthia. Laboratorio Nacional de Luz Síncrotron; BrasilFil: Tamura, Edilson. Laboratorio Nacional de Luz Síncrotron; BrasilFil: Garcia, Flávio. Laboratorio Nacional de Luz Síncrotron; BrasilFil: Carvalho, Edson J.. Laboratorio Nacional de Luz Síncrotron; BrasilFil: Neueschwander, Régis T.. Laboratorio Nacional de Luz Síncrotron; BrasilFil: Ramos, Aline Y.. Centre National de la Recherche Scientifique; FranciaFil: Tolentino, Hélio C. N.. Centre National de la Recherche Scientifique; FranciaFil: Caneiro, Alberto. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Área de Energía Nuclear. Instituto Balseiro; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Massa, Nestor Emilio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; ArgentinaFil: Martinez Lope, Maria Jesus. Instituto de Ciencia de Materiales de Madrid; España. Consejo Superior de Investigaciones Científicas; EspañaFil: Alonso, José Antonio. Instituto de Ciencia de Materiales de Madrid; España. Consejo Superior de Investigaciones Científicas; EspañaFil: Itié, Jean Paul. L'Orme des Merisiers. Synchrotron SOLEIL; Franci

Energy-dispersive X-ray absorption spectroscopy at LNLS: investigation on strongly correlated metal oxides

An energy-dispersive X-ray absorption spectroscopy beamline mainly dedicated to X-ray magnetic circular dichroism (XMCD) and material science under extreme conditions has been implemented in a bending-magnet port at the Brazilian Synchrotron Light Laboratory. Here the beamline technical characteristics are described, including the most important aspects of the mechanics, optical elements and detection set-up. The beamline performance is then illustrated through two case studies on strongly correlated transition metal oxides: an XMCD insight into the modifications of the magnetic properties of Cr-doped manganites and the structural deformation in nickel perovskites under high applied pressure.Facultad de Ciencias ExactasCentro de Química Inorgánic

Temperature and high-pressure dependent x-ray absorption of SmNiO3 at the Ni K and Sm L3 edges

International audienceWereport on x-ray absorption near-edge structure (XANES) and extended x-ray absorption finestructure (EXAFS) measurements of SmNiO3 from 20 Kto 600 Kand up to 38 GPa at the NiKand SmL3 edges. A multiple component pre-NiKedge tail is understood, originating from 1 s transitions to3d-4p states while a post-edge shoulder increases distinctively smoothly, at about the insulator tometal phase transition (TIM), due to the reduction of electron–phonon interactions as the Ni 3d andO2p band overlap triggers the metallic phase. This effect is concomitant with pressure-induced Ni-O-Niangle increments toward more symmetric Ni3+ octahedra of the rhombohedral R¯3c space group.Room temperature pressure-dependent Ni white line peak energies have an abrupt∼3.10±0.04 GPavalence discontinuity from non-equivalent Ni3+δ+Ni3–δ charge disproportionate net unresolvedabsorber turning at∼TIM into Ni3+ of the orthorhombic Pbnm metal oxide phase. At 20 Kthe overallwhite line response, still distinctive at TIM∼8.1±0.6 GPa is much smoother due to localization.Octahedral bond contraction up to 38 GPa and at 300 Kand 20 Kshow breaks in its monotonicincrease at the different structural changes. The SmL3 edge does not show distinctive behaviors eitherat 300 Kor 20 Kup to about 35 GPa but the perovskite Smcage, coordinated to eight oxygen atoms,undergoes strong uneven bond contractions at intermediate pressures where we found the coexistenceof octahedral and rhombohedral superexchange angle distortions.Wefound that the white linepressure-dependent anomaly may be used as an accurate alternative for delineating pressure–temperature phase diagrams