Determination of the S-ZnO structural interaction in thiol-capped ZnO nanoparticles: a sulfur K-edge XAS study.

ZnO nanoparticles capped with thiol molecules display room temperature ferromagnetism which has been associated with the structural details of the interface formed between the organic molecule and the ZnO core. Although the local order around sulfur atoms at the ZnS/ZnO interface has been related to the occurrence of the ferromagnetic like behavior, no direct structural determination has been obtained yet. We report here a detailed x-ray absorption spectroscopy study performed at the sulfur K-edge to determine the local structure around the sulfur atoms in these systems and how it is modified by varying the length of the organic molecule.

Structural determination of Bi-doped magnetite multifunctional nanoparticles for contrast imaging.

To determine with precision how Bi atoms are distributed in Bi-doped iron oxide nanoparticles their structural characterization has been carried out by X-ray absorption spectroscopy (XAS) recorded at the K edge of Fe and at the L3 edge of Bi. The inorganic nanoparticles are nominally hybrid structures integrating an iron oxide core and a bismuth oxide shell. Fe K-edge XAS indicates the formation of a structurally ordered, non-stoichiometric magnetite (Fe3-δO4) phase for all the nanoparticles. The XAS spectra show that, in the samples synthesized by precipitation in aqueous media and laser pyrolysis, the Bi atoms neither enter into the iron oxide spinel lattice nor form any other mixed Bi-Fe oxides. No modification of the local structure around the Fe atoms induced by the Bi atoms is observed at the Fe K edge. In addition, contrary to expectations, our results indicate that the Bi atoms do not form a well-defined Bi oxide structure. The XAS study at the Bi L3 edge indicates that the environment around Bi atoms is highly disordered and only a first oxygen coordination shell is observed. Indefinite [BiO6-x(OH)x] units (isolated or aggregated forming tiny amorphous clusters) bonded through hydroxyl bridges to the nanoparticle, rather than a well defined Bi2O3 shell, surround the nanoparticle. On the other hand, the XAS study indicates that, in the samples synthesized by thermal decomposition, the Bi atoms are embedded in a longer range ordered structure showing the first and second neighbors.

Interfacial magnetic coupling between Fe nanoparticles in Fe­Ag granular alloys.

The role of the interface in mediating interparticle magnetic interactions has been analysed in Fe50Ag50 and Fe55Ag45 granular thin films deposited by the pulsed laser deposition technique (PLD). These samples are composed of crystalline bcc Fe (2­4 nm) nanoparticles and fcc Ag (10­12 nm) nanoparticles, separated by an amorphous Fe50Ag50 interface, occupying around 20% of the sample volume, as determined by x-ray diffraction (XRD), x-ray absorption spectroscopy (XAS), and high resolution transmission electron microscopy (HRTEM). Interfacial magnetic coupling between Fe nanoparticles is studied by dc magnetization and x-ray magnetic circular dichroism (XMCD) measurements at the Fe K and Ag L2,3 edges. This paper reveals that these thin films present two magnetic transitions, at low and high temperatures, which are strongly related to the magnetic state of the amorphous interface, which acts as a barrier for interparticle magnetic coupling.

XAS and XMCD study of the influence of annealing on the atomic ordering and magnetism in an NiMnGa alloy.

The proper annealing of Ni(51)Mn(28)Ga(21) ribbon alloy gives rise to an increase of the saturation magnetization and of the magnetic order T(C) (up to 20 K) and martensitic transition T(M) (up to 10 K) temperatures. The combined x-ray absorption spectroscopy (XAS) and x-ray magnetic circular dichroism (XMCD) studies indicate that the annealing treatment drives the alloy to a more ordered structure without significantly affecting the local structure in terms of interatomic distances and bonding geometry. By contrast, the annealing strongly affects the near-edge absorption at the Mn K-edge while no effect is observed at either the Ni or Ga K-edge. These results suggest that annealing leads to a modification of the electronic structure of the Mn atoms while that of Ni and Ga atoms remains unvaried. However, strong XMCD signals are detected at both Ni and Ga K-edges whose amplitude increases after annealing. These results point out that despite the change of the magnetic properties of the system being mainly associated with the modification of the electronic properties of the Mn atoms, both Ni and Ga may play a non-negligible role through the polarization of the conduction band.

Ab initio x-ray absorption near-edge structure study of Ti K-edge in rutile.

This work reports a theoretical x-ray absorption near-edge structure (XANES) spectroscopy study at the Ti K-edge in TiO(2) rutile. We present detailed ab initio computations of the Ti K-edge XANES spectrum performed within the multiple-scattering framework. An extensive discussion is presented concerning the size of the cluster needed to reproduce the experimental spectrum, especially regarding the split main absorption line. In addition, the role of the exchange and correlation potential (ECP) in reproducing all the experimental XANES features is discussed. The best agreement between experimental data and computations is obtained by using real ECP potentials, i.e. the energy-dependent Dirac-Hara exchange potential, or by using only the real part of the energy-dependent Hedin-Lundqvist complex potential, together with an additional imaginary constant to account for the core-hole lifetime and the experimental resolution. The addition of the imaginary part of the HL potential worsens the agreement between the experimental and calculated spectra, indicating the failure of the complex part of the Hedin-Lundqvist ECP in accounting for the electron damping in these systems.

Orbital magnetic moment instability at the spin reorientation transition of Nd2Fe14B

Highly accurate soft-XMCD data recorded on a Nd2Fe14B single crystal, through the spin reorientation transition show that the average Fe orbital moment (a) is proportional to the macroscopic Fe anisotropy constant, and (b) diverges 15 K below the reorientation transition temperature. This divergence is indicative of a critical behavior and it is related to a tetragonal distortion. These results give experimental evidence of the mutual dependence between orbital moment, macroscopic magnetic anisotropy, and tetragonal distortion. Furthermore, it is argued that the critical behavior of the orbital moment is at the origin of similar divergences previously observed in Mossbauer and Hall-effect data.

Competing effects in the magnetic polarization of non-magnetic atoms.

The magnetic polarization of the Lu 5d states through the Ho(1-x)Lu(x)(Fe(1-y)Al(y))(2) series has been studied by means of x-ray magnetic circular dichroism. A combined study of the dichroic signals performed at the Fe K-, Ho L(2)- and Lu L(2,3)-edges gives a complete picture of the polarization scheme at the conduction band. The results show that in the presence of competing localized magnetic moments, µ(Fe)(3d) and µ(Ho)(4f), the dichroic signal at the Lu site is mainly due to the Fe atoms, the effect of the magnetic rare-earth being negligible. Estimation of the spin and orbital components of the Lu(5d) induced magnetic moment have been obtained by applying the magneto-optical sum rules derived for x-ray magnetic circular dichroism.

Magnetic disorder in diluted FexM100-x granular thin films (M=Au, Ag, Cu; x < 10 at.%).

Nanogranular thin films of Fe7Au93, Fe7Ag93 and Fe9Cu91 have been sputtered onto Si(100) substrates with the aim of studying the magnetic interactions. X-ray diffraction shows a major noble metal matrix with broad peaks stemming from (111) textured fcc-Au, Ag and Cu. The noble metal forms a nanogranular environment, as confirmed by transmission electron microscopy, with mean particle sizes below 10 nm. The high magnetoresistance (>6%) reveals the existence of Fe nanoparticles. X-ray absorption near edge spectroscopy confirms the presence of a bcc-Fe atom arrangement and some dissolved Fe atoms in the matrix, and XMCD shows the polarization of Au by the Fe nanoparticles. DC-magnetization displays a field-dependent irreversibility produced by the freezing of magnetic nanoparticles into a superspin-glass state. The hysteresis loops remain unsaturated at 5 K and 45 kOe. The coercivity displays a sharp temperature decrease towards a minimum below 50 K, levelling off at higher values, reaching Hc = 200 Oe at 300 K. Annealing of FeAu results in a double-peak zero field cooled magnetization and a slight decrease of the coercivity. The interpretation of the results supports the presence of Fe nanoparticles embedded in the major noble matrix, with some diluted Fe atoms/clusters.

X-ray absorption study of the local order around Mn in Mn:ZnO thin films: the role of vacancies and structural distortions.

This work reports an x-ray absorption near-edge structure spectroscopy (XANES) study at both Mn and Zn K edges in Zn(0.95)Mn(0.05)O thin films prepared with different sputtering gases (pure Ar, Ar/N(2) and Ar/O(2)). We have studied the local order around Mn in the films, with special emphasis on the role played by both oxygen and zinc vacancies and by the structural distortion associated with the substitution of Zn by Mn in the ZnO host. Our results indicate that the dependence of the magnetic properties of these Mn:ZnO thin films on the different sputtering gases used in the preparation is related to the structural distortion around Mn sites.

Geometrical structure of yttrium and metal-bromine complexes in solution: limitations of extended X-ray absorption fine structure analysis (EXAFS).

An extensive study on the appearance of multi-electron features in the X-ray absorption spectra of several yttrium(III)-based compounds has been performed. The existence of a multi-electron transition of non-negligible intensity within the extended X-ray absorption fine structure (EXAFS) region of the Y K-edge spectra has been proven. The impact of such features in the EXAFS analysis is made evident for aqueous solutions of YBr3 x 6H2O in liquid and glassy states in the concentration range 0.005-2.0 M, in which this transition induces an overestimation in the coordination numbers derived from EXAFS. We have performed theoretical computation of cross-sections for the double-electron processes at the K-edge of both Y and Br. These computations have been applied to the experimental EXAFS K-edge spectra of both Y and Br in several solids and in aqueous solutions. While in the case of Y K-edge spectra the presence of such multi-electron transitions was seen to seriously affect the standard EXAFS analysis, its influence in the case of Br K-edge spectra was determined to be negligible.

Double-channel excitation in the XAS spectra of divalent and trivalent iron complexes in water solution.

We present a detailed analysis of XAS spectra of divalent and trivalent iron complexes in water solutions. The interpretation of the spectra has been provided by multi-channel multiple scattering approach. On this basis, good agreement between experimental data and theoretical calculations has been obtained in both cases including two excitation channels in the final state.

New opportunities in trace elements structural characterization: high-energy X-ray absorption near-edge structure spectroscopy.

Garnets in lower crustal mafic and ultramafic rocks usually contain rare-earth elements (REE) in trace concentrations. Direct characterization of REE at trace levels in natural garnets is not available in the literature because of the difficulty of obtaining structural information by means of conventional diffraction methods. Here, the characterization of Nd at trace levels (176-1029 p.p.m.) in a set of natural garnets performed by means of Nd K-edge X-ray absorption near-edge structure spectroscopy is presented, showing the capability of high-energy XANES for REE in trace structural determinations.