Chemical state of complex uranium oxides.

We report here the first direct observation of U(V) in uranium binary oxides and analyze the gradual conversion of the U oxidation state in the mixed uranium systems. Our finding clarifies previous contradicting results and provides important input for the geological disposal of spent fuel, recycling applications, and chemistry of uranium species.

Electronic structure of Cu(3)N films studied by soft x-ray spectroscopy.

Soft x-ray emission spectroscopy was used to characterize the electronic structure of seven copper nitride films, one synthesized with atomic layer deposition (ALD) and six grown with chemical vapor deposition (CVD) at different preparation temperatures. Interpretation of the x-ray emission spectra was supported by calculations of the electronic structure for bulk pure Cu(3)N and Cu(3)N with: an excess of Cu atoms, oxygen or carbon impurities, and N vacancies. The calculations are shown to describe the experimental spectra quite well. Analysis of the x-ray spectra suggests that films grown in copper rich environments and above a cut-off temperature of approximately 360 °C have a growing fraction of copper enriched areas, while films prepared below this temperature do not have these areas with excess copper.

X-ray spectroscopic study of the charge state and local ordering of room-temperature ferromagnetic Mn-doped ZnO.

The charge state and local ordering of Mn doped into a pulsed laser deposited single-phase thin film of ZnO are investigated by using x-ray absorption spectroscopy at the O K-edge, Mn K-edge and L-edge, and x-ray emission spectroscopy at the O K-edge and Mn L-edge. This film is ferromagnetic at room temperature. EXAFS measurement shows that Mn(2+) replaces the Zn site in tetrahedral symmetry, and there is no evidence for either metallic Mn or MnO in the film. Upon Mn doping, the top of O 2p valence band extends into the bandgap, indicating additional charge carriers being created.

5 f -shell correlation effects in dioxides of light actinides studied by O 1s x-ray absorption and emission spectroscopies and first-principles calculations.

Soft x-ray emission and absorption spectroscopic data are reported for the O 1s region of a single crystal of UO2, a polycrystalline NpO2 sample, and a single crystal of PuO2. The experimental data are interpreted using first-principles correlated-electron calculations within the framework of the density functional theory with added Coulomb U interaction (DFT+U). A detailed analysis regarding the origin of different structures in the x-ray emission and x-ray absorption spectra is given and the effect of varying the intra-atomic Coulomb interaction-U for the 5 f electrons is investigated. Our data indicate that O 1s x-ray absorption and emission spectroscopies can, in combination with DFT+U calculations, successfully be used to study 5 f -shell Coulomb correlation effects in dioxides of light actinides. The values for the Coulomb U parameter in these dioxides are derived to be in the range of 4-5 eV.

Temperature dependence of the electrical resistivity and electronic structure of amorphous Fe100-xZrx films and multilayers.

The electrical resistivity of amorphous Fe(100-x)Zr(x) metal alloy films and multilayers has been investigated in a wide temperature and composition range. The overall behavior of the resistivity is consistent with bulk measurements, exhibiting prominent semiconductor-like changes at low temperatures. The transition from positive (metallic) to negative temperature coefficient of resistivity behavior is accompanied by minute changes in magnetoresistance and we can therefore rule out magnetic phase changes as being the cause for the observed changes in the resistivity. Using x-ray absorption and emission spectroscopies we are able to probe the unoccupied and occupied electronic densities of states. The corresponding spectra are found to significantly overlap, as expected for a metallic-like electronic structure and the absence of a band gap. Besides a broadening of the x-ray emission lines expected from an amorphous material, remarkably small differences are observed in the electronic structures when changing the amount of Zr. The resistivity data were modeled and agreement with the Mott variable range hopping model was found, indicating localized electronic states due the disordered structure of the Fe(100-x)Zr(x) alloys.

Atomic and electronic structure of amorphous Al-Zr alloy films.

Amorphous Al(73)Zr(27) alloy film, grown and then subjected to heat treatments at 400 and 700 °C, was studied using a combination of x-ray diffraction and soft x-ray spectroscopic techniques. The Al L(2,3) and Al K x-ray absorption spectroscopy (XAS) and Al L(2,3) x-ray emission spectroscopy (XES) used allowed probing the unoccupied and occupied Al 3s, d states and unoccupied Al 3p states in the sample studied. An irreversible transition from amorphous alloy to a mixture of polycrystalline alloy and amorphous alloy, and then to an amorphous oxide phase was observed. After the annealing at 400 °C the Al L(2,3) spectra obtained by XAS could be explained as sums of spectra from amorphous Al(73)Zr(27) alloy and (poly)crystalline Al. This indicates that the sample consists of a mixture of Al-rich crystalline and Zr-enhanced amorphous alloys, as compared to the stoichiometry of the as-deposited Al(73)Zr(27) sample, and that the electronic wavefunctions in the crystalline and amorphous regions can be considered to be confined within the respective regions. The relative amounts of Al atoms were found to be around 1:3 in the crystalline and amorphous phases, respectively, as deduced from the analysis of changes in the electronic structure using Al L(2,3) XAS data. The interpretation was confirmed by the Al K XAS and Al L(2,3) XES. Upon further annealing at 700 °C the polycrystalline phase transformed into amorphous oxide, while the amorphous alloy phase underwent gradual oxidation. The important finding was that the greater part of the sample remained in the amorphous state throughout the temperature regimes described.

Closed source experimental system for soft x-ray spectroscopy of radioactive materials.

An instrumental and experimental setup for soft x-ray spectroscopy meeting the requirements of a closed source for radioactivity is described. The system consists of a vacuum sealed cell containing the sample, mounted on a tubing system to ensure compatibility with most standard manipulators. The soft x rays penetrate a thin x-ray window separating the interior of the cell from the vacuum in the experimental chamber. Our first results for single crystal PuO(2) confirm the feasibility of experiments using the setup. The results are consistent with results of first principles calculations and previously recorded spectra obtained using a standard open source setup. The results show that the closed source experimental system can be used to collect valuable experimental data from radioactive materials.

Electronic structure of phospho-olivines Li(x)FePO4 (x = 0, 1) from soft-x-ray-absorption and -emission spectroscopies.

The electronic structure of the phospho-olivine Li(x)FePO4 was studied using soft-x-ray-absorption (XAS) and emission spectroscopies. Characteristic changes in the valence and conduction bands are observed upon delithation of LiFePO4 into FePO4. In LiFePO4, the Fe-3d states are localized with little overlap with the O-2p states. Delithiation of LiFePO4 gives stronger hybridization between Fe-3d states and O-2p states leading to delocalization of the O-2p states. The Fe L-edge absorption spectra yield "fingerprints" of the different valence states of Fe in LiFePO4 and FePO4. Resonant soft-x-ray-emission spectroscopy at the Fe L edge shows strong contributions from resonant inelastic soft x-ray scattering (RIXS), which is described using an ionic picture of the Fe-3d states. Together the Fe L-edge XAS and RIXS study reveals a bonding character of the Fe 3d-O2p orbitals in FePO4 in contrast to a nonbonding character in LiFePO4.